CN107337902B - Glass fiber and carbon nanotube co-modified epoxy composite material and preparation method thereof - Google Patents

Glass fiber and carbon nanotube co-modified epoxy composite material and preparation method thereof Download PDF

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CN107337902B
CN107337902B CN201710597854.6A CN201710597854A CN107337902B CN 107337902 B CN107337902 B CN 107337902B CN 201710597854 A CN201710597854 A CN 201710597854A CN 107337902 B CN107337902 B CN 107337902B
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杨国清
寇长珍
崔俊达
黎洋
王德意
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Xian University of Technology
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Abstract

The invention discloses a glass fiber and carbon nanotube co-modified epoxy composite material, which consists of the following components: 0.2g of carbon nano tube, 10-40g of glass fiber, 80g of curing agent, 0.1g of accelerating agent and 20g of coupling agent are added into every 100g of epoxy resin, so that the heat conducting property of the epoxy composite material is improved while the electrical insulation is considered. The invention also discloses a preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material.

Description

Glass fiber and carbon nanotube co-modified epoxy composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of epoxy composite materials, relates to a glass fiber and carbon nanotube co-modified epoxy composite material, and further relates to a preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material.
Background
With the increasing capacities of generator sets and transformers in the power system, the rated current flowing through the motor coil and the outlet bus is increased. The bus serves as an important carrier for electric energy transmission and distribution, a large amount of heat can be generated under the condition of large rated current operation, if the heat cannot be dissipated in time, the bus insulating layer can be continuously influenced by high temperature to accelerate aging, the service life of the bus insulating layer is further influenced, and even an electric power safety accident can be caused. Therefore, the development and research of various novel insulating and heat conducting materials are highly concerned by scholars at home and abroad.
Epoxy resin is one of the most widely used insulating materials in the high-voltage field, particularly in high-current and high-voltage equipment at present. However, the cured product has the defects of brittle quality, poor thermal conductivity, weak bonding force with the interface of a current-carrying conductor and the like[7]In order to widen the application of the epoxy resin in a power system, modification research on the epoxy resin is very important.
In the field of epoxy modification, it is one of the current research hotspots to improve the thermal conductivity of epoxy composite materials by filling high thermal conductivity micro-nano fillers, wherein, many researches are carried out by doping carbon nanotubes with epoxy. Research shows that a small amount of carbon nanotubes can improve the mechanical, electrical and optical properties of epoxy resin products to different degrees, but the effect of improving the thermal conductivity is not obvious; when the amount of the composite material is excessive, the thermal conductivity can be greatly improved, but the insulation property is sacrificed, and the problems of difficult dispersion, easy agglomeration and the like exist, so that various performances of the composite material are influenced. Glass fiber has the advantages of high mechanical strength, good electrical insulation, low price, wide source and the like, is commonly used as an epoxy polymer filler to improve the strength and the electrical insulation property, but the current research reports on the aspect of heat conduction are few.
Disclosure of Invention
The invention aims to provide a glass fiber and carbon nanotube co-modified epoxy composite material, which improves the heat conduction performance of the epoxy composite material while considering the electrical insulation of the epoxy composite material.
The invention also aims to provide a preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material.
The technical scheme adopted by the invention is that the glass fiber and carbon nanotube co-modified epoxy composite material comprises the following components: every 100g of epoxy resin is added with 0.2g of carbon nano tube, 10-40g of glass fiber, 80g of curing agent, 0.1g of accelerating agent and 20g of coupling agent.
Preferably, the diameter of the carbon nano tube is 40-60 nm, the length of the carbon nano tube is 5-15 mu m, and the purity of the carbon nano tube is more than or equal to 99%. Preferably, the length of the glass fiber is 0.1-0.3 mm, the diameter of the monofilament is 2-5 μm, the water absorption rate is less than or equal to 2%, and the breaking strength is more than or equal to 450 MPa.
Preferably, the curing agent, the accelerator and the coupling agent are MeHHPA, KH-560 and DMP-30 respectively.
The invention also provides a preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material, which is implemented according to the following steps:
step 1, respectively weighing the following components of epoxy resin, carbon nano tubes, glass fibers, a curing agent, an accelerator and a coupling agent according to a mass ratio, wherein 0.2g of the carbon nano tubes, 10-40g of the glass fibers, 80g of the curing agent, 0.1g of the accelerator and 20g of the coupling agent are added into every 100g of the epoxy resin;
step 2, carrying out surface acidification treatment on the carbon nano tube weighed in the step 1;
step 3, placing the acidified carbon nanotubes obtained in the step 2 and the glass fibers weighed in the step 1 in a constant-temperature drying oven for drying;
and 4, heating and diluting the epoxy resin weighed in the step 1 at 80-90 ℃ for 15-20 min, removing water, then sequentially adding the carbon nano tubes and the glass fibers dried in the step 3, stirring and dispersing for 40-50 min, after the carbon nano tubes and the glass fibers are uniformly dispersed, sequentially adding a curing agent, an accelerant and a coupling agent, continuously stirring for a certain time, then carrying out hot mold casting, and finally curing and forming to obtain the glass fiber and carbon nano tube co-modified epoxy composite material.
Preferably, step 2 is specifically:
step 2.1, mixing H with the purity of 98 wt%2SO4With HNO having a purity of 68 wt%3Mixing according to the volume ratio of 3:1 to obtain a mixed solution A;
step 2.2, putting the carbon nano tube weighed in the step 1 into the mixed liquid A, wherein the mass volume ratio of the carbon nano tube to the mixed liquid is as follows: 1: 100-10: 100, placing the mixture in an ultrasonic oscillation device to react for 2.5 to 3 hours at 50 ℃ to obtain a mixed solution B;
and 2.3, cleaning and neutralizing the mixed solution B by using deionized water until the mixed solution B is neutral, continuously cleaning for 3-5 times by using an acetone solvent, and drying to obtain the acidified carbon nano tube.
Preferably, the diameter of the carbon nano tube is 40-60 nm, the length of the carbon nano tube is 5-15 mu m, and the purity of the carbon nano tube is more than or equal to 99 percent; the length of the glass fiber is 0.1-0.3 mm, the diameter of the monofilament is 2-5 mu m, the water absorption rate is less than or equal to 2%, and the breaking strength is more than or equal to 450 MPa.
Preferably, the curing agent, the accelerator and the coupling agent are MeHHPA, KH-560 and DMP-30 respectively.
Preferably, the stirring dispersion in the step 4 is stirring dispersion for 40-50 min by adopting a mode of mechanical stirring and ultrasonic oscillation, and the stirring time is 20-30 min after the curing agent, the accelerator and the coupling agent are sequentially added.
The invention has the beneficial effects that the glass fiber filled epoxy resin can improve the electrical insulation of the epoxy composite material and the construction of the internal heat conducting network; the addition of a small amount of carbon nanotubes is beneficial to improving the interface bonding strength of the glass fiber and the epoxy resin, and simultaneously, the carbon nanotubes are compounded with the glass fiber to further improve the heat-conducting property of the composite material. When the bus insulation layer is used as a bus insulation layer material, the bus insulation property is ensured, and meanwhile, the heat generated in the bus operation process is timely dissipated, so that the bus insulation layer is prevented from being influenced by high temperature continuously to accelerate aging, the service life of the bus insulation layer is further influenced, and even electric power safety accidents can be possibly caused.
Drawings
FIG. 1 is C5SEM images of tensile sections of GF/EP composites assembled with unfilled carbon nanotubes;
FIG. 2 is B5SEM image of tensile section of GF/EP composite filled with carbon nano-tubes;
FIG. 3 is a high magnification view of FIG. 1;
FIG. 4 is a high magnification view of FIG. 2;
FIG. 5 is a graph of the relationship between the volume resistivity of the A-group composite and the content of carbon nanotubes;
FIG. 6 is a graph of the volume resistivity of B, C sets of composites versus glass fiber content;
FIG. 7 is a graph of the AC short time breakdown voltage test results for group A composites;
FIG. 8 is a graph of AC short time breakdown strength tests of B, C two sets of composites;
FIG. 9 is a graph of thermal conductivity versus glass fiber content for two sets of B, C samples.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a glass fiber and carbon nanotube co-modified epoxy composite material which comprises the following components: every 100g of epoxy resin is added with 0.2g of carbon nano tube, 10-40g of glass fiber, 80g of curing agent, 0.1g of accelerating agent and 20g of coupling agent.
Preferably, the diameter of the carbon nano tube is 40-60 nm, the length of the carbon nano tube is 5-15 mu m, and the purity of the carbon nano tube is more than or equal to 99%.
Preferably, the length of the glass fiber is 0.1-0.3 mm, the diameter of the monofilament is 2-5 μm, the water absorption rate is less than or equal to 2%, and the breaking strength is more than or equal to 450 MPa.
Preferably, the curing agent, the accelerator and the coupling agent are MeHHPA, KH-560 and DMP-30 respectively.
The invention also provides a preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material, which is implemented according to the following steps:
step 1, respectively weighing the following components of epoxy resin, carbon nano tubes, glass fibers, a curing agent, an accelerator and a coupling agent according to a mass ratio, wherein 0.2g of the carbon nano tubes, 10-40g of the glass fibers, 80g of the curing agent, 0.1g of the accelerator and 20g of the coupling agent are added into every 100g of the epoxy resin;
step 2, carrying out surface acidification treatment on the carbon nano tube weighed in the step 1; the method specifically comprises the following steps:
step 2.1, mixing H with the purity of 98 wt%2SO4With HNO having a purity of 68 wt%3Mixing according to the volume ratio of 3:1 to obtain a mixed solution A;
step 2.2, putting the carbon nano tube weighed in the step 1 into the mixed liquid A, wherein the mass volume ratio of the carbon nano tube to the mixed liquid is 1: 100-10: 100, placing the mixture in an ultrasonic oscillation device to react for 2.5 to 3 hours at 50 ℃ to obtain a mixed solution B;
step 2.3, washing and neutralizing the mixed solution B by using deionized water until the mixed solution B is neutral, then continuously washing for 3-5 times by using an acetone solvent, and drying to obtain acidified carbon nanotubes (C-MWNTs);
step 3, placing the acidified carbon nanotubes obtained in the step 2 and the glass fibers weighed in the step 1 in a constant-temperature drying oven for drying;
and 4, heating and diluting the epoxy resin weighed in the step 1 at 80-90 ℃ for 15-20 min, removing water, then sequentially adding the carbon nano tubes and the glass fibers dried in the step 3, stirring and dispersing for 40-50 min by adopting a mechanical stirring and ultrasonic oscillation mode, sequentially adding a curing agent, an accelerator and a coupling agent after the carbon nano tubes and the glass fibers are uniformly dispersed, continuously stirring for 20-30 min, then carrying out hot mold casting, and finally curing and forming to obtain the glass fiber and carbon nano tube co-modified epoxy composite material.
Preferably, the diameter of the carbon nano tube is 40-60 nm, the length of the carbon nano tube is 5-15 mu m, and the purity of the carbon nano tube is more than or equal to 99 percent; the length of the glass fiber is 0.1-0.3 mm, the diameter of the monofilament is 2-5 mu m, the water absorption rate is less than or equal to 2%, and the breaking strength is more than or equal to 450 MPa.
Preferably, the curing agent, the accelerator and the coupling agent are MeHHPA, KH-560 and DMP-30 respectively.
Example 1
The glass fiber and carbon nanotube co-modified epoxy composite material comprises the following components: every 100g of epoxy resin is added with 0.2g of carbon nano tube, 10g of glass fiber, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent.
The preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material is implemented according to the following steps:
step 1, weighing 100g of epoxy resin, 0.2g of carbon nano tube, 10g of glass fiber, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent according to the mass ratio;
step 2, carrying out surface acidification treatment on the carbon nano tube weighed in the step 1; the method specifically comprises the following steps:
step 2.1, mixing H with the purity of 98 wt%2SO4With HNO having a purity of 68 wt%3Mixing according to the volume ratio of 3:1 to obtain a mixed solution A;
step 2.2, putting the carbon nano tube weighed in the step 1 into the mixed liquid A, wherein the mass-volume ratio of the carbon nano tube to the mixed liquid is 1:100, and putting the mixture into an ultrasonic oscillation device to react for 2.5 hours at 50 ℃ to obtain mixed liquid B;
step 2.3, cleaning and neutralizing the mixed solution B by using deionized water until the mixed solution B is neutral, then continuously cleaning for 3-5 times by using an acetone solvent, and drying to obtain an acidified carbon nano tube;
step 3, placing the acidified carbon nanotubes obtained in the step 2 and the glass fibers weighed in the step 1 in a constant-temperature drying oven for drying;
and 4, heating and diluting the epoxy resin weighed in the step 1 at 80 ℃ for 20min, removing water, then sequentially adding the carbon nano tubes and the glass fibers dried in the step 3, stirring and dispersing for 40min by adopting a mechanical stirring and ultrasonic oscillation matched mode, sequentially adding a curing agent, an accelerant and a coupling agent after the carbon nano tubes and the glass fibers are uniformly dispersed, continuously stirring for 20min, then carrying out hot die casting, and finally curing and forming to obtain the glass fiber and carbon nano tube co-modified epoxy composite material.
Example 2
The glass fiber and carbon nanotube co-modified epoxy composite material comprises the following components: every 100g of epoxy resin is added with 0.2g of carbon nano tube, 15g of glass fiber, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent.
The preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material is implemented according to the following steps:
step 1, weighing 100g of epoxy resin, 0.2g of carbon nano tube, 15g of glass fiber, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent according to the mass ratio;
step 2, carrying out surface acidification treatment on the carbon nano tube weighed in the step 1; the method specifically comprises the following steps:
step 2.1, mixing H with the purity of 98 wt%2SO4With HNO having a purity of 68 wt%3Mixing according to the volume ratio of 3:1 to obtain a mixed solution A;
step 2.2, putting the carbon nano tube weighed in the step 1 into the mixed liquid A, wherein the mass volume ratio of the carbon nano tube to the mixed liquid is 2: 100, placing the mixture in an ultrasonic oscillation device to react for 3 hours at 50 ℃ to obtain a mixed solution B;
step 2.3, cleaning and neutralizing the mixed solution B by using deionized water until the mixed solution B is neutral, then continuously cleaning for 3-5 times by using an acetone solvent, and drying to obtain an acidified carbon nano tube;
step 3, placing the acidified carbon nanotubes obtained in the step 2 and the glass fibers weighed in the step 1 in a constant-temperature drying oven for drying;
and 4, heating and diluting the epoxy resin weighed in the step 1 at 85 ℃ for 20min, removing water, then sequentially adding the carbon nano tubes and the glass fibers dried in the step 3, stirring and dispersing for 45min by adopting a mechanical stirring and ultrasonic oscillation matched mode, sequentially adding a curing agent, an accelerant and a coupling agent after the carbon nano tubes and the glass fibers are uniformly dispersed, continuously stirring for 30min, then carrying out hot die casting, and finally curing and forming to obtain the glass fiber and carbon nano tube co-modified epoxy composite material.
Example 3
The glass fiber and carbon nanotube co-modified epoxy composite material comprises the following components: every 100g of epoxy resin is added with 0.2g of carbon nano tube, 15g of glass fiber, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent.
The preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material is implemented according to the following steps:
step 1, weighing 100g of epoxy resin, 0.2g of carbon nano tube, 20g of glass fiber, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent according to the mass ratio;
step 2, carrying out surface acidification treatment on the carbon nano tube weighed in the step 1; the method specifically comprises the following steps:
step 2.1, mixing H with the purity of 98 wt%2SO4With HNO having a purity of 68 wt%3Mixing according to the volume ratio of 3:1 to obtain a mixed solution A;
step 2.2, putting the carbon nano tube weighed in the step 1 into the mixed liquid A, wherein the mass volume ratio of the carbon nano tube to the mixed liquid is 5: 100, placing the mixture in an ultrasonic oscillation device to react for 3 hours at 50 ℃ to obtain a mixed solution B;
step 2.3, cleaning and neutralizing the mixed solution B by using deionized water until the mixed solution B is neutral, then continuously cleaning for 3-5 times by using an acetone solvent, and drying to obtain an acidified carbon nano tube;
step 3, placing the acidified carbon nanotubes obtained in the step 2 and the glass fibers weighed in the step 1 in a constant-temperature drying oven for drying;
and 4, heating and diluting the epoxy resin weighed in the step 1 at 90 ℃ for 15min, removing water, then sequentially adding the carbon nano tubes and the glass fibers dried in the step 3, stirring and dispersing for 50min by adopting a mechanical stirring and ultrasonic oscillation matched mode, sequentially adding a curing agent, an accelerant and a coupling agent after the carbon nano tubes and the glass fibers are uniformly dispersed, continuously stirring for 30min, then carrying out hot die casting, and finally curing and forming to obtain the glass fiber and carbon nano tube co-modified epoxy composite material.
Example 4
The glass fiber and carbon nanotube co-modified epoxy composite material comprises the following components: every 100g of epoxy resin is added with 0.2g of carbon nano tube, 25g of glass fiber, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent.
The preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material is implemented according to the following steps:
step 1, weighing 100g of epoxy resin, 0.2g of carbon nano tube, 25g of glass fiber, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent according to the mass ratio;
step 2, carrying out surface acidification treatment on the carbon nano tube weighed in the step 1; the method specifically comprises the following steps:
step 2.1, mixing H with the purity of 98 wt%2SO4With HNO having a purity of 68 wt%3Mixing according to the volume ratio of 3:1 to obtain a mixed solution A;
step 2.2, putting the carbon nano tube weighed in the step 1 into the mixed liquid A, wherein the mass volume ratio of the carbon nano tube to the mixed liquid is 8: 100, placing the mixture in an ultrasonic oscillation device to react for 3 hours at 50 ℃ to obtain a mixed solution B;
step 2.3, cleaning and neutralizing the mixed solution B by using deionized water until the mixed solution B is neutral, then continuously cleaning for 3-5 times by using an acetone solvent, and drying to obtain an acidified carbon nano tube;
step 3, placing the acidified carbon nanotubes obtained in the step 2 and the glass fibers weighed in the step 1 in a constant-temperature drying oven for drying;
and 4, heating and diluting the epoxy resin weighed in the step 1 at 85 ℃ for 18min, removing water, then sequentially adding the carbon nano tubes and the glass fibers dried in the step 3, stirring and dispersing for 40min by adopting a mechanical stirring and ultrasonic oscillation matched mode, sequentially adding a curing agent, an accelerant and a coupling agent after the carbon nano tubes and the glass fibers are uniformly dispersed, continuously stirring for 25min, then carrying out hot mold casting, and finally curing and forming to obtain the glass fiber and carbon nano tube co-modified epoxy composite material.
Example 5
The glass fiber and carbon nanotube co-modified epoxy composite material comprises the following components: every 100g of epoxy resin is added with 0.2g of carbon nano tube, 30g of glass fiber, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent.
The preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material is implemented according to the following steps:
step 1, weighing 100g of epoxy resin, 0.2g of carbon nano tube, 30g of glass fiber, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent according to the mass ratio;
step 2, carrying out surface acidification treatment on the carbon nano tube weighed in the step 1; the method specifically comprises the following steps:
step 2.1, mixing H with the purity of 98 wt%2SO4With HNO having a purity of 68 wt%3Mixing according to the volume ratio of 3:1 to obtain a mixed solution A;
step 2.2, putting the carbon nano tube weighed in the step 1 into the mixed liquid A, wherein the mass volume ratio of the carbon nano tube to the mixed liquid is as follows: 10: 100, placing the mixture in an ultrasonic oscillation device to react for 3 hours at 50 ℃ to obtain a mixed solution B;
step 2.3, cleaning and neutralizing the mixed solution B by using deionized water until the mixed solution B is neutral, then continuously cleaning for 3-5 times by using an acetone solvent, and drying to obtain an acidified carbon nano tube;
step 3, placing the acidified carbon nanotubes obtained in the step 2 and the glass fibers weighed in the step 1 in a constant-temperature drying oven for drying;
and 4, heating and diluting the epoxy resin weighed in the step 1 at 80 ℃ for 20min, removing water, then sequentially adding the carbon nano tubes and the glass fibers dried in the step 3, stirring and dispersing for 40min by adopting a mechanical stirring and ultrasonic oscillation matched mode, sequentially adding a curing agent, an accelerant and a coupling agent after the carbon nano tubes and the glass fibers are uniformly dispersed, continuously stirring for 30min, then carrying out hot die casting, and finally curing and forming to obtain the glass fiber and carbon nano tube co-modified epoxy composite material.
Example 6
The glass fiber and carbon nanotube co-modified epoxy composite material comprises the following components: every 100g of epoxy resin is added with 0.2g of carbon nano tube, 40g of glass fiber, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent.
The preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material is implemented according to the following steps:
step 1, weighing 100g of epoxy resin, 0.2g of carbon nano tube, 40g of glass fiber, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent according to the mass ratio;
step 2, carrying out surface acidification treatment on the carbon nano tube weighed in the step 1; the method specifically comprises the following steps:
step 2.1, mixing H with the purity of 98 wt%2SO4With HNO having a purity of 68 wt%3Mixing according to the volume ratio of 3:1 to obtain a mixed solution A;
step 2.2, putting the carbon nano tube weighed in the step 1 into the mixed liquid A, wherein the mass volume ratio of the carbon nano tube to the mixed liquid is 2: 100, placing the mixture in an ultrasonic oscillation device to react for 3 hours at 50 ℃ to obtain a mixed solution B;
step 2.3, cleaning and neutralizing the mixed solution B by using deionized water until the mixed solution B is neutral, then continuously cleaning for 3-5 times by using an acetone solvent, and drying to obtain an acidified carbon nano tube;
step 3, placing the acidified carbon nanotubes obtained in the step 2 and the glass fibers weighed in the step 1 in a constant-temperature drying oven for drying;
and 4, heating and diluting the epoxy resin weighed in the step 1 at 90 ℃ for 20min, removing water, then sequentially adding the carbon nano tubes and the glass fibers dried in the step 3, stirring and dispersing for 40min by adopting a mechanical stirring and ultrasonic oscillation matched mode, sequentially adding a curing agent, an accelerant and a coupling agent after the carbon nano tubes and the glass fibers are uniformly dispersed, continuously stirring for 30min, then carrying out hot die casting, and finally curing and forming to obtain the glass fiber and carbon nano tube co-modified epoxy composite material.
Further analyzing and comparing the characteristics of the glass fiber and carbon nanotube co-modified epoxy composite material, wherein three groups of comparison tests are respectively as follows: a is a C-MWNTs/EP composite material sample filled with carbon nano tubes independently, C group is a GF/EP composite material sample filled with glass fibers independently, and B group is a GF/C-MWNTs/EP sample prepared by the invention and filled with carbon nano tubes compositely. Table 1 shows the filler (glass fiber or carbon nanotube) content of three sets of composite samples, wherein B1-B6For the glass fiber and carbon nanotube co-modified epoxy composite materials prepared in examples 1-6, 80g of curing agent, 0.1g of accelerator and 20g of coupling agent were added to 100g of epoxy resin in three groups of comparative tests, and the experimental variables were carbon nanotube and glass fiber;
TABLE 1
Figure BDA0001356132930000121
1. Fracture morphology analysis of composite material sample
After a sample prepared by testing the glass fiber and carbon nanotube co-modified epoxy composite material is prepared, a Scanning Electron Microscope (SEM) is used for representing and analyzing the section of the sample and the dispersion condition of a filler, a ZC-36 type high resistivity is adopted for measuring the volume resistivity, and a test electrode is shown in figure 1, wherein the sample is a standard wafer, the diameter of the sample is 60mm, and the thickness of the sample is 2 mm.
As shown in FIG. 1 and FIG. 3, FIG. 1 is C5SEM image of tensile section of GF/EP composite material without filling carbon nanotube, FIG. 3 is a high magnification of FIG. 1. from FIG. 1, it can be seen that the fracture of the sample without filling carbon nanotube is flat and bright, and shows brittle fracture characteristic, and under the action of stress, the glass fiber in the sample is obviously pulled out, the polymer of the pulled out part is less wrapped, and the surface is smoother, which indicates that the interface between the glass fiber and the matrix is stickyThe strength is weak. As can be seen from fig. 3, at high magnification, it can be observed that the matrix fracture around the glass fiber is rough and fibrous, turning into a typical ductile fracture.
As shown in fig. 2 and 4, fig. 2 is B5The GF/EP composite filled with carbon nanotubes, that is, the SEM image of the tensile section of the C-MWNTs/EP/GF composite, fig. 4 is a high magnification of fig. 2, it can be seen from fig. 2 that, after doping the carbon nanotubes, it can be observed that the glass fibers are coated in the matrix epoxy resin, and it can be seen from fig. 4 that, under the action of external force, the glass fibers are almost broken in the matrix epoxy resin, and the polymer coating on the surface of the extracted portion is tight. Therefore, it can be concluded that filling a proper amount of carbon nanotubes can effectively improve the interface strength between the glass fiber and the epoxy resin, thereby affecting various properties of the composite material.
2. Composite Electrical Performance testing
2.1 volume resistivity
FIG. 5 is a graph showing the relationship between the volume resistivity and the carbon nanotube content of the A-group composite material.
As can be seen from fig. 5, the volume resistivity of the sample shows a gradually decreasing trend as the content of the carbon nanotubes increases. When the content of the carbon nano-tube is less than 0.6g, the volume resistivity of the material is reduced by only one order of magnitude and still stays at 1013From the above Ω · m, it can be inferred that the volume resistivity of the epoxy composite is less affected by filling a small amount of carbon nanotubes.
It is found from FIG. 5 that the insulation effect of the C-MWNTs/EP composite material is the best when the loading of the carbon nanotubes is 0.2 g. Therefore, the content of the carbon nanotubes was determined, and B, C sets of samples were prepared by adding glass fibers at different contents, and the volume resistivity thereof was measured, as shown in FIG. 6. As can be seen from FIG. 6, the volume resistivity of the B, C samples increased and then decreased with the addition of the glass fiber content, and the maximum value of 2.89X 10 was obtained around 30g13Ω · m, but the magnitude of the change in volume resistivity of the two sets of samples is still limited to within 1 order of magnitude. This indicates that the glass fiber itself is excellent in insulation property, but its size is in the order of micrometers and it is interfacial-bonded with resinThe caking property is poor, so the volume resistance of the two groups of epoxy composite materials is not obviously improved.
However, the B, C samples have different volume resistivities with the change of the glass fiber content, i.e. the volume resistivity curve of the B group is smoother, the whole volume resistivity is slightly higher than that of the C group, and the phenomenon of peak value back shift occurs.

Claims (4)

1. The preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material is characterized by comprising the following steps:
step 1, respectively weighing the following components of epoxy resin, carbon nano tubes, glass fibers, a curing agent, an accelerator and a coupling agent according to the mass ratio, wherein 0.2g of the carbon nano tubes, 40g of the glass fibers, 80g of the curing agent, 0.1g of the accelerator and 20g of the coupling agent are added into every 100g of the epoxy resin;
step 2, carrying out surface acidification treatment on the carbon nano tube weighed in the step 1;
step 2.1, mixing H with the purity of 98 wt%2SO4With HNO having a purity of 68 wt%3Mixing according to the volume ratio of 3:1 to obtain a mixed solution A;
step 2.2, putting the carbon nano tube weighed in the step 1 into the mixed liquid A, wherein the mass volume ratio of the carbon nano tube to the mixed liquid is 1: 100-10: 100, placing the mixture in an ultrasonic oscillation device to react for 2.5 to 3 hours at 50 ℃ to obtain a mixed solution B;
step 2.3, cleaning and neutralizing the mixed solution B by using deionized water until the mixed solution B is neutral, continuously cleaning for 3-5 times by using an acetone solvent, and drying to obtain an acidified carbon nano tube;
step 3, placing the acidified carbon nanotubes obtained in the step 2 and the glass fibers weighed in the step 1 in a constant-temperature drying oven for drying;
and 4, heating and diluting the epoxy resin weighed in the step 1 at 80-90 ℃ for 15-20 min, removing water, then sequentially adding the carbon nano tubes and the glass fibers dried in the step 3, stirring and dispersing for 40-50 min, after the carbon nano tubes and the glass fibers are uniformly dispersed, sequentially adding a curing agent, an accelerant and a coupling agent, continuously stirring for a certain time, then carrying out hot mold casting, and finally curing and forming to obtain the glass fiber and carbon nano tube co-modified epoxy composite material.
2. The preparation method of the glass fiber and carbon nanotube co-modified epoxy composite material according to claim 1, wherein the carbon nanotube has a diameter of 40-60 nm, a length of 5-15 μm, and a purity of not less than 99%; the length of the glass fiber is 0.1-0.3 mm, the diameter of the monofilament is 2-5 mu m, the water absorption rate is less than or equal to 2%, and the breaking strength is more than or equal to 450 MPa.
3. The method for preparing the glass fiber and carbon nanotube co-modified epoxy composite material as claimed in claim 1, wherein the curing agent, the accelerator and the coupling agent are MeHHPA, KH-560 and DMP-30, respectively.
4. The method for preparing the glass fiber and carbon nanotube co-modified epoxy composite material according to claim 1, wherein the stirring and dispersing in the step 4 is performed by adopting a mode of mechanical stirring and ultrasonic oscillation for 40-50 min, and the stirring time is 20-30 min after the curing agent, the accelerator and the coupling agent are sequentially added.
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