CN113416384A - CNTs @ CC heat-conducting filler and heat-conducting composite material based on same - Google Patents
CNTs @ CC heat-conducting filler and heat-conducting composite material based on same Download PDFInfo
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- CN113416384A CN113416384A CN202110776950.3A CN202110776950A CN113416384A CN 113416384 A CN113416384 A CN 113416384A CN 202110776950 A CN202110776950 A CN 202110776950A CN 113416384 A CN113416384 A CN 113416384A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
Abstract
The invention discloses a CNTs @ CC heat-conducting filler and a heat-conducting composite material based on the same. The carbon fiber cloth is used as a pre-constructed framework, the carbon nanotubes growing on the surface of the carbon fiber cloth in situ are used for connecting the carbon fibers, the thermal contact resistance between the radial carbon fibers is reduced, and meanwhile, a long-range ordered heat-conducting network structure is formed by the plain woven carbon fiber cloth framework, so that the heat-conducting performance of the composite material can be obviously improved.
Description
Technical Field
The invention relates to the technical field of heat-conducting composite materials, in particular to a CNTs @ CC heat-conducting filler and a heat-conducting composite material based on the same.
Background
With the continuous development of high-power electronic devices, the heat dissipation of electronic equipment has become a key problem in the development of miniaturization and integration of electronic devices. The polymer material has the characteristics of good electrical insulation, easy modification and processing, low cost, chemical corrosion resistance, good mechanical property and the like, and has wide prospect in the field of heat conduction materials. At present, the economic and effective method for improving the heat-conducting property of the high polymer material is to mix high heat-conducting filler. In the carbon-based filler, the carbon fibers are formed by stacking flaky graphite microcrystals along the axial direction of the fibers, so that the heat conduction of the carbon fibers is anisotropic, and the axial heat conductivity is far higher than that of the carbon fibers in the radial direction. The carbon fiber mainly comprises two types of polyacrylonitrile and asphalt, and the axial thermal conductivity of the polyacrylonitrile-based carbon fiber is about 8-70 W.m-1·K-1The axial thermal conductivity of the high-performance asphalt-based carbon fiber is about 530 to 1100 W.m-1·K-1However, the pitch-based carbon fiber is difficult to process into carbon fiber products, the production difficulty and the cost are obviously higher than those of polyacrylonitrile-based carbon fiber, and the PAN-based carbon fiber has obvious advantages in the aspects of tensile strength and the like. For carbon fiber composite materials, the improvement of the heat conductivity of the carbon fiber composite materials is mostly surrounded by the modification of the surface of the carbon fiber, or the improvement of the heat conductivity of the carbon fiber in the orientation direction by an ice template method, electric field orientation, magnetic field orientation and the like, but the surface functionalization is only effective in the aspect of reducing the interface thermal resistance, so that an efficient heat conduction path is difficult to construct in a matrix, and the preparation processes of the ice template method and the like have high cost and complex processes.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a preparation method of a CNTs @ CC heat-conducting filler and a heat-conducting composite material based on the same, and the technical problems to be solved are as follows: a pre-framework construction method is adopted, polyacrylonitrile-based carbon fiber cloth woven in a plain weave mode is used as a heat conduction network carrier, bimetallic Co/Zn-ZIF crystals grow on the surface of carbon fibers in situ, the crystals are calcined at high temperature to be converted into carbon nano tubes in situ, the carbon fibers are connected by virtue of the carbon nano tubes, the radial heat conduction capacity of the carbon fibers is fully improved, and meanwhile, a novel filler with a long-range ordered heat conduction network is constructed, and the heat conduction performance of the novel filler can be remarkably improved after the novel filler is compounded with epoxy resin.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly discloses a preparation method of a CNTs @ CC heat-conducting filler, which is characterized by comprising the following steps: firstly, modifying carbon fiber cloth CC by concentrated nitric acid to obtain functional carbon fiber cloth; and then growing a bimetallic Co/Zn-ZIF crystal on the surface of the functionalized carbon fiber cloth in situ, and finally calcining at high temperature to convert the Co/Zn-ZIF crystal into carbon nano tube CNTs in situ, thereby obtaining the CNTs @ CC heat-conducting filler. The method specifically comprises the following steps:
preparation of step 1, fCC
Immersing the carbon fiber cloth in concentrated nitric acid, and then placing the carbon fiber cloth in a hydrothermal reaction kettle to react for 6 hours at the temperature of 95-100 ℃ to obtain functional carbon fiber cloth, which is recorded as fCC;
Pouring 50mL of aqueous solution containing 1mmol of zinc nitrate hexahydrate and 2mmol of cobalt nitrate hexahydrate into 50mL of aqueous solution containing 20mmol of 2-methylimidazole, and stirring for 3-5 min to obtain a precursor solution; vertically immersing fCC obtained in the step 1 into the precursor liquid, standing for 3 hours to obtain carbon fiber cloth with bimetal Co/Zn-ZIF crystals growing on the surface, and marking the carbon fiber cloth as Co/Zn-ZIF @ fCC;
Placing the Co/Zn-ZIF @ fCC obtained in the step (2) in a tube furnace, adding dicyandiamide as a carbon source, wherein the dicyandiamide is positioned at the upstream of the Co/Zn-ZIF @ fCC according to the argon flow direction; firstly, calcining for 2 hours at 400 ℃, then heating to 1000 ℃ and calcining for 2-6 hours to convert Co/Zn-ZIF crystals into carbon nano tubes in situ;
immersing the calcined sample in 0.5mol/L H2SO4And etching the solution for 6-12 hours to remove unstable cobalt, thereby obtaining the CNTs @ CC heat-conducting filler.
Preferably, in step 1, the carbon fiber cloth is polyacrylonitrile-based carbon fiber cloth.
Preferably, in the step 3, the adding amount of the dicyandiamide is 2-3 times of the mass of the Co/Zn-ZIF @ fCC.
Preferably, in step 3, the temperature increase rate of the calcination is 5 ℃/min.
The CNTs @ CC heat-conducting filler obtained by the preparation method can be used for preparing heat-conducting composite materials. The thermal conductive composite material is obtained by coating epoxy resin on two surfaces of the CNTs @ CC thermal conductive filler and curing. Specifically, the preparation method of the heat-conducting composite material comprises the following steps:
uniformly mixing epoxy resin, a catalyst and a curing agent, and degassing in vacuum to remove bubbles to obtain an epoxy resin mixed solution;
and (2) dropwise adding the epoxy resin mixed solution to one surface of the CNTs @ CC heat-conducting filler, carrying out vacuum-assisted infiltration for 10-30 min at 40-60 ℃, then dropwise adding the epoxy resin mixed solution to the other surface of the CNTs @ CC heat-conducting filler, carrying out vacuum-assisted infiltration for 10-30 min at 40-60 ℃, and finally curing for 1h at 110-120 ℃ to obtain the CNTs @ CC/EP heat-conducting composite material.
Preferably, the epoxy resin is bisphenol F epoxy resin, the catalyst is methylhexahydrophthalic anhydride, and the curing agent is 2,4, 6-tris (dimethylaminomethyl) phenol.
Preferably, the volume ratio of the epoxy resin to the catalyst to the curing agent is 95-105: 5.
The invention has the beneficial effects that:
1. the carbon fiber cloth is used as a pre-constructed framework, the carbon nanotubes growing on the surface of the carbon fiber cloth in situ are used for connecting the carbon fibers, the thermal contact resistance between the radial carbon fibers is reduced, and meanwhile, a long-range ordered heat-conducting network structure is formed by the plain woven carbon fiber cloth framework, so that the heat-conducting performance of the composite material can be obviously improved.
2. According to the invention, Co/Zn-ZIF crystals are converted into carbon nano-tubes (CNTs) in situ through high-temperature calcination, a large amount of carbon source can be provided when the Co/Zn-ZIF crystals formed by two metal ligands are pyrolyzed, Co ions are reduced into Co nano-particles and catalyze to grow the carbon nano-tubes through high-temperature calcination at 1000 ℃, and Zn is removed through evaporation at over 900 ℃.
Drawings
Fig. 1 is SEM images of carbon fiber cloth used in examples 1 and 2 of the present invention, wherein (a) and (b) are high-density carbon fiber cloth and low-density carbon fiber cloth, respectively;
FIG. 2 is a digital photograph of Co/Zn-ZIF @ fCC obtained in example 1 of the present invention;
FIG. 3 is an SEM image of Co/Zn-ZIF @ fCC obtained in example 1 of the present invention, wherein (a) and (b) correspond to different magnifications;
FIG. 4 is a SEM photograph of CNTs @ CC obtained in example 1 of the present invention;
FIG. 5 is a SEM image of CNTs @ CC/EP composite obtained in example 1 of the present invention;
FIG. 6 is a graph showing a comparison of thermal conductivity of samples obtained in examples 1 and 2 of the present invention and comparative examples 1 and 2.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
The thermal diffusivity of the samples obtained in the following examples and comparative examples was measured by using a laser thermal conductivity meter (LFA467, Netzsch, germany).
Example 1
In the embodiment, the CNTs @ CC/EP heat-conducting composite material is prepared by the following steps:
preparation of step 1, fCC
Cutting high-density carbon fiber cloth into 3 x 3cm2And placing the carbon fiber cloth and 60mL of concentrated nitric acid (commercial concentrated nitric acid, no dilution, mass fraction of about 68%) in a 100mL hydrothermal reaction kettle, and reacting at 100 ℃ for 6h to obtain the functionalized carbon fiber cloth, which is recorded as fCC.
Pouring 50mL of aqueous solution containing 1mmol of zinc nitrate hexahydrate and 2mmol of cobalt nitrate hexahydrate into 50mL of aqueous solution containing 20mmol of 2-methylimidazole, and stirring for 3min to obtain a precursor solution; and (3) vertically immersing fCC obtained in the step (1) into the precursor solution, standing for 3 hours to obtain the carbon fiber cloth with the surface growing bimetal Co/Zn-ZIF crystals, and marking as Co/Zn-ZIF @ fCC.
Placing the Co/Zn-ZIF @ fCC obtained in the step (2) in a tube furnace, adding 0.6g of dicyandiamide as a carbon source, wherein the dicyandiamide is positioned at the upstream of the Co/Zn-ZIF @ fCC according to the argon flow direction; firstly calcining at 400 ℃ for 2h, then heating to 1000 ℃ and calcining for 6h to convert Co/Zn-ZIF crystals into carbon nano tubes in situ;
immersing the calcined sample in 0.5mol/L H2SO4Etching in the solution for 12h to remove unstable cobalt, thus obtaining the CNTs @ CC heat-conducting filler.
Step 4, preparing the CNTs @ CC/EP composite material
Uniformly mixing bisphenol F type epoxy resin, methyl hexahydrophthalic anhydride serving as a catalyst and 2,4, 6-tris (dimethylaminomethyl) phenol serving as a curing agent according to the volume ratio of 100:100:5, and degassing in vacuum to remove bubbles to obtain epoxy resin mixed solution;
and (2) dropwise adding an epoxy resin mixed solution on one surface of the CNTs @ CC heat-conducting filler, carrying out vacuum-assisted infiltration for 20min at 40 ℃, then dropwise adding an epoxy resin mixed solution on the other surface of the CNTs @ CC heat-conducting filler, carrying out vacuum-assisted infiltration for 20min at 40 ℃, and finally curing for 1h at 120 ℃ to obtain the CNTs @ CC/EP heat-conducting composite material.
Example 2
This example prepares CNTs @ CC/EP composite in the same manner as in example 1, except that a low-density woven carbon fiber cloth is used as the raw material.
Comparative example 1
The comparative example prepares a CC/EP composite as follows:
cutting high-density carbon fiber cloth CC into 3 x 3cm2；
Uniformly mixing bisphenol F type epoxy resin, methyl hexahydrophthalic anhydride serving as a catalyst and 2,4, 6-tris (dimethylaminomethyl) phenol serving as a curing agent according to the volume ratio of 100:100:5, and degassing in vacuum to remove bubbles to obtain epoxy resin mixed solution;
and dropwise adding the epoxy resin mixed solution on one surface of the CC, carrying out vacuum-assisted infiltration at 40 ℃ for 20min, then dropwise adding the epoxy resin mixed solution on the other surface of the CC, carrying out vacuum-assisted infiltration at 40 ℃ for 20min, and finally curing at 120 ℃ for 1h to obtain the CC/EP heat-conducting composite material.
Comparative example 2
In this example, a CC/EP composite was prepared in the same manner as in comparative example 1 except that a low-density woven carbon fiber cloth was used as a raw material.
Fig. 1 is an SEM image of the carbon fiber cloth used in the above embodiment, wherein (a) and (b) are a high-density carbon fiber cloth and a low-density carbon fiber cloth, respectively, and it can be seen from the SEM image that the weaving density of the two carbon cloths is significantly different under the same magnification, and the high-weaving-density carbon cloth forms a denser heat-conducting network in the polymer matrix. FIG. 2 is a digital photograph of Co/Zn-ZIF @ fCC prepared in example 1, showing that the whole of the carbon cloth after growing the crystal turns purple. FIG. 3 is an SEM image of Co/Zn-ZIF @ fCC prepared in example 1 at different magnifications, and it can be seen that dense leaf-type crystals with a size of several micrometers are grown on the surface of the carbon fiber. FIG. 4 is an SEM image of CNTs @ CC obtained in example 1, and it can be seen that the bimetallic Co/Zn-ZIF crystals of micron size are completely converted into carbon nanotubes in situ after high temperature calcination.
FIG. 5 is an SEM image of the CNTs @ CC/EP thermally conductive composite material obtained in example 1, and it can be seen that carbon fibers are connected by carbon nanotubes.
As can be seen from the results of the thermal diffusivity test of the two composite materials of CNTs @ CC/EP and CC/EP with different weaving densities in FIG. 6, the thermal conductivity of the composite material is obviously improved after carbon tubes are grown in situ on the surface of the carbon cloth, and the thermal conductivity is better when the carbon cloth with high weaving density is used as the raw material, because the higher the weaving density is, the more the thermal conductivity paths are.
According to the invention, after the carbon nanotubes grow on the surface of the carbon fiber cloth and are compounded with the epoxy resin, the plain woven carbon cloth constructs a long-range ordered heat conduction network in the matrix, and the carbon fiber axial high heat conduction performance is fully utilized, and meanwhile, the carbon fiber carbon tube connection is adopted, so that the carbon fiber indirect thermal contact resistance can be further reduced, and the heat conduction performance of the composite material is obviously improved.
The present invention is not limited to the above exemplary embodiments, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of CNTs @ CC heat-conducting filler is characterized by comprising the following steps: firstly, modifying carbon fiber cloth CC by concentrated nitric acid to obtain functional carbon fiber cloth; and then growing a bimetallic Co/Zn-ZIF crystal on the surface of the functionalized carbon fiber cloth in situ, and finally calcining at high temperature to convert the Co/Zn-ZIF crystal into carbon nano tube CNTs in situ, thereby obtaining the CNTs @ CC heat-conducting filler.
2. The method of claim 1, comprising the steps of:
preparation of step 1, fCC
Immersing the carbon fiber cloth in concentrated nitric acid, and then placing the carbon fiber cloth in a hydrothermal reaction kettle to react for 6 hours at the temperature of 95-100 ℃ to obtain functional carbon fiber cloth, which is recorded as fCC;
step 2, preparation of Co/Zn-ZIF @ fCC
Pouring 50mL of aqueous solution containing 1mmol of zinc nitrate hexahydrate and 2mmol of cobalt nitrate hexahydrate into 50mL of aqueous solution containing 20mmol of 2-methylimidazole, and stirring for 3-5 min to obtain a precursor solution; vertically immersing fCC obtained in the step 1 into the precursor liquid, standing for 3 hours to obtain carbon fiber cloth with bimetal Co/Zn-ZIF crystals growing on the surface, and marking the carbon fiber cloth as Co/Zn-ZIF @ fCC;
step 3, preparation of CNTs @ CC
Placing the Co/Zn-ZIF @ fCC obtained in the step (2) in a tube furnace, adding dicyandiamide as a carbon source, wherein the dicyandiamide is positioned at the upstream of the Co/Zn-ZIF @ fCC according to the argon flow direction; firstly, calcining for 2 hours at 400 ℃, then heating to 1000 ℃ and calcining for 2-6 hours to convert Co/Zn-ZIF crystals into carbon nano tubes in situ;
immersing the calcined sample in 0.5mol/L H2SO4And etching the solution for 6-12 hours to remove unstable cobalt, thereby obtaining the CNTs @ CC heat-conducting filler.
3. The method of claim 2, wherein: in the step 1, the carbon fiber cloth is polyacrylonitrile-based carbon fiber cloth.
4. The method of claim 2, wherein: in the step 3, the adding amount of the dicyandiamide is 2-3 times of the mass of the Co/Zn-ZIF @ fCC.
5. The method of claim 2, wherein: in step 3, the heating rate of the calcination is 5 ℃/min.
6. The CNTs @ CC heat-conducting filler obtained by the preparation method of any one of claims 1-5.
7. A thermally conductive composite material, comprising: the thermal conductive composite material is obtained by coating epoxy resin on two surfaces of the CNTs @ CC thermal conductive filler and curing.
8. A method for preparing the heat conductive composite material of claim 7, wherein: epoxy resin, a catalyst and a curing agent are uniformly mixed, and vacuum degassing is carried out to remove bubbles to obtain epoxy resin mixed solution.
And (2) dropwise adding the epoxy resin mixed solution to one surface of the CNTs @ CC heat-conducting filler, carrying out vacuum-assisted infiltration for 10-30 min at 40-60 ℃, then dropwise adding the epoxy resin mixed solution to the other surface of the CNTs @ CC heat-conducting filler, carrying out vacuum-assisted infiltration for 10-30 min at 40-60 ℃, and finally curing for 1h at 110-120 ℃ to obtain the CNTs @ CC/EP heat-conducting composite material.
9. The method of claim 8, wherein: the epoxy resin is bisphenol F type epoxy resin, the catalyst is methylhexahydrophthalic anhydride, and the curing agent is 2,4, 6-tris (dimethylaminomethyl) phenol.
10. The method of claim 8, wherein: the volume ratio of the epoxy resin to the catalyst to the curing agent is 95-105: 5.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150329761A1 (en) * | 2014-05-14 | 2015-11-19 | Aleksandar GRUJICIC | Fiber and nanomaterial composite material and method for making the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150329761A1 (en) * | 2014-05-14 | 2015-11-19 | Aleksandar GRUJICIC | Fiber and nanomaterial composite material and method for making the same |
Non-Patent Citations (2)
| Title |
|---|
| JEONGHUN KIM: "CNTs grown on nanoporous carbon from zeolitic imidazolate frameworks for supercapacitors", 《CHEM COMM》 * |
| 任冲等: "基于原位生长CNTs/CFF/EP层状复合材料的成型工艺", 《中国有色金属学报》 * |
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