CN114855453A - Preparation method of high-thermal-conductivity composite material with self-assembled fiber-like monolithic structure - Google Patents
Preparation method of high-thermal-conductivity composite material with self-assembled fiber-like monolithic structure Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 83
- 239000002243 precursor Substances 0.000 claims abstract description 47
- 238000003825 pressing Methods 0.000 claims abstract description 23
- 239000011258 core-shell material Substances 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 230000008014 freezing Effects 0.000 claims abstract description 16
- 238000007710 freezing Methods 0.000 claims abstract description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004327 boric acid Substances 0.000 claims abstract description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 238000003837 high-temperature calcination Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- -1 KH-550 Chemical compound 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 238000009413 insulation Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 23
- 229910052582 BN Inorganic materials 0.000 description 22
- 239000000463 material Substances 0.000 description 21
- 238000002791 soaking Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 210000005056 cell body Anatomy 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
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Abstract
The invention discloses a preparation method of a high-thermal-conductivity composite material with a self-assembled fiber-like monolithic structure, which comprises the following steps: the precursor solution composed of boric acid and melamine forms fiber self-assembly orientation arrangement under the conditions of voltage and freezing, and the composite material with the fiber-imitated monolithic structure is obtained by pressing after calcining and coating treatment. The high-thermal-conductivity composite material with the fiber-like monolithic structure, prepared by the invention, fully utilizes the self-assembly behavior of the precursor solution under the external voltage and freezing conditions, effectively adjusts the orientation arrangement of the precursor fibers, forms the structure of the inner core shell after calcination and coating treatment, and prepares the fiber-like monolithic structure composite material with a shorter thermal conduction path through parallel fiber axial pressing treatment, can quickly transfer heat, has high thermal conductivity and good mechanical properties, and has wide application prospects in the fields of aerospace, thermal conduction insulation and the like.
Description
Technical Field
The invention belongs to the technical field of heat-conducting composite materials, and relates to a preparation method of a high-heat-conducting composite material with a self-assembled fiber-like monolithic structure.
Background
Boron Nitride (BN) is a novel functional material, has the characteristics of high temperature resistance, large heat conductivity, good insulativity, high specific surface area, excellent chemical stability and the like, and is widely applied to the fields of aerospace, heat conduction and insulation, energy storage, catalytic adsorption and the like. The thermal conductivity is between 300- 9 Omega, is an ideal filler for preparing the composite material with both heat conduction and insulation properties. The heat conduction process is similar to the electrical conduction process, and the heat conductivity depends on whether a heat conduction path or a heat conduction chain exists in the composite material. It is known that increasing the number of heat conduction paths and increasing the packing density of the material can make the filler particles easily contact with each other to form heat conduction paths, thereby improving the heat conduction performance of the polymer. However, the high filler density leads to difficult dispersion of BN in the matrix, so that the mechanical properties of the composite are drastically reduced. Therefore, it is necessary to prepare a composite material with high thermal conductivity on the basis of ensuring the mechanical properties.
The fibrous monolith structure is formed by arranging fibrous cell bodies in a certain mode, and separating and integrating relatively thin cell interfaces into a block body. The special structure can lead the crack to deflect, proliferate, transversely expand and the like when the material is fractured, further lead the crack to be passivated, and further improve the fracture toughness and the fracture work of the material. However, current fibrous monolith structures typically require mechanical lay-up of the fibers, which is extremely disadvantageous for smaller size fibers. If the fiber can be arranged in a self-assembly orientation manner in the forming process, and then the composite material with the fiber-like monolithic structure is prepared, the heat-conducting property of the material can be favorably improved, and the mechanical property of the material can also be improved. Therefore, how to self-assemble the high-thermal-conductivity composite material with the imitated fiber monolithic structure is a key for solving the problem.
Chinese patent "preparation method of a kind of honeycomb-shaped high heat conduction material" (application number: CN201910696122.1, grant number: CN110421958B, published as 2021.09.10) discloses a preparation method of a kind of honeycomb-shaped high heat conduction material, which is prepared by impregnating and coating BN nanosheets after electrostatic spinning, then carrying out full coverage treatment by nano silver, and then laminating and hot pressing. The method fully utilizes the extremely high in-plane thermal conductivity of BN, the thermal conduction path is constructed through the connection of nano silver, and the thermal resistance of the interface is reduced by reducing the fiber pores through the hot pressing of the laminated layers, so that the prepared honeycomb-like high thermal conductivity composite material has high thermal conductivity. However, the preparation process of the method is complex, the heat conduction path on the surface of the fiber is difficult to completely penetrate, and the influence on the mechanical property of the composite material is small.
Chinese patent "a bionic fiber monolithic structure boron nitride high-temperature self-lubricating material and a preparation method thereof" (application number: CN202110458373.3, authorization number: CN113511913A, published: 2021.04.27) discloses a bionic fiber monolithic structure boron nitride high-temperature self-lubricating material, which takes c-BN as a fiber cell body and h-BN of the same different phase as an interface layer, wherein the c-BN fiber cell body plays a role in high bearing, and the strength of the material is improved; the h-BN weak interface lubricating phase has a lubricating effect, and the toughness and service reliability of the material are improved. The method improves the mechanical property of the material, but the preparation process is more complex and has little influence on the heat-conducting property of the material.
Chinese patent "A preparation method of a directional heat-conducting wear-resistant composite brake material" (application No. CN202010244809.4, No. CN111365393B, published as 2021.09.10) discloses a preparation method of a directional heat-conducting wear-resistant composite brake material, which is obtained by preparing wear-resistant ceramic slurry and preparing a directional arrangement BN fiber cylinder. The material has the advantages that the wear resistance of the material is ensured, the directional heat conducting performance of the material is improved, and the generated heat can be rapidly and directionally led out along the three layers of heat conducting channels in the braking process. However, in the method, the heat-conducting filler is filled in the reserved pore channel, the preparation process is complex, the operation difficulty is high, and the mechanical property of the composite material is difficult to improve by the structure.
Chinese patent "a device and method for preparing heat-conducting insulating material based on magnetization modification" (application No. CN201911282854.2, No. CN110903503B, published as 2020.09.11) discloses a device and method for preparing heat-conducting insulating material based on magnetization modification, which comprises the steps of generating nano ferroferric oxide particles on the surface of BN, preparing magnetic coated particles, applying a magnetic field in stages in the curing process, orienting the magnetic particles in the composite material, constructing an ordered heat-conducting channel, and improving the heat conductivity of the epoxy composite material. The preparation method is complex in preparation process, mutual communication is difficult to achieve when the BN filling amount is low, and the mechanical property of the composite material is difficult to improve by the structure when the BN filling amount is high.
Disclosure of Invention
The invention aims to provide a preparation method of a high-thermal-conductivity composite material with a self-assembled fiber-like monolithic structure, which solves the problems that the mechanical property of the composite material is reduced due to the complex preparation process and the high filling of a thermal-conductive filler in the prior art.
The technical scheme adopted by the invention is as follows:
a preparation method of a high-thermal-conductivity composite material with a self-assembled fiber-like monolithic structure is implemented by the following steps:
step 1, adding boric acid, melamine and an additive into a solvent, heating and stirring in a water bath to obtain a precursor solution;
step 2, applying voltage to the upper end and the lower end of the precursor solution obtained in the step 1, placing the precursor solution on a low-temperature plate for freezing, and then obtaining a precursor fiber framework which is self-assembled and oriented;
step 3, carrying out high-temperature calcination treatment on the precursor fiber framework obtained in the step 2 in a nitrogen environment, and drying after dipping in a polymer solution to obtain the oriented inner core-shell fibers;
and 4, performing pressing treatment on the inner core shell fibers obtained in the step 3 in a manner of being parallel to the fiber axial direction to obtain the self-assembled fiber-like monolithic structure high-thermal-conductivity composite material.
The invention is also characterized in that:
in the step 1, the precursor solution consists of the following substances in percentage by mass: 3 to 15 percent of boric acid, 1 to 8 percent of melamine, 0.05 to 0.2 percent of additive, 76.8 to 95.95 percent of solvent, and the total of the components is 100 percent.
In the step 1, the additive is any one of sodium dodecyl benzene sulfonate, KH-550, sodium dodecyl sulfate, polyvinylpyrrolidone, polyvinyl alcohol and the like, the solvent is a mixed solvent consisting of water and one or more of ethanol, tert-butyl alcohol, isopropanol and the like, and the volume of the water accounts for 60-100%.
In the step 1, the water bath temperature is 60-95 ℃, and the water bath time is 0.5-4 h.
In the step 2, the voltage applied to the upper end and the lower end of the precursor solution is 5 kV-20 kV, the freezing temperature of a low-temperature plate is-50 ℃ to-20 ℃, the freezing time is 4 h-8 h, and the vacuum drying process parameters are as follows: the vacuum degree is 0.1Pa to 20Pa, and the drying time is 24h to 48 h.
In the step 3, the high-temperature calcination temperature is 1000-1500 ℃, and the calcination time is 2-6 h.
The polymer solution in the step 3 comprises the following substances in percentage by mass: 20-40% of polymer and 60-80% of solvent, wherein the polymer is any one of polyvinylidene fluoride, polystyrene, polycaprolactone, polyacrylonitrile and polymethyl methacrylate, and the solvent is one or more of N, N-dimethylformamide, acetone, chloroform, tetrahydrofuran and dimethyl sulfoxide.
In the step 3, the dipping temperature is 25-50 ℃, the dipping time is 1-3 min, and the dipping times are 1-5; the drying temperature is 60-90 ℃, and the drying time is 10-30 min.
In the step 4, the pressing treatment is carried out under the pressure of 10MPa to 30MPa, the temperature of 160 ℃ to 200 ℃ and the pressing time of 5min to 20 min.
The invention has the beneficial effects that:
the invention can obtain the high-thermal-conductivity composite material with the imitated fiber monolithic structure through self-assembly, fully utilizes the self-assembly behavior of the precursor solution under the external voltage and freezing conditions, effectively adjusts the orientation arrangement of the precursor fibers, forms the structure of the inner core shell after calcination and coating treatment, and then obtains the high-thermal-conductivity composite material with the imitated fiber monolithic structure after pressing along the axial direction of the fibers.
Drawings
Fig. 1 is a schematic cross-sectional view of a self-assembled fiber-like monolithic structure high thermal conductivity composite material prepared in this example 1.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The technical scheme adopted by the invention is that the preparation method of the high-thermal-conductivity composite material with the self-assembled fiber-like monolithic structure is implemented according to the following steps:
step 1, preparing a precursor solution:
adding boric acid, melamine and an additive into a solvent, wherein the solvent comprises the following substances in percentage by mass: 3 to 15 percent of boric acid, 1 to 8 percent of melamine, 0.05 to 0.2 percent of additive, 76.8 to 95.95 percent of solvent, and the total of the components is 100 percent. Wherein the additive is any one of sodium dodecyl benzene sulfonate, KH-550, sodium dodecyl sulfate, polyvinylpyrrolidone, polyvinyl alcohol and the like, the solvent is a mixed solvent consisting of water and one or more of ethanol, tert-butyl alcohol, isopropanol and the like, and the volume of the water accounts for 60-100%. Heating and stirring in water bath at 60-95 ℃ for 0.5-4 h to obtain precursor solution.
Step 2, self-assembly orientation arrangement;
and (2) applying a voltage of 5 kV-20 kV to the upper end and the lower end of the precursor solution obtained in the step (1), placing the precursor solution on a low-temperature plate at the temperature of minus 50 ℃ to minus 20 ℃ for freezing for 4 h-8 h, and then performing vacuum drying for 24 h-48 h under the condition that the vacuum degree is 0.1 Pa-20 Pa to obtain the precursor fiber framework in self-assembly orientation arrangement.
And 3, calcining and surface coating treatment:
and (2) performing high-temperature calcination treatment on the precursor fiber framework obtained in the step (2) in a nitrogen environment, wherein the calcination temperature is 1000-1500 ℃, the calcination time is 2-6 h, the precursor fiber framework is soaked for 1-5 times by using a polymer solution with a certain concentration under the conditions that the temperature is 25-50 ℃ and the time is 1-3 min, and the polymer solution comprises the following substances in percentage by mass: 20-40% of polymer and 60-80% of solvent, wherein the polymer is any one of polyvinylidene fluoride, polystyrene, polycaprolactone, polyacrylonitrile and polymethyl methacrylate, the solvent is one or more of N, N-dimethylformamide, acetone, chloroform, tetrahydrofuran and dimethyl sulfoxide, and the fiber is dried at 60-90 ℃ for 10-30 min to obtain the oriented inner core-shell fiber.
Step 4, pressing the fiber-imitated monolithic structure:
and (4) performing pressing treatment on the inner core shell fibers obtained in the step (3) in parallel with the fiber axial direction, and pressing for 5-20 min under the conditions that the pressure is 10-30 MPa and the temperature is 160-200 ℃ to obtain the high-thermal-conductivity composite material with the self-assembled fiber-like monolithic structure.
According to the invention, a precursor solution composed of boric acid and melamine is selected, the voltages at the upper end and the lower end are controlled, the freezing temperature of a low-temperature plate is adjusted, and the self-assembly behavior of the precursor solution is fully utilized, so that precursor fibers are arranged in an oriented manner in the forming process; through controlling calcination temperature and coating treatment process, make fibre and polymer in the impregnating solution in close contact with, adjust impregnation concentration and number of times control shell portion polymer thickness, obtain the inner core shell fibre of orientation arrangement, core BN fibre has formed shorter heat conduction path, can be fast with heat transfer, shell portion polymer connection fibre cell body, through follow-up parallel fiber axial pressing treatment, make inner core shell fibre directional solidification, thereby the combined material of imitative fibre monolithic structure has been prepared, not only show excellent heat conductivility, combined material's mechanical properties has still been promoted.
The invention prepares the high-thermal-conductivity composite material with the imitated fiber monolithic structure by self-assembly, fully utilizes the self-assembly behavior of the precursor solution under the external voltage and freezing conditions, effectively adjusts the orientation arrangement of the precursor fibers, forms the structure of the inner core shell after calcination and coating treatment, prepares the imitated fiber monolithic structure composite material with a shorter thermal conduction path by axial pressing treatment of parallel fibers, can quickly transfer heat, has high thermal conductivity and good mechanical property, and has wide application prospect in the fields of aerospace, thermal conduction insulation and the like.
Example 1 PVDF-BN COMPOSITE MATERIAL WITH IMITATED FIBER MONO-STONE STRUCTURE
Adding 3g of boric acid, 1g of melamine and 0.05g of sodium dodecyl benzene sulfonate into 95.95g of water, heating and stirring in a water bath at 95 ℃ for 0.5h to obtain a precursor solution, applying 5kV voltage to the upper end and the lower end of the precursor solution, placing the precursor solution on a low-temperature plate at-20 ℃ for freezing for 8h, and then performing vacuum drying for 48h under the condition of vacuum degree of 20Pa to obtain the precursor fiber framework in self-assembly orientation arrangement. And (2) carrying out high-temperature calcination treatment in a nitrogen environment, wherein the calcination temperature is 1000 ℃, the calcination time is 6h, soaking for 1min at 25 ℃ by using a polymer solution (2g of polyvinylidene fluoride is added into 8g of N, N-dimethylformamide), soaking for 5 times, and drying for 30min at 60 ℃ to obtain the oriented inner core-shell fiber. And (3) performing pressing treatment on the fibers of the inner core shell in parallel with the fiber axial direction, and pressing for 20min under the conditions of 10MPa of pressure and 160 ℃ to obtain the PVDF-BN high-thermal-conductivity composite material with the fiber-like monolithic structure.
Table 1 shows the comparison of the properties of the fiber-like monolithic PVDF-BN composite, the BN fiber reinforced PVDF composite, and the BN particle reinforced PVDF composite prepared by the method of the present invention in example 1. Wherein the BN fiber or particle reinforced composite material is randomly distributed under the same content. As can be seen from table 1, the tensile strength of the BN particle reinforced PVDF composite material is the lowest, which is only 5.67MPa, and the tensile strength of the randomly distributed BN fiber reinforced PVDF composite material is slightly higher, but is also only 5.82MPa, compared to the two, the tensile strength of the imitated fiber monolithic structure PVDF-BN composite material at the same content is the highest, which can reach 8.96MPa, and the thermal conductivity along the axial direction of the fiber can reach 6.32W/(m · K), which is 2.38 times that of the randomly distributed BN fiber reinforced PVDF composite material. The fracture toughness of the PVDF-BN composite material with the fiber-like monolithic structure is improved and the tensile strength of the PVDF-BN composite material is increased because the BN fibers arranged in parallel inhibit the fracture of the composite material. In addition, the high-thermal-conductivity BN fiber oriented arrangement also contributes to the rapid heat transfer, so that the thermal conductivity of the composite material is effectively improved, and the thermal conductivity of the composite material is increased.
TABLE 1 comparison of Properties of PVDF-BN COMPOSITE MATERIAL, BN FIBER REINFORCED PVDF COMPOSITE MATERIAL AND BN PARTICLE REINFORCED PVDF COMPOSITE MATERIAL IN EXAMPLE 1
FIG. 1 is a schematic cross-sectional view of a PVDF-BN composite material with a fiber-like monolithic structure prepared in the invention. As can be seen from FIG. 1, after the self-assembly process, the BN fibers are oriented and arranged, and are wrapped by PVDF, and the BN fibers and the PVDF are tightly combined, so that the composite material with the imitated fiber monolithic structure is obtained after pressing.
Example 2 PS-BN composite Material having a pseudo-fiber monolithic Structure
Adding 15g of boric acid, 8g of melamine and 0.2g of polyvinylpyrrolidone into 76.8g of mixed solvent (water volume accounts for 60 percent and tert-butyl alcohol accounts for 40 percent), heating and stirring in a water bath at 60 ℃ for 4 hours to obtain a precursor solution, applying 20kV voltage to the upper end and the lower end of the precursor solution, placing the precursor solution on a low-temperature plate at 50 ℃ below zero for freezing for 4 hours, and then performing vacuum drying for 24 hours under the condition of 0.1Pa of vacuum degree to obtain the precursor fiber skeleton in self-assembly orientation arrangement. And (2) carrying out high-temperature calcination treatment in a nitrogen environment, wherein the calcination temperature is 1500 ℃, the calcination time is 2 hours, soaking the fiber in a polymer solution (4g of polystyrene is added into a mixed solvent of 4g of N, N-dimethylformamide and 2g of acetone) at 50 ℃ for 3min, soaking for 1 time, and drying at 90 ℃ for 10min to obtain the oriented inner core-shell fiber. And (3) performing pressing treatment on the fibers of the inner core shell in parallel with the fiber axial direction, and pressing for 5min under the conditions of the pressure of 30MPa and the temperature of 200 ℃ to obtain the PS-BN high-thermal-conductivity composite material with the fiber-imitated monolithic structure.
Example 3 imitation fiber monolithic Structure PAN-BN composite
Adding 9g of boric acid, 3g of melamine and 0.1g of KH-550 into a mixed solvent (water volume accounts for 80% and ethanol 20%), heating and stirring in a water bath at 80 ℃ for 3h to obtain a precursor solution, applying 10kV voltage to the upper end and the lower end of the precursor solution, placing the precursor solution on a low-temperature plate at-40 ℃ for freezing for 3h, and then performing vacuum drying for 36h under the condition of 5Pa of vacuum degree to obtain the precursor fiber framework in self-assembly orientation arrangement. And (2) performing high-temperature calcination treatment in a nitrogen environment, wherein the calcination temperature is 1300 ℃, the calcination time is 3h, soaking the fiber in a polymer solution (3g of polyacrylonitrile is added into a mixed solvent of 5g of N, N-dimethylformamide and 2g of chloroform) at 30 ℃ for 2min, soaking for 3 times, and drying at 80 ℃ for 20min to obtain the oriented inner core-shell fiber. And (3) performing pressing treatment on the fibers of the inner core shell in parallel with the fiber axial direction, and pressing for 10min under the conditions of the pressure of 20MPa and the temperature of 180 ℃ to obtain the PAN-BN high-thermal-conductivity composite material with the fiber-imitated monolithic structure.
Example 4 PMMA-BN COMPOSITE MATERIAL WITH SIMULATED FIBER MONO-STONE STRUCTURE
Adding 7g of boric acid, 2g of melamine and 0.15g of sodium dodecyl sulfate into a mixed solvent (the volume of water accounts for 70% of that of isopropanol 30%), heating and stirring in a water bath at 90 ℃ for 2h to obtain a precursor solution, applying a voltage of 15kV to the upper end and the lower end of the precursor solution, placing the precursor solution on a low-temperature plate at minus 30 ℃ for freezing for 4h, and then performing vacuum drying for 40h under the condition of a vacuum degree of 10Pa to obtain the precursor fiber framework in self-assembly orientation arrangement. And (2) carrying out high-temperature calcination treatment in a nitrogen environment, wherein the calcination temperature is 1100 ℃, the calcination time is 3.5h, soaking the fiber in a polymer solution (2.5g of polymethyl methacrylate is added into a mixed solvent of 6g of acetone and 1.5g of tetrahydrofuran) at 40 ℃ for 2.5min, soaking for 2 times, and drying at 70 ℃ for 25min to obtain the oriented inner core-shell fiber. And (3) performing pressing treatment on the fibers of the inner core shell in parallel with the fiber axial direction, and pressing for 15min under the conditions of 25MPa of pressure and 160 ℃ to obtain the PAN-BN high-thermal-conductivity composite material with the fiber-imitated monolithic structure.
Claims (9)
1. A preparation method of a high-thermal-conductivity composite material with a self-assembled fiber-like monolithic structure is characterized by comprising the following steps:
step 1, adding boric acid, melamine and an additive into a solvent, heating and stirring in a water bath to obtain a precursor solution;
step 2, applying voltage to the upper end and the lower end of the precursor solution obtained in the step 1, placing the precursor solution on a low-temperature plate for freezing, and then obtaining a precursor fiber framework which is self-assembled and oriented;
step 3, carrying out high-temperature calcination treatment on the precursor fiber skeleton obtained in the step 2 in a nitrogen environment, and drying after polymer solution impregnation to obtain oriented inner core-shell fibers;
and 4, performing pressing treatment on the inner core shell fibers obtained in the step 3 in a manner of being parallel to the fiber axial direction to obtain the self-assembled fiber-like monolithic structure high-thermal-conductivity composite material.
2. The preparation method of the self-assembled fiber-like monolithic structural high thermal conductivity composite material according to claim 1, wherein the precursor solution in the step 1 comprises the following substances in percentage by mass: 3 to 15 percent of boric acid, 1 to 8 percent of melamine, 0.05 to 0.2 percent of additive, 76.8 to 95.95 percent of solvent, and the total of the components is 100 percent.
3. The method for preparing the self-assembled high thermal conductivity composite material with the imitated fiber monolithic structure according to claim 2, wherein the additive in the step 1 is any one of sodium dodecyl benzene sulfonate, KH-550, sodium dodecyl sulfate, polyvinylpyrrolidone and polyvinyl alcohol, the solvent is a mixed solvent of water and one or more of ethanol, tert-butyl alcohol and isopropanol, and the volume of the water accounts for 60-100%.
4. The preparation method of the self-assembled fiber-like monolithic structural high thermal conductivity composite material according to claim 2, wherein the water bath temperature in the step 1 is 60-95 ℃ and the water bath time is 0.5-4 h.
5. The preparation method of the self-assembled fiber-like monolithic structure high thermal conductivity composite material according to claim 1, wherein the voltage applied to the upper and lower ends of the precursor solution in the step 2 is 5 kV-20 kV, the cryopanel freezing temperature is-50 ℃ to-20 ℃, the freezing time is 4 h-8 h, and the vacuum drying process parameters are as follows: the vacuum degree is 0.1Pa to 20Pa, and the drying time is 24h to 48 h.
6. The preparation method of the self-assembled fiber-like monolithic structure high thermal conductivity composite material according to claim 1, wherein the high temperature calcination temperature in step 3 is 1000 ℃ to 1500 ℃, and the calcination time is 2h to 6 h.
7. The method for preparing the self-assembled fiber-like monolithic structural high thermal conductivity composite material according to claim 1, wherein the polymer solution in the step 3 is composed of the following substances in percentage by mass: 20-40% of polymer and 60-80% of solvent, wherein the polymer is any one of polyvinylidene fluoride, polystyrene, polycaprolactone, polyacrylonitrile and polymethyl methacrylate, and the solvent is one or more of N, N-dimethylformamide, acetone, chloroform, tetrahydrofuran and dimethyl sulfoxide.
8. The preparation method of the self-assembled fiber-like monolithic structure high thermal conductivity composite material according to claim 1, wherein in the step 3, the dipping temperature is 25 ℃ to 50 ℃, the dipping time is 1min to 3min, and the dipping times are 1 to 5 times; the drying temperature is 60-90 ℃, and the drying time is 10-30 min.
9. The method for preparing the self-assembled fiber-like monolithic structural high thermal conductivity composite material according to claim 1, wherein the pressing treatment in the step 4 is performed under a pressure of 10MPa to 30MPa, at a temperature of 160 ℃ to 200 ℃ and for a pressing time of 5min to 20 min.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265122A (en) * | 2008-04-02 | 2008-09-17 | 西安理工大学 | Method for preparing porous ceramic material under electrostatic field by refrigeration drying technique |
| CN103072959A (en) * | 2013-02-01 | 2013-05-01 | 湖北工业大学 | Preparation method of porous boron nitride |
| CN104788959A (en) * | 2015-03-31 | 2015-07-22 | 中国科学院化学研究所 | Thermal conductive composite material provided with orientation structure and preparation method of thermal conductive composite material |
| WO2017167941A1 (en) * | 2016-03-31 | 2017-10-05 | Total Research & Technology Feluy | Process for the preparation of carbon fibers precursor or carbon slit tapes precursor |
| CN107604477A (en) * | 2017-08-29 | 2018-01-19 | 暨南大学 | A kind of electric field orientation chitosan nano fiber and preparation method and application |
| US20180249593A1 (en) * | 2017-02-28 | 2018-08-30 | Rogers Coporation | Methods for the manufacture of thermal interfaces, thermal interfaces, and articles comprising the same |
| CN110128792A (en) * | 2019-06-04 | 2019-08-16 | 中国科学院深圳先进技术研究院 | A kind of hot interface composites and its preparation method and application |
| CN110421958A (en) * | 2019-07-30 | 2019-11-08 | 西安理工大学 | The preparation method of one type honeycomb highly heat-conductive material |
| CN112877810A (en) * | 2021-02-01 | 2021-06-01 | 山东大学 | Preparation method of porous boron nitride fiber with high specific surface area |
-
2022
- 2022-06-17 CN CN202210687090.0A patent/CN114855453B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265122A (en) * | 2008-04-02 | 2008-09-17 | 西安理工大学 | Method for preparing porous ceramic material under electrostatic field by refrigeration drying technique |
| CN103072959A (en) * | 2013-02-01 | 2013-05-01 | 湖北工业大学 | Preparation method of porous boron nitride |
| CN104788959A (en) * | 2015-03-31 | 2015-07-22 | 中国科学院化学研究所 | Thermal conductive composite material provided with orientation structure and preparation method of thermal conductive composite material |
| WO2017167941A1 (en) * | 2016-03-31 | 2017-10-05 | Total Research & Technology Feluy | Process for the preparation of carbon fibers precursor or carbon slit tapes precursor |
| US20180249593A1 (en) * | 2017-02-28 | 2018-08-30 | Rogers Coporation | Methods for the manufacture of thermal interfaces, thermal interfaces, and articles comprising the same |
| CN107604477A (en) * | 2017-08-29 | 2018-01-19 | 暨南大学 | A kind of electric field orientation chitosan nano fiber and preparation method and application |
| CN110128792A (en) * | 2019-06-04 | 2019-08-16 | 中国科学院深圳先进技术研究院 | A kind of hot interface composites and its preparation method and application |
| CN110421958A (en) * | 2019-07-30 | 2019-11-08 | 西安理工大学 | The preparation method of one type honeycomb highly heat-conductive material |
| CN112877810A (en) * | 2021-02-01 | 2021-06-01 | 山东大学 | Preparation method of porous boron nitride fiber with high specific surface area |
Non-Patent Citations (2)
| Title |
|---|
| MENGJIE WANG ET AL.: "Enhanced thermal conductivity of poly(vinylidene fluoride)/boron nitride nanosheet composites at low filler content", 《COMPOSITES PART A: APPLIED SCIENCE AND MANUFACTURING》, vol. 109, 30 June 2018 (2018-06-30), pages 321 - 329, XP085389070, DOI: 10.1016/j.compositesa.2018.03.023 * |
| 黄青武 等: "氮化硼纤维合成工艺与结构表征", 《硅酸盐通报》, vol. 39, no. 1, 31 January 2020 (2020-01-31), pages 266 - 270 * |
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