CN114855453B - Preparation method of self-assembled fiber-imitated monolithic structure high-heat-conductivity composite material - Google Patents
Preparation method of self-assembled fiber-imitated monolithic structure high-heat-conductivity composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 72
- 239000002243 precursor Substances 0.000 claims abstract description 47
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000003825 pressing Methods 0.000 claims abstract description 19
- 239000011258 core-shell material Substances 0.000 claims abstract description 17
- 230000008014 freezing Effects 0.000 claims abstract description 15
- 238000007710 freezing Methods 0.000 claims abstract description 15
- 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
- 238000001338 self-assembly Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 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 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003837 high-temperature calcination Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000007598 dipping method Methods 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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 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
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 238000009413 insulation Methods 0.000 abstract description 5
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 27
- 229910052582 BN Inorganic materials 0.000 description 26
- 239000000463 material Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000013475 authorization Methods 0.000 description 3
- 210000005056 cell body Anatomy 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 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
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000011664 nicotinic acid 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
- 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
- D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
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- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
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Abstract
The invention discloses a preparation method of a self-assembled fiber-imitated monolithic structure high-heat-conductivity composite material, which specifically comprises the following steps: the precursor solution composed of boric acid and melamine forms fiber self-assembly orientation arrangement under voltage and freezing conditions, and the fiber-imitated monolithic structure composite material is obtained by calcining, coating and pressing. The high-heat-conductivity composite material with the fiber-imitating monolithic structure prepared by the invention fully utilizes the self-assembly behavior of the precursor solution under external voltage and freezing conditions, effectively adjusts the orientation arrangement of precursor fibers, forms the structure of an inner core shell by the fibers after calcining and coating treatment, prepares the fiber-imitating monolithic structure composite material with shorter heat conduction path, high heat conduction and good mechanical property by parallel fiber axial compression treatment, and has wide application prospect in the fields of aerospace, heat conduction and 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 self-assembled high-heat-conducting composite material with a fiber-imitated 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 300W/(m.K), which is slightly lower than that of graphene (1500W/(m.K)), but the resistance value can reach 2.multidot.10 9 Omega is an ideal filler for preparing composite materials with heat conduction and insulation properties. The thermal conduction process is similar to the electrical conduction process, and the thermal conductivity depends on whether a thermal conduction path or a thermal conduction chain exists inside the composite material. It is known to increase the number of heat transfer channels and increase the packing density of the lifter, which can facilitate the contact of filler particles with each other to form heat transfer channels, thereby improving the heat transfer properties of the polymer. However, the high filler density results in a difficult dispersion of BN in the matrix, so that the mechanical properties of the composite material are drastically reduced. Therefore, it is necessary to prepare a composite material with high heat conductivity on the basis of ensuring mechanical properties.
The fibrous monolith structure is a structure in which fibrous cells are arranged in a manner such that relatively thin cell interfaces are separated and integrated into a single block. The special structure can lead cracks to deflect, proliferate, transversely expand and the like when the material breaks, further passivate the cracks, and further improve the fracture toughness and the fracture work of the material. However, current fibrous monolith structures typically require mechanical laying of the fibers, which is extremely disadvantageous for smaller size fibers. If the fibers can be self-assembled and oriented in the forming process, the composite material with the fiber-like monolithic structure can be further prepared, so that the heat conduction performance of the material can be improved, and the mechanical property of the material can be improved. Therefore, how to self-assemble and prepare the high-heat-conductivity composite material with the imitated fiber monolith structure is the key for solving the problem.
Chinese patent (application number: CN201910696122.1, authorization number: CN110421958B, bulletin day: 2021.09.10) discloses a preparation method of a honeycomb-like high-heat-conductivity material, which comprises the steps of immersing and coating BN nano-sheets after electrostatic spinning, and carrying out full-coverage treatment by nano-silver and lamination hot pressing to prepare the honeycomb-like high-heat-conductivity composite material. The method fully utilizes the in-plane thermal conductivity of BN (boron nitride) to construct a heat conduction path through nano silver connection, and stacks hot pressing to reduce fiber pores so as to reduce interface thermal resistance, and the prepared honeycomb-like high heat conduction composite material has high heat conductivity. However, the preparation process is complex, the heat conduction path on the fiber surface is difficult to completely penetrate, and the influence on the mechanical property of the composite material is small.
Chinese patent (CN 202110458373.3, CN113511913A, 2021.04.27) discloses a high-temperature self-lubricating material with a bionic fiber monolith structure, which is prepared from c-BN serving as a fibrous cell body and h-BN of the same kind and different phases serving as an interface layer, wherein the c-BN fibrous cell body plays a high bearing role and improves the strength of the material; the h-BN weak interface lubricating phase plays a role in lubricating, 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 complex, and the influence on the heat conduction property of the material is small.
Chinese patent (application number: CN202010244809.4, authorization number: CN111365393B, bulletin day: 2021.09.10) discloses a preparation method of a directional heat-conducting wear-resistant composite brake material, wherein a directional arranged BN fiber cylinder is prepared by preparing wear-resistant ceramic slurry, so that the directional heat-conducting wear-resistant composite brake material is obtained. The material has high wear resistance and high directional heat conducting performance, and the heat produced during braking may be led out fast along the three heat conducting channels. However, the method fills the heat-conducting filler through the reserved pore canal, the preparation process is complex, the operation difficulty is high, and the structure is difficult to improve the mechanical property of the composite material.
The Chinese patent (application number: CN201911282854.2, authorization number: CN110903503B, bulletin day: 2020.09.11) discloses a device and a method for preparing a heat-conducting and insulating material based on magnetization modification, wherein magnetic coating particles are prepared by generating nano ferroferric oxide particles on the surface of BN, a magnetic field is applied in stages in the curing process, magnetic particles in a composite material are oriented, an ordered heat-conducting channel is constructed, and the heat conductivity of the epoxy composite material is improved. The preparation process is complex, the BN is difficult to communicate with each other when the BN is low in filling amount, and the structure is difficult to improve the mechanical property of the composite material when the BN is high in filling amount.
Disclosure of Invention
The invention aims to provide a preparation method of a self-assembled fiber-imitated monolithic structure high-heat-conductivity composite material, which solves the problems of complex preparation process and reduced mechanical property of the composite material caused by high filling of heat-conductivity filler in the prior art.
The technical scheme adopted by the invention is as follows:
the preparation method of the self-assembled fiber-imitated monolithic structure high-heat-conductivity composite material comprises the following steps:
step 1, adding boric acid, melamine and additives into a solvent, and heating and stirring in a water bath to obtain a precursor solution;
step 2, applying voltage to the upper and lower ends of the precursor solution obtained in the step 1, placing the precursor solution on a low-temperature plate for freezing out, and then obtaining a precursor fiber skeleton which is arranged in a self-assembly orientation manner through vacuum drying;
step 3, calcining the precursor fiber skeleton obtained in the step 2 at a high temperature in a nitrogen environment, and performing drying treatment after impregnation by a polymer solution to obtain the oriented arranged inner core-shell fibers;
and 4, axially pressing the core-shell fiber parallel fibers obtained in the step 3 to obtain the self-assembled fiber-imitated monolithic structure high-heat-conductivity composite material.
The invention is also characterized in that:
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 100 percent of the total.
The additive in the step 1 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 composed of water and one or more of ethanol, tertiary butanol, isopropanol and the like, and the volume ratio of the water is 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 upper end and the lower end of the precursor solution are applied with voltage of 5 kV-20 kV, the freezing temperature of a low-temperature plate is minus 50 ℃ to minus 20 ℃, the freezing time is 4 h-8 h, and the vacuum drying process parameters are as follows: vacuum degree is 0.1 Pa-20 Pa, and drying time is 24 h-48 h.
The high-temperature calcination temperature in the step 3 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.
The dipping temperature in the step 3 is 25-50 ℃, the dipping time is 1-3 min, and the dipping times are 1-5 times; the drying temperature is 60-90 ℃ and the drying time is 10-30 min.
The pressing treatment in the step 4 is carried out under the pressure of 10MPa to 30MPa, the temperature of 160 ℃ to 200 ℃ and the pressing time of 5min to 20min.
The beneficial effects of the invention are as follows:
the method can self-assemble the high-heat-conductivity composite material with the fiber-like monolithic structure, fully utilizes the self-assembly behavior of the precursor solution under external voltage and freezing conditions, effectively adjusts the orientation arrangement of precursor fibers, forms the structure of an inner core shell by the fibers after calcining and coating treatment, and then presses the fibers axially to obtain the high-heat-conductivity composite material with the fiber-like monolithic structure, thereby not only having a shorter heat conduction path, being capable of rapidly transmitting heat and showing excellent heat conduction performance, but also improving the mechanical property of the material by the fiber-like monolithic structure and having wide application prospect in the fields of aerospace, heat conduction and insulation and the like.
Drawings
Fig. 1 is a schematic cross-sectional view of a self-assembled fibrous monolith-structured high thermal conductivity composite prepared in this example 1.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The technical scheme adopted by the invention is that the preparation method of the self-assembled high-heat-conductivity composite material with the fiber-imitated monolithic structure is implemented according to the following steps:
step 1, preparing a precursor solution:
boric acid, melamine and additives are added into a solvent, and the solvent 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 100 percent of the total. 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 composed of water and one or more of ethanol, tertiary butanol, isopropanol and the like, and the volume ratio of water is 60-100%. Heating and stirring in water bath at 60-95 deg.c for 0.5-4 hr to obtain precursor solution.
Step 2, self-assembling orientation arrangement;
and (2) applying a voltage of 5 kV-20 kV to the upper and lower ends of the precursor solution obtained in the step (1), placing the precursor solution on a low-temperature plate at-50 ℃ to-20 ℃ for freezing for 4-8 hours, and then carrying out vacuum drying for 24-48 hours under the vacuum degree of 0.1 Pa-20 Pa to obtain the precursor fiber skeleton with self-assembled orientation arrangement.
Step 3, calcining and surface coating treatment:
carrying out high-temperature calcination treatment on the precursor fiber skeleton obtained in the step 2 in a nitrogen environment, wherein the calcination temperature is 1000-1500 ℃, the calcination time is 2-6 h, and the precursor fiber skeleton is impregnated for 1-5 times under the conditions that the temperature is 25-50 ℃ and the time is 1-3 min by a polymer solution with a certain concentration, wherein 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 inner core-shell fiber in orientation arrangement is obtained by drying at 60-90 ℃ for 10-30 min.
Step 4, pressing the fiber-imitating monolith structure:
and (3) carrying out pressing treatment on the parallel fiber axial direction of the core-shell fiber obtained in the step (3), and pressing for 5-20 min under the conditions of the pressure of 10-30 MPa and the temperature of 160-200 ℃ to obtain the self-assembled high-heat-conductivity composite material with the fiber-imitated monolithic structure.
The method selects the precursor solution composed of boric acid and melamine, controls the voltage at the upper end and the lower end, adjusts the freezing temperature of the low-temperature plate, fully utilizes the self-assembly behavior of the precursor solution, and ensures that precursor fibers are arranged in an oriented manner in the forming process; the calcination temperature and the coating treatment process are controlled, so that the fiber is tightly contacted with the polymer in the impregnating solution, the thickness of the shell part polymer is controlled by adjusting the impregnating concentration and times, the core BN fiber which is arranged in an oriented way is obtained, a shorter heat conduction path is formed by the core BN fiber, the heat can be quickly transferred, the shell part polymer is connected with the fiber cell body, and the core shell fiber is directionally solidified through the subsequent axial pressing treatment of parallel fibers, so that the composite material with the fiber-imitated monolithic structure is prepared, not only is excellent heat conduction performance shown, but also the mechanical property of the composite material is improved.
The invention prepares the high heat conduction composite material of the fiber-like monolithic structure by self-assembly, fully utilizes the self-assembly behavior of the precursor solution under external voltage and freezing conditions, effectively adjusts the orientation arrangement of precursor fibers, forms the structure of an inner core shell by the fibers after calcination and coating treatment, prepares the high heat conduction and good mechanical property fiber-like monolithic structure composite material with shorter heat conduction path by parallel fiber axial compression treatment, can quickly transfer heat, and has wide application prospect in the fields of aerospace, heat conduction and insulation, and the like.
Example 1 fiber-imitated monolithic structure PVDF-BN composite material
3g of boric acid, 1g of melamine and 0.05g of sodium dodecyl benzene sulfonate are added into 95.95g of water, a precursor solution is obtained after heating and stirring for 0.5h in a water bath at 95 ℃, a voltage of 5kV is applied to the upper end and the lower end of the precursor solution, the precursor solution is placed on a low-temperature plate at-20 ℃ for freezing for 8h, and then a precursor fiber skeleton arranged in a self-assembled orientation is obtained through vacuum drying for 48h under the condition of 20Pa of vacuum degree. High-temperature calcination treatment is carried out in a nitrogen environment, the calcination temperature is 1000 ℃ and the calcination time is 6 hours, and the oriented arranged inner core-shell fibers are obtained by soaking a polymer solution (2 g of polyvinylidene fluoride is added into 8g of N, N-dimethylformamide) for 1min at 25 ℃ for 5 times and drying at 60 ℃ for 30min. And (3) carrying out pressing treatment on the parallel fiber axial direction of the core-shell fiber, and pressing for 20min at the temperature of 160 ℃ under the pressure of 10MPa to obtain the PVDF-BN high heat conduction composite material with the fiber-imitated monolithic structure.
Table 1 shows the performance comparisons of the PVDF-BN composite material with simulated fiber monolith structure, the BN fiber reinforced PVDF composite material and the BN particle reinforced PVDF composite material prepared by the method of the invention in example 1. Wherein the BN fiber or the particle reinforced composite material is obtained by random distribution 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 and is only 5.67MPa, the tensile strength of the BN fiber reinforced PVDF composite material which is randomly distributed is slightly higher, but is also only 5.82MPa, compared with the tensile strength of the PVDF-BN composite material which is of the imitated fiber monolith structure and has the same content, the tensile strength is the highest and 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 BN fiber reinforced PVDF composite material which is randomly distributed. The fiber-imitated monolithic PVDF-BN composite material has the advantages that the BN fibers which are arranged in parallel in the fiber-imitated monolithic PVDF-BN composite material inhibit the fracture of the composite material, so that the fracture toughness of the composite material can be improved, and the tensile strength of the composite material can be increased. In addition, the high-heat-conductivity BN fiber directional arrangement is also favorable for quick heat transfer, so that the heat conducting performance of the BN fiber is effectively improved, and the heat conductivity of the composite material is increased.
TABLE 1 comparison of properties of PVDF-BN composite material with fiber-like monolith structure, 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 of simulated fiber monolith structure prepared in the present invention. As can be seen from fig. 1, BN fibers are arranged in an oriented manner after the self-assembly process, PVDF is used for wrapping the BN fibers, the BN fibers and the PVDF are tightly combined, and the composite material with the fiber-like monolith structure is obtained after the BN fibers and the PVDF are pressed.
EXAMPLE 2 fiber-imitated monolithic Structure PS-BN composite material
15g of boric acid, 8g of melamine and 0.2g of polyvinylpyrrolidone are added into 76.8g of mixed solvent (the water volume ratio is 60 percent and the tertiary butanol is 40 percent), a precursor solution is obtained after heating and stirring for 4 hours in a water bath at 60 ℃, 20kV voltage is applied to the upper end and the lower end of the precursor solution, the precursor solution is placed on a low-temperature plate at-50 ℃ for 4 hours of freezing, and then the precursor fiber skeleton which is arranged in a self-assembly orientation is obtained through vacuum drying for 24 hours under the condition of 0.1Pa of vacuum degree. High-temperature calcination treatment is carried out in a nitrogen environment, the calcination temperature is 1500 ℃, the calcination time is 2 hours, and the oriented arranged inner core-shell fiber is obtained by soaking a polymer solution (4 g of polystyrene is added into 4g of mixed solvent of N, N-dimethylformamide and 2g of acetone) for 3 minutes at 50 ℃, soaking for 1 time and drying at 90 ℃ for 10 minutes. And (3) carrying out pressing treatment on the parallel fiber axial direction of the inner core shell fiber, and pressing for 5min at the pressure of 30MPa and the temperature of 200 ℃ to obtain the PS-BN high heat conduction composite material with the fiber-imitated monolithic structure.
Example 3 fiber-imitated monolith structured PAN-BN composite material
9g of boric acid, 3g of melamine and 0.1g of KH-550 are added into a mixed solvent (the water volume ratio is 80% and 20% of ethanol), a precursor solution is obtained after heating and stirring for 3 hours in a water bath at 80 ℃, 10kV voltage is applied to the upper end and the lower end of the precursor solution, the precursor solution is placed on a low-temperature plate at-40 ℃ for 3 hours, and then the precursor fiber skeleton which is arranged in a self-assembly orientation is obtained through vacuum drying for 36 hours under the vacuum degree of 5 Pa. High-temperature calcination treatment is carried out in a nitrogen environment, the calcination temperature is 1300 ℃, the calcination time is 3 hours, and the oriented arranged inner core-shell fiber is obtained by soaking a polymer solution (3 g of polyacrylonitrile is added into 5g of mixed solvent of N, N-dimethylformamide and 2g of chloroform) for 2 minutes at 30 ℃ for 3 times and drying at 80 ℃ for 20 minutes. And (3) carrying out pressing treatment on the parallel fiber axial direction of the core outer shell fiber, and pressing for 10min under the condition of the pressure of 20MPa and the temperature of 180 ℃ to obtain the PAN-BN high heat conduction composite material with the fiber-imitated monolithic structure.
Example 4 fiber-like monolith-structured PMMA-BN composite material
7g of boric acid, 2g of melamine and 0.15g of sodium dodecyl sulfate are added into a mixed solvent (the water volume ratio is 70 percent and the isopropyl alcohol is 30 percent), a precursor solution is obtained after heating and stirring for 2 hours in a water bath at 90 ℃, 15kV voltage is applied to the upper end and the lower end of the precursor solution, the precursor solution is placed on a low-temperature plate at the temperature of minus 30 ℃ for freezing for 4 hours, and then a precursor fiber skeleton arranged in a self-assembly orientation is obtained through vacuum drying for 40 hours under the condition of 10Pa of vacuum degree. High-temperature calcination treatment is carried out in a nitrogen environment, the calcination temperature is 1100 ℃, the calcination time is 3.5h, and the oriented arranged inner core-shell fiber is obtained by soaking a polymer solution (2.5 g of polymethyl methacrylate is added into a mixed solvent of 6g of acetone and 1.5g of tetrahydrofuran) for 2.5min at 40 ℃ for 2 times and drying at 70 ℃ for 25 min. And (3) carrying out pressing treatment on the parallel fiber axial direction of the core-shell fiber, and pressing for 15min at the temperature of 160 ℃ under the pressure of 25MPa to obtain the PAN-BN high-heat-conductivity composite material with the fiber-imitated monolithic structure.
Claims (4)
1. The preparation method of the self-assembled fiber-imitated monolithic structure high-heat-conductivity composite material is characterized by comprising the following steps of:
step 1, adding boric acid, melamine and additives 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 skeleton which is arranged in a self-assembly orientation manner through vacuum drying;
step 3, calcining the precursor fiber skeleton obtained in the step 2 at a high temperature in a nitrogen environment, and performing drying treatment after impregnation by a polymer solution to obtain the oriented arranged inner core-shell fibers;
step 4, pressing the core-shell fiber obtained in the step 3 in parallel fiber axial direction to obtain a self-assembled fiber-imitated monolithic structure high-heat-conductivity composite material;
the precursor solution in the step 1 comprises the following substances in percentage by mass: boric acid 3-15%, melamine 1-8%, additive 0.05-0.2%, solvent 76.8-95.95%, the total sum of the above substances is 100%;
the additive in the step 1 is any one of sodium dodecyl benzene sulfonate, KH-550, sodium dodecyl sulfate, polyvinylpyrrolidone and polyvinyl alcohol, and the solvent is water or a mixed solvent composed of water and one or more of ethanol, tertiary butanol and isopropanol, wherein the volume ratio of water is 60% -100%;
the water bath temperature in the step 1 is 60-95 ℃ and the water bath time is 0.5-4 h;
in the step 2, the upper end and the lower end of the precursor solution are applied with voltage of 5 kV-20 kV, the freezing temperature of a low-temperature plate is minus 50 ℃ to minus 20 ℃, the freezing time is 4 h-8 h, and the vacuum drying process parameters are as follows: vacuum degree is 0.1 Pa-20 Pa, and drying time is 24 h-48 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.
2. The method for preparing the self-assembled fiber-imitated monolithic structured high-thermal-conductivity composite material according to claim 1, wherein the high-temperature calcination temperature in the step 3 is 1000-1500 ℃ and the calcination time is 2-6 h.
3. The method for preparing the self-assembled fiber-imitated monolithic structured high-thermal-conductivity composite material according to claim 1, wherein the dipping temperature in the step 3 is 25-50 ℃, the dipping time is 1-3 min, and the dipping times are 1-5 times; the drying temperature is 60-90 ℃ and the drying time is 10-30 min.
4. The method for preparing the self-assembled fiber-imitated monolithic structured high-thermal-conductivity composite material according to claim 1, wherein the pressure of the pressing treatment in the step 4 is 10-30 MPa, the temperature is 160-200 ℃, and the pressing time is 5-20 min.
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