CN114250064A - Flexible high-thermal-conductivity polymer-based composite material and preparation method thereof - Google Patents
Flexible high-thermal-conductivity polymer-based composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114250064A CN114250064A CN202210050447.4A CN202210050447A CN114250064A CN 114250064 A CN114250064 A CN 114250064A CN 202210050447 A CN202210050447 A CN 202210050447A CN 114250064 A CN114250064 A CN 114250064A
- Authority
- CN
- China
- Prior art keywords
- composite material
- boron nitride
- honeycomb
- slurry
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 title claims abstract description 12
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052582 BN Inorganic materials 0.000 claims abstract description 59
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 38
- 239000010432 diamond Substances 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000011049 filling Methods 0.000 claims abstract description 8
- 238000001764 infiltration Methods 0.000 claims abstract description 4
- 230000008595 infiltration Effects 0.000 claims abstract description 4
- 238000009825 accumulation Methods 0.000 claims abstract 2
- 230000000149 penetrating effect Effects 0.000 claims abstract 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 230000008014 freezing Effects 0.000 claims description 16
- 238000007710 freezing Methods 0.000 claims description 16
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000000945 filler Substances 0.000 description 23
- 239000003822 epoxy resin Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002591 computed tomography Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Ceramic Products (AREA)
Abstract
The invention discloses a flexible high-thermal-conductivity polymer-based composite material and a preparation method thereof, wherein inside the composite material, flaky boron nitride is orderly arranged and assembled with a honeycomb-shaped primary thermal-conductive network, diamond particles are directionally filled in honeycomb holes to realize local high-density accumulation, and an efficient thermal-conductive composite network penetrating through the material is formed, wherein the honeycomb structure is complete, the hole diameter is 1-150 mu m, the wall thickness is 1-30 mu m, the direction of a boron nitride layer is consistent with the axial direction of the holes, and the layers are in a continuous lap joint state. The preparation method of the composite material is characterized in that the one-way frozen boron nitride organic slurry is utilized to realize that two-dimensional flaky boron nitride forms a heat-conducting framework with a honeycomb structure; putting the heat-conducting framework into a muffle furnace for high-temperature heat treatment; and filling the diamond particles and the polymer slurry in the holes of the honeycomb by using a vacuum infiltration method, and curing to obtain the composite material.
Description
Technical Field
The invention relates to the technical field of thermal interface material preparation, in particular to a flexible high-thermal-conductivity polymer-based composite material and a preparation method thereof.
Background
The high heat flux density of the core part of the electronic equipment is a main reason for restricting the further development of the electronic equipment, how to timely radiate heat and prolong the service life becomes a problem which needs to be solved urgently by an electronic device, and the thermal interface material fills the air gap between a radiator and a chip and aims to adapt to the irregularity of a solid-solid contact surface and eliminate the gap, thereby ensuring the effective heat transfer of a thermal interface. The flexible high-thermal-conductivity polymer-based composite material filled with high-thermal-conductivity metal or ceramic particles becomes the key research point of high-end thermal interface materials, the obtained composite material has the advantages of light weight, easiness in processing, good gap filling property and the like, but at present, the improvement of the thermal conductivity coefficient of the material mainly depends on the increase of the volume fraction of the high-thermal-conductivity filler. However, the higher the volume fraction of the thermally conductive filler, the greater the composite hardness, and the more effective the thermal interface material at the gap is filled, while the manufacturing cost is also increased. Therefore, desirable filled thermal interface materials also desirably have as low a volume fraction of filler as possible while achieving high thermal conductivity.
Disclosure of Invention
The invention provides a flexible high-thermal-conductivity polymer-based composite material and a preparation method thereof, and aims to solve the problems that the heat conductivity coefficient of the existing thermal interface material is mainly improved by increasing the volume fraction of a high-thermal-conductivity filler, but the higher the volume fraction of the heat-conductivity filler is, the higher the hardness of the composite material is, the higher the effective and high filling effect of the thermal interface material at a gap is, and the preparation cost is increased.
The invention is achieved by the following specific technical means: the preparation of the composite material comprises the following steps:
preparation of S1 boron nitride slurry: citric acid is used as a dispersing agent, polyvinylpyrrolidone is used as an adhesive, and the mass ratio of the citric acid to the polyvinylpyrrolidone to tertiary butanol is 1: 2: 116. firstly, ultrasonically dispersing citric acid in tert-butyl alcohol, and then adding polyvinylpyrrolidone for ultrasonic treatment for 10 min. Adding boron nitride according to the volume fraction of 3-7% and carrying out ultrasonic treatment for 6 h. Obtaining uniformly dispersed boron nitride slurry;
preparation of S2 boron nitride framework: firstly, pouring boron nitride slurry subjected to ultrasonic treatment into a polytetrafluoroethylene mold, placing the mold into a vacuum drying oven for degassing for 20min, then placing the mold on a freezing platform, wherein the temperature of the freezing platform is-40-10 ℃, the ambient temperature is 25 ℃, the freezing time is 20-30 min, then placing a sample into a freezing drying oven for 12h, finally placing the sample into a muffle furnace, heating and sintering at the temperature of 800-1100 ℃ at the speed of 5-10 ℃/min, and keeping the temperature for 20-60min to obtain a boron nitride honeycomb framework;
preparation of S3 boron nitride/diamond composite material: uniformly stirring the components A and B of the epoxy resin in proportion, adding diamond with the mass fraction of 0-20%, continuously and uniformly stirring to prepare slurry, simultaneously vacuumizing the slurry of the diamond and a boron nitride framework for 5min, then adding the boron nitride framework into the diamond slurry in a vacuum environment, performing vacuum infiltration, wherein the vacuum degree is not lower than 100Pa, the time is 10-60min, and finally curing at 60 ℃ for not less than 1h to obtain the boron nitride/diamond composite material.
The composite material base material is not limited to epoxy resin, silica gel, gel and other materials with the same processability, and the heat conducting filler is not limited to boron nitride, silicon carbide, diamond, alumina and other zero, one or two-dimensional materials. The method has important guiding significance for the application of the ice template method in the preparation of the thermal interface material in the future.
The principle of the invention is as follows:
the three-dimensional boron nitride framework is prepared by a one-way ice template method, and then the boron nitride honeycomb framework after heat treatment is taken as a template to realize local high-density filling of diamond in the boron nitride honeycomb framework structure, so that the thermal conductivity of the composite material is effectively improved. The method realizes the directional distribution and bridging of the mixed filler, fully exerts the synergistic effect between the fillers, and realizes the great improvement of the heat conductivity of the composite material by constructing an efficient heat conduction path only by depending on a small amount of the fillers. The ice template method constructs a highly ordered and directionally arranged 3D filler network, and the secondary template method is a new method for preparing a composite material by using a polymer-based mixed heat-conducting filler based on further research on the original ice template method. The method is simple to operate, saves cost, can design the shape of the product and is suitable for batch production. The hexagonal Boron Nitride Nanosheet (BNNSs) is a wide-band-gap insulating material, the theoretical thermal conductivity of few layers of the nanosheets is as high as 2000W/(m.K), the thermal expansion coefficient is low, the mechanical property is excellent, and the hexagonal boron nitride nanosheet is an ideal filler for insulating high-thermal-conductivity nanocomposite materials. The diamond material has a large phonon mean free path and high thermal conductivity, and the diamond spheroidal shape is favorable for becoming an excellent heat-conducting filler.
Compared with the prior art, the invention has the following innovation points and beneficial effects:
1. the heat-conducting fillers in the composite material are in contact with each other, and the wall of the boron nitride honeycomb hole realizes bridging of non-adjacent diamond particles, thereby being beneficial to improving the gain effect of the composite heat-conducting network.
2. In the composite material, the boron nitride framework is subjected to heat treatment, so that the bonding capability among the stacked flaky boron nitride is enhanced, the framework can bear pressure integrally, and the composite material has certain mechanical strength;
3. the construction of the three-dimensional framework of the composite material does not depend on the large-proportion filling of the heat-conducting filler to enhance the overall heat-conducting performance, and turns to the construction of more effective heat-conducting passages and heat-conducting networks in the composite material, and the heat-conducting performance of the composite material can be greatly improved only by a small amount of filler;
4. the invention realizes the bridging effect of the heat conduction path by using the fillers with different sizes and shapes of boron nitride and diamond, and the diamond forms a close packing structure in the boron nitride honeycomb channel, so that heat is transferred at high speed along the direction of a 'viaduct' with low thermal resistance, and the heat conduction efficiency is high;
5. according to the method, the boron nitride framework is used as the template, and the diamond is soaked in the framework gap in vacuum, so that not only are heat conduction paths between the same kind of heat conduction fillers constructed, but also heat conduction paths between the boron nitride and the diamond are constructed, and the advantages of the mixed fillers are exerted to the maximum extent through the efficient heat conduction paths;
6. the composite material prepared by the invention has low density which is not higher than 1.8g/cm3The material has wide application prospect in the fields of aerospace, national defense war industry, portable communication and the like with higher requirements on the lightweight of the heat management material.
Drawings
FIG. 1 is a process flow diagram of the present invention for preparing a flexible high thermal conductivity polymer matrix composite;
FIG. 2 is an SEM micrograph of "honeycomb" cells with different N3 freezing temperatures, a) freezing temperature of-20 deg.C, b) freezing temperature of-40 deg.C;
FIG. 3 is an XRD representation of pure epoxy, a composite material prepared before and after heat treatment of N3A, and W3;
SEM electron micrographs of boron nitride "honeycomb" skeleton and composite in the example of fig. 4, (a) cross-sectional view of N3A boron nitride skeleton; (b) a cross-sectional view of the W0 composite; (c) a longitudinal section of the W3 composite; (d) a partial enlarged view of fig. (c);
FIG. 5 is a CT image of the W3 composite material in example.
Detailed Description
The embodiments of the present invention will be described in further detail with reference to the drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
(1) Citric acid is used as a dispersing agent, polyvinylpyrrolidone is used as an adhesive, and the mass ratio of the citric acid to the polyvinylpyrrolidone to tertiary butanol is 1: 2: 116 preparing organic slurry, adding boron nitride according to the mixture ratio of 3 percent, 5 percent and 7 percent in volume fraction, and carrying out ultrasonic treatment for 6 hours to obtain uniformly dispersed boron nitride slurry, and marking the uniformly dispersed boron nitride slurry as samples N1, N2 and N3
(2) Pouring the boron nitride slurry subjected to ultrasonic treatment into a polytetrafluoroethylene mold, placing the mold into a vacuum drying oven to degas for 20min, then placing the mold on a freezing platform, wherein the freezing temperature is-20 ℃ (A) and-40 ℃ (B) respectively, the time is 30min, then placing a sample into a freezing drying oven for 12h, and finally placing the sample into a muffle furnace to heat up to 1000 ℃ and keep the temperature for 30min, thus obtaining the boron nitride honeycomb framework. Designated as samples N1A, N1B, N2A, N2B, N3A, and N3B, respectively.
(3) Uniformly stirring the components A and B in proportion, adding diamond in the components A and B in volume fractions of 0, 2%, 7%, 12% and 20%, simultaneously vacuumizing the uniformly stirred slurry and the boron nitride framework for 5min, then adding the boron nitride framework into the slurry in a vacuum environment, performing vacuum infiltration for 1h, and then curing for 1h at 60 ℃ to obtain the directional boron nitride composite material. And testing the heat-conducting property of the boron nitride composite material by using a laser heat-conducting instrument. Samples W0, W1, W2, W3, and W4 were taken when the organic slurry was 7%, the freezing temperature was-20 ℃, and the volume fraction of diamond was different, respectively.
Table 1 composite materials were prepared by varying the volume fraction of the organic slurry under the precondition that the diamond volume fraction was 0 and the freezing temperature was-20 ℃, and the measured thermal conductivity was as follows:
TABLE 1
| Sample numbering | N1A | N2A | N3A |
| Volume fraction of organic slurry | 3％ | 5％ | 7％ |
| Coefficient of thermal conductivity (W/m. K) | 0.473 | 0.703 | 0.833 |
From the above table, when the volume fraction of boron nitride is 7%, the thermal conductivity coefficient is the highest, and is 0.833W/m · K, and experiments prove that when the volume fraction of boron nitride is higher than 7%, the slurry concentration is high, and the ordered and regular boron nitride framework is not easy to be prepared by the directional freezing method. Therefore, the volume fraction of boron nitride with the highest thermal conductivity is higher than 7% for the subsequent experiment.
Table 2 composite materials prepared by varying the volume fraction of diamond under the precondition that the organic slurry is 7% and the freezing temperature is-20 ℃ in volume fraction, the measured thermal conductivity coefficient is as follows:
TABLE 2
| Sample numbering | W1 | W2 | W3 | W4 |
| Volume fraction of diamond | 2％ | 7％ | 12％ | 20％ |
| Coefficient of thermal conductivity (W/m. K) | 1.169 | 1.944 | 2.720 | 4.598 |
Table 3 on the premise of 7% of the organic slurry, correspondingly weighing 2%, 7%, 12%, 20% by volume of diamond, uniformly stirring the epoxy resin a and the epoxy resin B in a ratio, adding boron nitride and diamond into the epoxy resin, continuously stirring uniformly, placing into a vacuum drying oven, vacuumizing for 5min, and then curing for 1h at 60 ℃ to obtain a composite material with randomly distributed fillers, wherein samples are respectively labeled as S1, S2, S3 and S4, and the thermal conductivity coefficients are measured as follows:
TABLE 3
| Sample numbering | S1 | S2 | S3 | S4 |
| Volume fraction of diamond | 2％ | 7％ | 12％ | 20％ |
| Coefficient of thermal conductivity (W/m. K) | 0.424 | 0.437 | 0.471 | 0.518 |
The pore size of the "honeycomb" framework was observed by SEM using samples N3A and N3B, as shown in FIG. 2, the pore size was adjustable from 1 μm to 150 μm.
XRD characterization is carried out on the pure epoxy resin, the composite material prepared before and after the heat treatment of the sample N3A and the W3 composite material, and the test parameters are as follows: the scanning speed of the full spectrum (0-90 ℃) is 10 DEG/min, the result is shown in figure 3, the obtained boron nitride honeycomb framework after heat treatment contains a small amount of boron oxide, the sintering between the boron nitride frameworks is realized, and the W3 composite material is characterized to be composed of boron nitride, diamond and a polymer matrix.
Performing SEM representation on the boron nitride framework corresponding to N3A in the example, wherein the result is shown in FIG. 4(a), the boron nitride honeycomb holes observed on the cross section are regularly arranged, the pore size is uniform, and the inner wall of the hole is smooth and flat; the filling condition of the hole of the boron nitride honeycomb framework corresponding to W0 is observed as shown in a picture (b), and the polymer matrix is well filled in the hole of the boron nitride; taking W3 as a research object to carry out SEM characterization, and observing the longitudinal section view and the diamond filling condition as shown in the figures (c) and (d), the results prove that the boron nitride skeleton structure is complete after the diamond is filled, the diamond forms a close packing structure in the boron nitride skeleton, the contact between the same type of filler and different types of fillers is realized, and the efficient heat conduction path between the fillers is favorably constructed.
The characterization of the CT scan using W3 as the study object is shown in fig. 3, where the diamond nanoparticles in the gray part are oriented along the heat propagation direction, which proves the ordered, local high-density packing of diamond in the boron nitride "honeycomb".
Compared with the thermal conductivity data of S4, N3A and W4 composite materials, after simple blending, the addition of the diamond improves the thermal conductivity of the composite material to a certain degree, and the thermal conductivity of the thermal conductive filler is far higher than that of epoxy resin; but more noteworthy, under the condition of not changing the material and the addition amount, the boron nitride secondary template guides the diamond particles to realize highly ordered directional arrangement, so that the heat conductivity coefficient of the composite material is greatly improved to 4.598W/m.K, and compared with a filler network which is randomly distributed, the heat conductivity coefficient is improved by 7.87 times to the maximum, which shows that the composite heat conductivity network formed by the diamond and the boron nitride effectively increases the efficient heat conduction path in the composite material, thereby improving the heat conductivity of the composite material.
The embodiments of the present invention have been presented for purposes of illustration and description, and are not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (10)
1. A flexible high thermal conductivity polymer-based composite material, characterized in that the microstructure of the composite material is: inside the composite material, the flaky boron nitride is orderly arranged and assembled with a honeycomb-shaped primary heat-conducting network, and the diamond particles are directionally filled in the honeycomb holes to realize local high-density accumulation, so that the efficient heat-conducting composite network penetrating through the material is formed.
2. The composite material of claim 1, wherein the honeycomb structure is complete, the pore diameter is 1-150 μm, the wall thickness is 1-30 μm, the direction of the boron nitride sheet layer is consistent with the axial direction of the hole, and the sheet layers are in a continuous overlapping state.
3. The composite material of claim 1, wherein the diamond particles are packed in high density in partial boron nitride honeycomb holes to form high-efficiency heat conducting channels, and the diamond particle size is 500nm-10 μm.
4. A method for preparing a composite material according to claims 1-3, characterized in that it comprises the following steps:
s1, preparation of boron nitride slurry: the one-way frozen boron nitride organic slurry is utilized to realize that two-dimensional flaky boron nitride forms a heat conducting framework with a honeycomb structure;
s2, preparation of boron nitride framework: putting the heat-conducting framework with the boron nitride honeycomb structure into a muffle furnace for high-temperature heat treatment;
s3, preparation of the composite material: and filling the diamond particles and the polymer slurry in the holes of the honeycomb by using a vacuum infiltration method, and curing to obtain the composite material.
5. The method for preparing the composite material according to claim 4, wherein the slurry in step S1 uses tert-butyl alcohol as a solvent, citric acid as a dispersing agent, and polyvinylpyrrolidone as a binder.
6. The method for preparing a composite material according to claim 4, wherein the volume fraction of boron nitride in the slurry in step S1 is 3-20%.
7. The method for preparing a composite material according to claim 4, wherein the volume fraction of diamond in the slurry in the step S1 is 0-20%.
8. The method for preparing the composite material according to claim 4, wherein the freezing platform temperature in the step S1 is-40 ℃ to 10 ℃, the ambient temperature is 25 ℃, and the freezing time is 20min to 30 min.
9. The method for preparing the composite material according to claim 4, wherein the temperature rise rate of the high-temperature heat treatment in the step S2 is 5-10 ℃/min, the sintering temperature is 800-1100 ℃, and the holding time is 20-60 min.
10. The preparation method of the composite material according to claim 4, wherein the vacuum impregnation in the step S3 comprises the steps of simultaneously vacuumizing the framework and the slurry and impregnating in a vacuum environment, wherein the vacuum degree is more than or equal to 100Pa, the time duration is 10-60min, and then curing at 60 ℃ for more than or equal to 1 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210050447.4A CN114250064A (en) | 2022-01-17 | 2022-01-17 | Flexible high-thermal-conductivity polymer-based composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210050447.4A CN114250064A (en) | 2022-01-17 | 2022-01-17 | Flexible high-thermal-conductivity polymer-based composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114250064A true CN114250064A (en) | 2022-03-29 |
Family
ID=80796576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210050447.4A Pending CN114250064A (en) | 2022-01-17 | 2022-01-17 | Flexible high-thermal-conductivity polymer-based composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114250064A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028999A (en) * | 2022-04-28 | 2022-09-09 | 苏州大学 | Flexible heat storage and conduction sheet and preparation method thereof |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105062007A (en) * | 2015-08-31 | 2015-11-18 | 中国科学院深圳先进技术研究院 | High-thermal-conductivity polymer composite material and preparation method and application thereof |
| CN105733191A (en) * | 2016-03-21 | 2016-07-06 | 中南大学 | Different-dimensionality high-heat-conductivity material enhanced and polymer based composite and preparation method thereof |
| CN105755307A (en) * | 2016-03-21 | 2016-07-13 | 中南大学 | Reinforced composite adopting honeycomb structure and preparation method |
| CN106433564A (en) * | 2016-08-08 | 2017-02-22 | 上海交通大学 | Graphene aerogel compounded and enhanced paraffin type phase change heat storage material and preparation method thereof |
| CN106700427A (en) * | 2016-12-30 | 2017-05-24 | 深圳先进技术研究院 | Boron nitride/epoxy resin composite material and preparation method thereof |
| CN109289896A (en) * | 2018-11-01 | 2019-02-01 | 大连理工大学 | A kind of monoblock type nitridation B catalyst and application |
| CN109666263A (en) * | 2019-01-04 | 2019-04-23 | 浙江大学 | The preparation method and product of a kind of boron nitride/epoxy resin composite material and application |
| CN109762204A (en) * | 2018-12-14 | 2019-05-17 | 中国科学院深圳先进技术研究院 | Three-dimensional structure boron nitride-graphene oxide hybrid material, preparation method and as filler heat-conductive composite material purposes |
| 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 |
| CN111154126A (en) * | 2020-01-16 | 2020-05-15 | 哈尔滨工业大学 | Preparation method of nano-diamond modified boron nitride high-flexibility high-thermal-conductivity composite film |
| CN111344339A (en) * | 2017-11-16 | 2020-06-26 | 3M创新有限公司 | Polymer matrix composite comprising thermally conductive particles and method of making the same |
| CN112175238A (en) * | 2020-10-22 | 2021-01-05 | 安徽大学 | Preparation method of boron nitride nanosheet-carbon nanotube heat-conducting filler and heat-conducting composite material |
| CN112745636A (en) * | 2020-12-29 | 2021-05-04 | 哈尔滨工业大学（深圳） | Polymer-based metal aerogel composite thermal interface material and preparation method thereof |
| CN113372882A (en) * | 2021-06-07 | 2021-09-10 | 山东国烯新材料创新中心有限公司 | Boron nitride-based unidirectional insulation composite phase-change material and preparation method thereof |
| CN113912914A (en) * | 2021-12-07 | 2022-01-11 | 北京石墨烯技术研究院有限公司 | Polymer-based composite heat conduction material and preparation method and application thereof |
-
2022
- 2022-01-17 CN CN202210050447.4A patent/CN114250064A/en active Pending
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105062007A (en) * | 2015-08-31 | 2015-11-18 | 中国科学院深圳先进技术研究院 | High-thermal-conductivity polymer composite material and preparation method and application thereof |
| CN105733191A (en) * | 2016-03-21 | 2016-07-06 | 中南大学 | Different-dimensionality high-heat-conductivity material enhanced and polymer based composite and preparation method thereof |
| CN105755307A (en) * | 2016-03-21 | 2016-07-13 | 中南大学 | Reinforced composite adopting honeycomb structure and preparation method |
| CN106433564A (en) * | 2016-08-08 | 2017-02-22 | 上海交通大学 | Graphene aerogel compounded and enhanced paraffin type phase change heat storage material and preparation method thereof |
| CN106700427A (en) * | 2016-12-30 | 2017-05-24 | 深圳先进技术研究院 | Boron nitride/epoxy resin composite material and preparation method thereof |
| CN111344339A (en) * | 2017-11-16 | 2020-06-26 | 3M创新有限公司 | Polymer matrix composite comprising thermally conductive particles and method of making the same |
| CN109289896A (en) * | 2018-11-01 | 2019-02-01 | 大连理工大学 | A kind of monoblock type nitridation B catalyst and application |
| CN109762204A (en) * | 2018-12-14 | 2019-05-17 | 中国科学院深圳先进技术研究院 | Three-dimensional structure boron nitride-graphene oxide hybrid material, preparation method and as filler heat-conductive composite material purposes |
| CN109666263A (en) * | 2019-01-04 | 2019-04-23 | 浙江大学 | The preparation method and product of a kind of boron nitride/epoxy resin composite material 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 |
| CN111154126A (en) * | 2020-01-16 | 2020-05-15 | 哈尔滨工业大学 | Preparation method of nano-diamond modified boron nitride high-flexibility high-thermal-conductivity composite film |
| CN112175238A (en) * | 2020-10-22 | 2021-01-05 | 安徽大学 | Preparation method of boron nitride nanosheet-carbon nanotube heat-conducting filler and heat-conducting composite material |
| CN112745636A (en) * | 2020-12-29 | 2021-05-04 | 哈尔滨工业大学（深圳） | Polymer-based metal aerogel composite thermal interface material and preparation method thereof |
| CN113372882A (en) * | 2021-06-07 | 2021-09-10 | 山东国烯新材料创新中心有限公司 | Boron nitride-based unidirectional insulation composite phase-change material and preparation method thereof |
| CN113912914A (en) * | 2021-12-07 | 2022-01-11 | 北京石墨烯技术研究院有限公司 | Polymer-based composite heat conduction material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| XIAOLIANG ZENG: "Ice-Templated Assembly Strategy to Construct 3D Boron Nitride Nanosheet Networks in Polymer Composites for Thermal Conductivity Improvement", 《SMALL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028999A (en) * | 2022-04-28 | 2022-09-09 | 苏州大学 | Flexible heat storage and conduction sheet and preparation method thereof |
| CN115028999B (en) * | 2022-04-28 | 2024-05-10 | 苏州大学 | Flexible heat storage and conduction sheet and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | A roadmap review of thermally conductive polymer composites: critical factors, progress, and prospects | |
| Wu et al. | Epoxy composites with high cross-plane thermal conductivity by constructing all-carbon multidimensional carbon fiber/graphite networks | |
| Li et al. | Bubble-templated rGO-graphene nanoplatelet foams encapsulated in silicon rubber for electromagnetic interference shielding and high thermal conductivity | |
| Xiao et al. | Preparation of highly thermally conductive epoxy resin composites via hollow boron nitride microbeads with segregated structure | |
| CN107434905B (en) | heat-conducting polymer composite material and preparation method and application thereof | |
| KR101007621B1 (en) | Metal-based composite material containing both micron-size carbon fiber and nano-size carbon fiber | |
| CN104943223B (en) | There is graphite flake and the preparation method of high thermal conductivity coefficient along plane and thickness direction simultaneously | |
| CN113150544B (en) | Oriented boron nitride @ polydopamine @ silver hybrid nanosheet flexible thermal interface material and preparation method thereof | |
| Yoon et al. | Review on three-dimensional ceramic filler networking composites for thermal conductive applications | |
| KR101886435B1 (en) | High radiant heat composites containing hybrid filler containing expended graphite filled with expandable polymeric beads and a fabrication process thereof | |
| Jiao et al. | Pie-rolling-inspired construction of vertical carbon fiber high thermal conductivity hybrid networks | |
| CN112251026A (en) | Heat-conducting gasket with fillers orderly arranged in inclined manner and preparation method thereof | |
| CN114250064A (en) | Flexible high-thermal-conductivity polymer-based composite material and preparation method thereof | |
| Chen et al. | Preparation of AlN ceramic bonded carbon by gelcasting and spark plasma sintering | |
| CN112538336B (en) | Liquid metal solid-liquid coupling type multilayer thermal interface material and preparation method thereof | |
| Li et al. | Liquid bridge: liquid metal bridging spherical BN largely enhances the thermal conductivity and mechanical properties of thermal interface materials | |
| CN109987954A (en) | A kind of tungsten carbide enhancing graphite-base composite material and preparation method | |
| Tian et al. | Designing insulative SiC coating layer on the artificial graphite particle to achieve synergy of wave absorption and thermal conduction | |
| CN111554466A (en) | Heat-conducting wave-absorbing composite magnetic sheet with periodic structure and preparation method thereof | |
| CN103966533B (en) | A kind of diamond heat-conducting composite and preparation method thereof | |
| Wu et al. | Novel in-situ constructing approach for vertically aligned AlN skeleton and its thermal conductivity enhancement effect on epoxy | |
| Wu et al. | Construction of three-dimensional interconnected boron nitride/sliver networks within epoxy composites for enhanced thermal conductivity | |
| CN113308160A (en) | Efficient heat dissipation coating for surface of aluminum alloy radiator and preparation method thereof | |
| Guo et al. | Magnetically assisted construction of Al2O3 platelets dual network and its excellent thermal conductivity in epoxy resin composites | |
| CN110117484B (en) | Preparation method of heat-conducting silicone gel composite sheet with directionality |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220329 |