CN114250064A - Flexible high-thermal-conductivity polymer-based composite material and preparation method thereof - Google Patents
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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.
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