CN110564159A - Light polymer nano composite material with isolation structure and preparation method thereof - Google Patents

Light polymer nano composite material with isolation structure and preparation method thereof Download PDF

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CN110564159A
CN110564159A CN201910904140.4A CN201910904140A CN110564159A CN 110564159 A CN110564159 A CN 110564159A CN 201910904140 A CN201910904140 A CN 201910904140A CN 110564159 A CN110564159 A CN 110564159A
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李琳
赵帅
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Qingdao University of Science and Technology
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Abstract

The invention discloses a light polymer nano composite material with an isolation structure and a preparation method thereof, belonging to the technical field of high polymer materials. The composite material comprises a polymer matrix, hollow microspheres and nano-fillers. Wherein the polymer matrix is a "sea phase", i.e. a continuous phase; the hollow microspheres as the island phase can play a role in volume exclusion in the matrix while reducing the density of the composite material, so that the nano filler can form a compact three-dimensional network in the matrix at a low content, and finally the preparation of the light polymer nano composite material with an isolated structure is realized. The preparation method of the composite material comprises the following steps: firstly, coating the nano filler on the surface of the hollow microsphere, then uniformly dispersing the coated hollow microsphere in a polymer matrix, and finally processing and molding. The flame-retardant and heat-conducting composite material has excellent functions of flame retardance, electric conduction, heat conduction or electromagnetic shielding and the like, and can be applied to the high-end technical fields of aerospace, transportation, electronic communication and the like.

Description

Light polymer nano composite material with isolation structure and preparation method thereof
Technical Field
The invention relates to the field of preparation of nano composite materials, in particular to a light polymer nano composite material with an isolation structure and a preparation method thereof.
Background
The polymer composite material with low filler content and high performance has wide application requirements in high-end technical fields of aerospace, transportation, electronic communication and the like. The construction idea of the polymer composite material with the isolation structure provides a potential solution for the preparation of the polymer composite material with low cost and high performance. In the polymer composite material with an isolation structure, the polymer particles exert the effect of volume exclusion so that the filler is distributed around the polymer particles in a concentrated manner instead of being randomly distributed in the whole polymer matrix, thereby effectively improving the utilization efficiency of the filler, reducing the percolation threshold of the composite material and realizing high functionality of the composite material under low filler content (prog.Polym.Sci.,2014,39, 1908-1933; ZL 201510256234.7; ZL 201510489940.6).
the traditional construction methods of polymer composite materials with an isolation structure include a direct compression molding method, a backfill method and an incompatible polymer blending method. Due to the limitations of these manufacturing methods, the spread of the application of "barrier structure" polymer composites is greatly limited. For example, direct compression molding processes prepare the polymer/filler core-shell particles and then compression mold them directly (Carbon,2017,121, 267-273). The key to the success of this process is that the polymer particles can maintain a high modulus or viscosity at the forming temperature and pressure to avoid matrix flow disruption of the filler network. Thus, this method not only has great matrix selectivity and molding limitations, but also results in poor mechanical properties of the final composite due to poor continuity of the matrix (prog. polym. sci.,2014,39, 1908-1933). The backfilling method is that a three-dimensional porous filler framework is constructed firstly, and then a polymer matrix is backfilled for molding. The construction of the low-shrinkage and high-strength three-dimensional porous filler framework is the key to the success of the method. Although the "isolated structure" polymer nanocomposite prepared by the method has the most complete and uniform three-dimensional filler network, the construction of the three-dimensional porous filler skeleton not only requires complex and inefficient preparation processes such as a freeze-drying hydrogel/dispersion method, a chemical vapor deposition method or a template method, but also the problems of high shrinkage and low strength caused by the porosity of the skeleton are difficult to avoid (nat. Commun.,2012,3,1241). Incompatible polymer blending is a process of selecting appropriate polymer combinations and proportions to selectively distribute the filler at the one-phase/two-phase interface of the incompatible blend by precisely controlling mixing process parameters, filler surface properties, etc. (ACS appl. Although this method is applicable to conventional polymer processing techniques (compounding, extrusion, injection, etc.), the success of this method is also limited due to the complex effects of many kinetic and thermodynamic factors on the choice of filler distribution.
Therefore, the development of a novel preparation method of the polymer composite material with the isolation structure, which is simple and can be suitable for most polymer matrixes and traditional polymer processing technologies, has important practical significance for constructing the polymer nanocomposite material with low filler content and high performance. The inventor subject group prepares a silicone rubber nano composite material (with the publication number of CN110003657A) with an isolation structure in the early stage, silicone rubber micro domains and nano fillers distributed around the silicone rubber micro domains, the silicone rubber micro domains play a volume repulsion role to isolate the nano fillers into a three-dimensional network structure, and the surface of the nano fillers is provided with groups capable of interacting with the surface of the silicone rubber micro domains. Although the composite material has good performance, the preparation yield of the silicone rubber microspheres is low, the process is complex, and the composite material is not suitable for industrial popularization.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a lightweight polymer nanocomposite with an insulation structure, which is capable of achieving high functionality at a low filler content, and a method for preparing the same.
The basic principle of the invention is that the hollow microspheres loaded with nano-fillers on the surface are added into a polymer matrix, the isolation structure characteristic is endowed to the composite material through the volume exclusion effect of the hollow microspheres, and the light characteristic is endowed to the composite material through the low density of the hollow microspheres. In addition, the density of the hollow microspheres can be improved through a nano filler loading technology, so that the floating characteristic of the hollow microspheres is reduced, and the operability of the hollow microspheres in the adding process is improved.
The light polymer nano composite material with the isolation structure comprises a polymer matrix, hollow microspheres and nano fillers, wherein groups loaded on the surfaces of the nano fillers are uniformly distributed on the surfaces of the hollow microspheres through interaction with the groups loaded on the surfaces of the hollow microspheres to form hollow microsphere @ nano filler core-shell particles, and the hollow microsphere @ nano filler core-shell particles are uniformly distributed in the polymer matrix. Wherein the polymer matrix is a "sea phase", i.e. a continuous phase; the hollow microspheres as an island phase can play a role in volume exclusion in the matrix while reducing the density of the composite material, and promote the nano filler to form a compact three-dimensional network in the matrix at a lower content. The size of the hollow microsphere is 0.1-100 μm, and the mass fraction is 1-30 wt%; the mass fraction of the nano filler is 0.1 wt% -10 wt%.
The preparation method of the light polymer nano composite material with the isolation structure, provided by the invention, comprises the following steps:
1) Surface modification of the nano filler: the surface of the nano filler is modified by a physical or chemical method, groups which can strongly interact with the groups on the surface of the hollow microsphere are introduced into the surface of the nano filler, and then the nano filler is dispersed in water to obtain the nano filler water dispersion.
2) Surface modification of hollow microspheres: the surface of the hollow microsphere is modified by a physical or chemical method, groups which can strongly interact with groups on the surface of the nano filler are introduced into the surface of the hollow microsphere, and the hollow microsphere is dispersed in water to obtain the hollow microsphere water dispersion.
3) Preparation of hollow microsphere @ nanofiller core-shell particles: according to the composition of the pre-prepared polymer nano composite material, the hollow microsphere dispersion liquid and the nano filler dispersion liquid with certain volume are mixed, and then the mixture is filtered or centrifugally separated and dried to obtain the hollow microsphere @ nano filler core-shell particles.
4) Preparation of light nanocomposite with an isolation structure: the hollow microsphere @ nano filler core-shell particles are uniformly dispersed in a polymer matrix, and then the mixture is processed and molded to prepare the light polymer nano composite material with the isolation structure.
In the preparation method, the nano-filler in the step (1) is at least one selected from 0-dimensional, 1-dimensional and 2-dimensional nano-fillers, specifically at least one selected from silica, carbon black, fullerene, carbon nanotube, graphene, metal particles, metal compounds, boric acid, borate, borax, halloysite nanotube, hydroxyapatite, clay with the number of layers less than or equal to 20, graphite with the number of layers less than or equal to 20, boron nitride with the number of layers less than or equal to 20, black phosphorus with the number of layers less than or equal to 20, and derivatives thereof. The hollow microspheres in the step (2) are at least one selected from glass hollow microspheres, carbon hollow microspheres and polymer hollow microspheres.
The light polymer nanocomposite with the isolation structure can be used as a material with flame retardant, electric conduction, heat conduction or electromagnetic shielding functions, and can be applied to high-end technical fields of aerospace, transportation, electronic communication and the like.
Compared with the prior art, the polymer nano composite material prepared by the invention has the advantages that the nano filler is isolated by the hollow microspheres and is extruded in the limited space between the hollow microspheres in a three-dimensional dense distribution manner, the utilization efficiency of the nano filler can be obviously improved, and therefore, the nano filler is lower in use amount in order to obtain the polymer nano composite material with the same performance. Compared with the traditional random structure polymer nanocomposite, the polymer nanocomposite with the isolation structure has obvious advantages in the aspects of light weight, flame retardance, electric conduction, heat conduction, electromagnetic shielding and other functionalities. In addition, compared with the traditional method, the preparation method of the polymer nanocomposite with the isolation structure has the advantages of simple process, high preparation efficiency, suitability for most polymer matrixes and traditional polymer processing processes and the like, and is suitable for industrial popularization.
Drawings
Fig. 1 is a scanning electron microscope photograph of the polymethyl methacrylate (PMMA) hollow microspheres @ graphene core-shell particles of example 1 at a magnification of 500 times.
Fig. 2 is a scanning electron micrograph of PMMA hollow microsphere @ graphene core-shell particles of example 1 at 3000 times magnification.
FIG. 3 is a scanning electron micrograph of PMMA hollow microspheres @ graphene core-shell particles of example 1 at 10000 times magnification.
fig. 4 is a photograph of a flame retardant performance test of the light polystyrene/black phosphorus nanosheet nanocomposite with the isolating structure of example 2.
Detailed Description
The invention is explained in further detail below by means of specific embodiments with reference to the drawings. It is to be understood that the following examples are intended to illustrate the invention and are not intended to limit its scope.
Example 1
The light silicone rubber/graphene nano composite material with the isolation structure is structurally characterized in that: the graphene is isolated by the PMMA hollow microspheres and is distributed around the PMMA hollow microspheres in a concentrated mode to form a three-dimensional graphene network. The PMMA hollow microspheres have the size of 40-80 microns, the mass fraction of 5 wt%, and the mass fraction of graphene is 1 wt%. The composite material is prepared by the following steps:
1) Surface modification of graphene: cationic surfactant trimethyl octadecyl ammonium bromide is used as a dispersing auxiliary agent, 2-dimensional nano filler graphene (pioneer nano, XF182-1) is dispersed in water through ultrasound or shearing to obtain a graphene dispersion liquid with positive charges on the surface, the concentration of the graphene is 10mg/mL, and the concentration of the trimethyl octadecyl ammonium bromide is 0.1 mg/mL.
2) Surface modification of PMMA hollow microspheres: the method comprises the steps of adopting an anionic surfactant sodium dodecyl benzene sulfonate as a dispersing auxiliary agent, and dispersing PMMA hollow microspheres (60F, Qingdao Xinnuo chemical Co., Ltd.) in water through ultrasound or shearing to obtain a dispersion liquid of PMMA hollow microspheres with negative charges on the surface, wherein the concentration of the PMMA hollow microsphere dispersion liquid is 10mg/mL, and the concentration of the sodium dodecyl benzene sulfonate is 0.1 mg/mL.
3) Preparing PMMA hollow microspheres @ graphene core-shell particles: mixing the volume ratio of 5: 1, filtering, separating and drying to obtain PMMA hollow microspheres @ graphene core-shell particles, wherein graphene is coated on the surfaces of the PMMA microspheres through electrostatic action.
4) Preparing a light silicone rubber/graphene nano composite material with an isolation structure: dissolving addition type liquid silicone rubber (Mylar RTV615, matrix resin: cross-linking agent: 10: 1) in chloroform to prepare a silicone rubber solution with the concentration of 90 wt%, then adding PMMA hollow microspheres @ graphene core-shell particles according to the mass fraction of 6 wt%, stirring and mixing uniformly, finally pouring the mixture into a mold, removing bubbles and chloroform under vacuum assistance, and curing at 25 ℃ for 24h under the pressure of 5MPa to obtain the light silicone rubber/graphene nano composite material with an isolation structure.
The laser particle size analyzer test shows that the particle size of the PMMA hollow microspheres is in the range of 40-80 μm, and is consistent with the observation result of a scanning electron microscope (figure 1). Fig. 1-3 are scanning electron microscope pictures of PMMA hollow microsphere @ graphene core-shell particles under different magnifications, with the increase of the magnifications, graphene folds coated on the surface of the PMMA hollow microsphere can be observed more and more clearly, and the whole PMMA hollow microsphere is uniformly coated by graphene.
The density of the nanocomposite material was 0.28g/cm3The electrical conductivity is 3.8X 10-5s/m, thermal conductivity 0.366W/(mK). If only graphene is mixed in the silicone rubber solution according to the preparation process conditions of the composite material in the step 4) of the embodiment, the density of the prepared silicone rubber/graphene nanocomposite material with the random structure is 1.1g/cm3Conductivity of 2.3X 10-10S/m, thermal conductivity 0.263W/(mK). In contrast, the light silicone rubber/graphene nanocomposite with the isolation structureThe density of the composite material is reduced by 75%, the electric conductivity is improved by-5 orders of magnitude, and the heat conductivity is improved by 39%, which shows that the prepared silicon rubber/graphene nano composite material with the isolation structure is light in weight, and the effective utilization rate of graphene is far higher than that of the silicon rubber/graphene nano composite material with the random structure.
Example 2
the light polystyrene/black phosphorus nanosheet nanocomposite with the isolation structure is structurally characterized in that: the black phosphorus nanosheets are isolated by the hollow glass spheres and are distributed around the hollow glass spheres in a concentrated manner to form a three-dimensional black phosphorus nanosheet network. The size of the hollow glass sphere is 0.1-50 μm, the mass fraction is 30 wt%, and the mass fraction of the black phosphorus nanosheet is 0.1 wt%. The composite material is prepared by the following steps:
1) Surface modification of black phosphorus nanosheets: the method comprises the steps of dispersing black phosphorus nanosheets (pioneer nano XF207) in water by using a non-ionic surfactant polyvinyl alcohol as a dispersing aid through ultrasound or shearing to obtain a black phosphorus nanosheet dispersion liquid with hydroxyl on the surface, wherein the concentration of the black phosphorus nanosheet dispersion liquid is 1mg/mL, and the concentration of polyvinyl alcohol is 0.01 mg/mL.
2) Surface modification of hollow glass microspheres: the preparation method comprises the steps of adopting a nonionic surfactant polyvinylpyrrolidone as a dispersing aid, and dispersing hollow glass microspheres (provided by Thermo Scientific) in water through ultrasound or shearing to obtain a hollow glass microsphere dispersion liquid with pyrrolidone groups on the surface, wherein the concentration of the hollow glass microsphere dispersion liquid is 10mg/mL, and the concentration of polyvinylpyrrolidone is 0.5 mg/mL.
3) Preparation of hollow glass microsphere @ black phosphorus nanosheet core-shell particles: mixing the volume ratio of 30: 1, mixing the hollow glass microsphere dispersion liquid and the black phosphorus nanosheet dispersion liquid, performing centrifugal separation and drying to obtain the hollow glass microsphere @ black phosphorus nanosheet core-shell particle, wherein the black phosphorus nanosheet is coated on the surface of the hollow glass microsphere through a hydrogen bonding effect.
4) Preparing a light polystyrene/black phosphorus nanosheet nanocomposite material with an isolation structure: mixing 30.1 wt% of hollow glass microsphere @ black phosphorus nanosheet core-shell particles into polystyrene (China petrochemical, GH660) in a melting and blending mode, and then transferring the mixture to a mold for compression molding to obtain the light polystyrene/black phosphorus nanosheet nanocomposite with the isolation structure. The melt blending conditions were: a double-roller open mill, the temperature is 180 ℃, and the time is 8 min; the molding conditions were: the temperature is 180 ℃, the pressure is 15MPa, and the time is 10 min.
The laser particle size analyzer tests show that the size of the hollow glass ball is in the range of 0.1-10 mu m. The nano composite material is difficult to ignite, has weak flame and less smoke during combustion, has the self-extinguishing characteristic (shown in figure 4) of leaving fire, and has the flame retardant property reaching V-0 level, so the material is an excellent flame retardant material. If only black phosphorus nanosheets are mixed into polystyrene according to the preparation process conditions of the composite material in the step 4) of the embodiment to prepare the polystyrene/black phosphorus nanocomposite material with the random structure, in order to obtain similar flame retardant performance, the usage amount of the black phosphorus nanosheets is not less than 30 wt%.
Example 3
The light silicone rubber/single-wall carbon nanotube nano composite material with the isolation structure is structurally characterized in that: the single-walled carbon nanotubes are isolated by the hollow carbon microspheres and are intensively distributed around the hollow carbon microspheres to form a three-dimensional single-walled carbon nanotube network. The size of the hollow carbon microsphere is 70-100 μm, and the mass fraction is 1 wt%; the mass fraction of the single-walled carbon nanotube is 10 wt%. The composite material is prepared by the following steps:
1) Surface modification of single-walled carbon nanotubes: 1g of single-walled carbon nanotube (pioneer nanometer, XFS22) is subjected to reflux acidification treatment by adopting 30mL of aqua regia, the reaction condition is 100 ℃ for 1h, carboxyl is modified on the surface of the single-walled carbon nanotube, the single-walled carbon nanotube is re-dispersed in water after being washed, and the concentration of the single-walled carbon nanotube dispersion liquid is 5 mg/mL.
2) Surface modification of hollow carbon microspheres: the surface of a hollow carbon microsphere (5g, provided by Japan Marine chemical research) is chemically modified by adopting a silane coupling agent gamma-aminopropyltriethoxysilane (1 wt% ethanol solution, 50mL), an amine group is modified on the surface of the hollow carbon microsphere, the hollow carbon microsphere is redispersed in water after being washed, and the concentration of a hollow carbon microsphere dispersion solution is 5 mg/mL.
3) the preparation method of the hollow carbon microsphere @ single-walled carbon nanotube core-shell particle comprises the following steps: mixing the components in a volume ratio of 1: 10, reacting at 80 ℃ for 6 hours, centrifuging, and drying to obtain the hollow carbon microsphere @ single-walled carbon nanotube core-shell particles, wherein the single-walled carbon nanotube is coated on the surface of the hollow carbon microsphere through an amido bond.
4) Preparing a light silicone rubber/single-walled carbon nanotube nano composite material with an isolation structure: dissolving addition type liquid silicone rubber (Mylar RTV615, matrix resin: cross-linking agent: 10: 1) in chloroform to prepare a silicone rubber solution with the concentration of 90 wt%, adding hollow carbon microspheres and single-walled carbon nanotube core-shell particles according to the mass fraction of 11 wt%, stirring and mixing uniformly, finally pouring the mixture into a mold, removing bubbles and chloroform under vacuum assistance, and curing at 65 ℃ for 6h under the pressure of 5MPa to obtain the light silicone rubber/single-walled carbon nanotube nano composite material with an isolation structure.
The test of the laser particle size analyzer shows that the particle size of the hollow carbon microsphere is between 70 and 100 mu m. The density of the nanocomposite material is 0.48g/cm3The electric conductivity is 33S/m, the thermal conductivity is 0.787W/(m.K), and the average electromagnetic shielding effectiveness in an X wave band is 38 dB. If only the single-walled carbon nanotube is mixed in the silicone rubber solution according to the preparation process conditions of the composite material of step 4) of the embodiment, the density of the prepared silicone rubber/single-walled carbon nanotube nano composite material with the random structure is 1.3g/cm3Conductivity of 2.3X 10-3S/m, the thermal conductivity is 0.421W/(m.K), and the average electromagnetic shielding effectiveness in the X wave band is 23 dB. Compared with the silicon rubber/single-walled carbon nanotube nano composite material with the random structure, the density of the light silicon rubber/single-walled carbon nanotube nano composite material with the isolation structure is reduced by 63%, the electric conductivity is improved by 4 orders of magnitude, the heat conductivity is improved by 87%, and the electromagnetic shielding efficiency is improved by 65%, which shows that the prepared silicon rubber/single-walled carbon nanotube nano composite material with the isolation structure is not only light, but also the formed three-dimensional single-walled carbon nanotube network is more complete and compact than the silicon rubber/single-walled carbon nanotube nano composite material with the random structure, and can be used as a light antistatic material, a heat conducting material.

Claims (6)

1. the light polymer nano composite material with the isolation structure is characterized by comprising a polymer matrix, hollow microspheres and nano fillers, wherein groups loaded on the surfaces of the nano fillers are uniformly distributed on the surfaces of the hollow microspheres through interaction with the groups loaded on the surfaces of the hollow microspheres to form hollow microsphere @ nano filler core-shell particles, and the hollow microsphere @ nano filler core-shell particles are uniformly distributed in the polymer matrix.
2. The light-weight polymer nanocomposite with an isolation structure as claimed in claim 1, wherein the hollow microspheres have a size of 0.1 μm to 100 μm and a mass fraction of 1 wt% to 30 wt%; the mass fraction of the nano filler is 0.1 wt% -10 wt%.
3. a method of making a light weight polymer nanocomposite with insulation according to claim 1, comprising the steps of:
(1) surface modification of the nano filler: carrying out surface modification on the nano filler by a physical or chemical method, introducing groups capable of having strong interaction with groups on the surface of the hollow microsphere on the surface of the nano filler, and then dispersing in water to obtain nano filler water dispersion;
(2) Surface modification of hollow microspheres: carrying out surface modification on the hollow microspheres by a physical or chemical method, introducing groups capable of having strong interaction with groups on the surfaces of the nano fillers on the surfaces of the hollow microspheres, and then dispersing the groups in water to obtain a hollow microsphere water dispersion;
(3) Preparation of hollow microsphere @ nanofiller core-shell particles: mixing a hollow microsphere dispersion liquid and a nano filler dispersion liquid with a certain volume according to the composition of a polymer nano composite material to be prepared, and filtering or centrifugally separating and drying to obtain hollow microsphere @ nano filler core-shell particles;
(4) Preparation of light nanocomposite with an isolation structure: the hollow microsphere @ nano filler core-shell particles are uniformly dispersed in a polymer matrix, and then the mixture is processed and molded to prepare the light polymer nano composite material with the isolation structure.
4. The method for preparing a light weight polymer nanocomposite with insulation structure as claimed in claim 3, wherein the nano filler in the step (1) is at least one selected from 0-dimensional, 1-dimensional and 2-dimensional nano fillers; the hollow microspheres in the step (2) are at least one selected from glass hollow microspheres, carbon hollow microspheres and polymer hollow microspheres.
5. The method of claim 4, wherein the nano-filler is at least one of silica, carbon black, fullerene, carbon nanotube, graphene, metal particles, metal compounds, boric acid, borate, borax, halloysite nanotube, hydroxyapatite, clay with number of layers less than or equal to 20, graphite with number of layers less than or equal to 20, boron nitride with number of layers less than or equal to 20, black phosphorus with number of layers less than or equal to 20, and derivatives thereof.
6. The polymer nanocomposite as claimed in claim 1, which can be used as a flame retardant, electrically conductive, thermally conductive or electromagnetic shielding functional material.
CN201910904140.4A 2019-09-24 2019-09-24 Light polymer nano composite material with isolation structure and preparation method thereof Pending CN110564159A (en)

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CN112375392A (en) * 2020-11-25 2021-02-19 德阳中碳新材料科技有限公司 Preparation method of graphene heat-conducting interface material
CN113453526A (en) * 2021-06-29 2021-09-28 深圳先进电子材料国际创新研究院 Low-compression-stress electromagnetic shielding material and preparation method thereof
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CN114373970A (en) * 2021-12-29 2022-04-19 上海应用技术大学 Proton exchange membrane with high proton conductivity and high durability as well as preparation method and application thereof
CN115044140A (en) * 2022-07-01 2022-09-13 安徽卡洛塑业科技有限公司 Preparation process of environment-friendly flame-retardant polystyrene material
CN115340748A (en) * 2021-05-12 2022-11-15 中国科学院理化技术研究所 Light high-strength electromagnetic shielding composite material based on conductive hollow microspheres and preparation method and application thereof
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CN111534016A (en) * 2020-06-01 2020-08-14 中国科学院合肥物质科学研究院 Electronic packaging material with heat conduction and electromagnetic shielding performance and preparation method thereof
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CN114373970A (en) * 2021-12-29 2022-04-19 上海应用技术大学 Proton exchange membrane with high proton conductivity and high durability as well as preparation method and application thereof
CN115044140A (en) * 2022-07-01 2022-09-13 安徽卡洛塑业科技有限公司 Preparation process of environment-friendly flame-retardant polystyrene material
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CN115612179A (en) * 2022-11-01 2023-01-17 黄晓 Low-dimensional nano high-thermal-conductivity material coated hollow microsphere composite thermal conductive filler and preparation method and application thereof
WO2024093718A1 (en) * 2022-11-01 2024-05-10 黄晓 Hollow microsphere composite thermally-conductive filler coated with low-dimensional nanometer high-thermal-conductivity material, preparation method therefor, and use thereof

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