CN110128792B - Thermal interface composite material and preparation method and application thereof - Google Patents
Thermal interface composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a thermal interface composite material and a preparation method and application thereof, wherein the thermal interface composite material comprises a carbon fiber framework and a polymer matrix which fills and coats the carbon fiber framework; the carbon fibers in the carbon fiber skeleton are arranged in a single orientation. The carbon fibers in the oriented arrangement establish a heat conduction channel in the vertical direction of the thermal interface composite material, and the carbon fibers are mutually contacted and connected in the direction, so that the overall interface thermal resistance of the material is reduced, and the out-of-plane thermal conductivity of the thermal interface composite material is greatly improved; and the carbon fiber framework and the polymer matrix are mutually cooperated, so that the thermal interface composite material has high glass transition temperature and good mechanical properties such as strength, toughness and the like. The thermal interface composite material provided by the invention has excellent heat conduction and mechanical properties, the preparation method is simple and easy to operate, and the thermal interface composite material is a novel heat conduction material with large-scale industrial production prospect.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a thermal interface composite material and a preparation method and application thereof.
Background
The miniaturization and high integration of the electronic components endow the electronic product with more functions and higher efficiency, and simultaneously, the working power of unit volume in the electronic product is greatly improved, thereby bringing about a serious heat dissipation problem. The heat dissipation of the electronic components directly leads to the temperature rise and thermal stress increase of the electronic equipment, and poses serious threat to the working reliability of the microelectronic equipment. The most important heat dissipation design of electronic components is to connect the chip with the substrate and the substrate heat dissipation system by means of thermal interface materials, and the industry generally believes that the bottleneck of future electronic product development is not the design of hardware and the heat dissipation system, but whether effective thermal interface materials can be prepared. Therefore, in order to solve the problem of structural heat dissipation of electrical and electronic equipment, the development of a novel thermal interface material with excellent thermal conductivity becomes a research hotspot in the international electrical and electronic field, and the main idea of developing the thermal interface material is to design a composite material formed by interaction of a polymer and multiple thermal conductive fillers.
CN102286207A discloses a thermoplastic polymer-based heat-conducting composite material and a preparation method thereof, the heat-conducting composite material comprises a thermoplastic polymer matrix, heat-conducting fillers and auxiliary heat-conducting materials, wherein the thermoplastic polymer matrix is at least one of polyphenylene sulfide, acrylonitrile-styrene-butadiene copolymer, nylon, polyethylene, polycarbonate, polyvinyl chloride, polypropylene, polystyrene or silicon rubber and other high polymer materials, the auxiliary heat conduction material is a thermoplastic polymer incompatible with the thermoplastic polymer matrix, the heat conduction filler is at least one of graphite, carbon nano tube, carbon black, silicon nitride, boron nitride, aluminum oxide, magnesium oxide, copper powder, aluminum powder or magnesium powder, and the volume ratio of the thermoplastic polymer matrix to the auxiliary heat conduction material is (50-95): (5-50), the heat-conducting filler accounts for 5-40 wt% of the thermoplastic polymer matrix.
CN103665772A discloses a method for preparing a carbon nanotube array flexible thermal interface material compounded with epoxy resin, the composite material takes a carbon nanotube array as a heat conducting framework, epoxy resin is used for compounding, a toughening agent is added to improve tensile toughness, and the end of a carbon nanotube is polished on the surface to be exposed as a thermal interface contact layer; wherein the average tube diameter of the carbon nano tube array is 80nm, the height of the carbon nano tube array is 0.4-1 mm, and the toughening agent is dibutyl phthalate. The thermal interface material obtained by the preparation method has good heat conduction performance and certain soft tensile toughness, and can be attached to a thermal interface to help the interface to dissipate heat.
The application of single-layer graphene and multi-layer graphene in the thermal interface material is researched by Khan M.F.Shahil and the like, and the research shows that when the filling amount of the single-layer graphene and the multi-layer graphene in the material is 2% of volume fraction, the thermal conductivity coefficient of the prepared thermal interface material can reach 14W/(m.K); in addition, graphene and silver micro/nanoparticles are compounded with an epoxy resin matrix as a mixed heat dissipation filler to obtain a thermal interface material with the filling amount of the mixed heat dissipation filler being 5% by volume fraction, and the thermal conductivity of the thermal interface material can be increased by 500% compared with that of a silver-epoxy resin thermal interface material (Khan m.f. sharp, et al. solid State Communications,2012,152(15): 1331). The improvement of the thermal conductivity of the graphene to the epoxy resin and related mechanisms are reported by Tangbo and the like, and the thermal conductivity of the epoxy resin can be remarkably improved by the graphene, and when the content of the graphene is 15%, the thermal conductivity of the epoxy resin can be improved to 24 times; the functional group on the surface of the graphene can effectively reduce the interface contact thermal resistivity between the graphene and the epoxy resin, and promote the phonon mode between the graphene and the epoxy resin to be more matched (Tangbo and the like, preparation of graphene-based epoxy resin composite thermal interface material and thermal performance [ J ], silicate science report, 2017, 45 and 126).
However, in the prior art, the thermal interface material based on the compound powder type heat-conducting filler has the problems of difficult processing, high cost and the like, and the material with high proportion of compound powder and good heat-conducting property is often reduced in mechanical property, poor in toughness and not corrosion-resistant; the thermal interface material added with the carbon nano tube has excellent performance, but the carbon nano tube has complex preparation process and high cost and is not suitable for industrial application; graphene, as a two-dimensional heat conducting material, has anisotropic heat conducting properties, so that a thermal interface material based on graphene exhibits good in-plane heat conductivity, but has low out-of-plane heat conductivity, and is difficult to realize good out-of-plane heat dissipation performance.
Therefore, the development of a thermal interface composite material which has excellent heat dissipation performance, particularly good out-of-plane heat dissipation performance, low cost and high mechanical performance and is suitable for industrial application is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a thermal interface material and a preparation method and application thereof, wherein a carbon fiber framework in the thermal interface material is a framework structure which plays a role in heat conduction, and carbon fibers are arranged along a single orientation, so that the thermal interface material has excellent heat conduction performance, and especially has the characteristic of out-of-plane high heat conduction in the direction of the oriented arrangement of the carbon fibers; the interaction of the polymer matrix and the carbon fiber skeleton provides good mechanical strength and processability for the thermal interface material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present disclosure provides a thermal interface composite material, which includes a carbon fiber skeleton, and a polymer matrix filling and coating the carbon fiber skeleton; the carbon fibers in the carbon fiber skeleton are arranged in a single orientation.
In the thermal interface composite material provided by the invention, the carbon fiber framework is a heat-conducting filler which plays a main heat conduction role, wherein the carbon fiber not only has inherent intrinsic characteristics of high heat conduction, high temperature resistance, corrosion resistance and the like of a carbon material, but also has high strength, high toughness and processability of a fiber material, so that the framework structure constructed on the basis of the carbon fiber can play excellent heat conduction performance and reduce the interface thermal resistance of the thermal interface composite material on one hand, and can play a role in enhancing and toughening a polymer matrix by being used as the filler and the polymer matrix which are mutually cooperated, thereby improving the mechanical properties such as the strength, the toughness and the like of the whole thermal interface composite material. More importantly, in the carbon fiber framework of the thermal interface composite material, the carbon fibers are directionally arranged along a single orientation, a heat conduction channel is established along the axial direction of the carbon fibers, and the carbon fibers are mutually contacted and connected in the axial direction, so that the interface thermal resistance of the material is converted from a carbon fiber-polymer matrix to the carbon fiber-carbon fibers, the overall interface thermal resistance of the material is reduced, and the out-of-plane thermal conductivity of the thermal interface composite material is greatly improved. In conclusion, the thermal interface composite material provided by the invention has excellent heat conductivity and mechanical properties through the mutual matching of the carbon fiber framework and the polymer matrix, and particularly has the characteristic of high out-of-plane heat conductivity.
Preferably, the material of the polymer matrix is a thermosetting polymer;
preferably, the thermosetting polymer is selected from any one or a combination of at least two of epoxy resin, phenolic resin, polyurethane, polyimide, urea resin or organic silicon resin, and is further preferably epoxy resin;
preferably, the volume percentage of the polymer matrix is 80-99%, such as 81%, 83%, 85%, 87%, 89%, 90%, 93%, 85%, 97%, 99% or 100% based on 100% of the total volume of the thermal interface composite, and the specific values therebetween are not exhaustive for the sake of brevity and simplicity.
In the thermal interface composite material provided by the invention, the selection of the polymer matrix is mainly based on two aspects of mechanical property and chemical stability. The material of the high polymer matrix selected in the invention is thermosetting polymer, has mechanical properties such as good mechanical strength, high toughness, good processability and the like, is stable in chemical property, resistant to corrosion and high temperature, and can be matched with a carbon fiber framework to form a heat-conducting composite material with excellent performance. According to the invention, the epoxy resin is further screened in the preferred scheme, the epoxy resin has low density, corrosion resistance, stable chemical property and good elasticity, and can meet the performance requirement of the thermal interface composite material on a high polymer matrix.
Preferably, the diameter of the carbon fiber is 1 to 15 μm, such as 2 μm, 4 μm, 5 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 13 μm, 14 μm or 15 μm, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive and the specific values included in the range are further preferably 9 to 12 μm.
Preferably, the length of the carbon fiber is 50 to 300 μm, such as 55 μm, 60 μm, 65 μm, 70 μm, 80 μm, 90 μm, 100 μm, 130 μm, 150 μm, 170 μm, 190 μm, 200 μm, 250 μm, 270 μm or 300 μm, and the specific values therebetween are limited by space and for the sake of brevity, the invention does not exhaust the specific values included in the range, and more preferably 150 to 200 μm.
In the thermal interface composite material, the carbon fiber framework constructed by the oriented arrangement of the carbon fibers is the key point for providing the thermal conductivity, and the scale of the carbon fibers can influence the overall performance of the material. If the size of the carbon fiber exceeds the range defined by the invention and the length of the carbon fiber is less than 50 mu m, the length-diameter ratio of the carbon fiber is low, the order of a skeleton structure formed by the directional arrangement of the carbon fiber is not obvious, a good heat conduction channel cannot be formed in the axial direction of the carbon fiber, and the high out-of-plane heat conduction performance is difficult to provide for the material; when the length is more than 300 μm, the aspect ratio of the carbon fiber is too large, and it is difficult to provide mechanical support in the axial direction of the carbon fiber to form a stable skeleton structure, so that a stable carbon fiber skeleton structure cannot be constructed.
Preferably, the volume percentage of the carbon fiber is 1-20%, such as 2%, 3%, 5%, 7%, 9%, 10%, 13%, 15%, 17%, 19% or 20% based on 100% of the total volume of the thermal interface composite, and the specific values therebetween are limited by space and for brevity, the invention does not exhaust the specific values included in the range, and more preferably 3-15%.
The thermal interface composite material provided by the invention limits the volume percentage of the carbon fiber to be 1-20%, if the volume percentage is lower than 1%, the proportion of the heat-conducting filler carbon fiber in the material is too low, and the carbon fiber cannot play a good heat-conducting effect, so that the material does not have heat-conducting property; if the volume percentage of the carbon fibers is higher than 20%, the formed carbon fiber skeleton structure has too high density, the porosity in the skeleton is low, and sufficient polymer matrix cannot be filled in the skeleton, so that the overall mechanical property of the thermal interface composite material is poor, and later-stage application is not facilitated.
Preferably, the carbon fiber is subjected to surface functionalization treatment;
preferably, the carbon fiber is a surface-hydrophilically treated carbon fiber.
Preferably, the thermal interface composite further comprises a binder;
preferably, the binder is a hydrophilic binder;
preferably, the hydrophilic adhesive is a cellulose adhesive, a polyvinyl alcohol adhesive or a cyanoacrylate adhesive;
preferably, the cellulose binder is sodium carboxymethyl cellulose and/or hydroxyethyl cellulose;
preferably, the mass ratio of the binder to the carbon fibers is (1-5): 1, for example, 1.1:1, 1.3:1, 1.5:1, 1.8:1, 2:1, 2.3:1, 2.5:1, 2.8:1, 3:1, 3.3:1, 3.5:1, 3.8:1, 4:1, 4.3:1, 4.5:1, 4.8:1 or 4.9: 1.
In the thermal interface composite material, in order to obtain a stable carbon fiber framework structure, a binder is required to be added during the preparation of the carbon fiber framework, and the binder and the carbon fiber are connected based on intermolecular interaction such as hydrogen bonds, so that the constructed carbon fiber framework structure is firmer, and the thermal interface composite material is beneficial to the next preparation and subsequent application.
In another aspect, the present invention provides a method of making a thermal interface composite as described above, the method comprising the steps of:
(1) preparing a carbon fiber framework: mixing carbon fibers with an aqueous solution of a binder to obtain a carbon fiber suspension, and then freezing and drying the carbon fiber suspension to obtain the carbon fiber skeleton with the carbon fibers arranged along a single orientation;
(2) preparing a thermal interface composite material: and (3) mixing a liquid polymer with the carbon fiber skeleton obtained in the step (1), and performing suction filtration and curing to obtain the thermal interface composite material.
Preferably, the carbon fiber in the step (1) is subjected to surface functionalization treatment;
preferably, the surface functionalization treatment is a hydrophilic treatment;
preferably, the method of hydrophilic treatment comprises plasma treatment and/or acidification treatment.
The carbon fiber skeleton in the thermal interface composite material is obtained by freeze-drying a carbon fiber aqueous solution, and in order to ensure that the carbon fiber has good dispersibility and uniform distribution in water and does not generate agglomeration or sedimentation to obtain a suspension with good dispersion of the carbon fiber, the carbon fiber needs to be subjected to surface hydrophilic treatment, including plasma treatment and/or acid liquor treatment, so that the surface of the carbon fiber is provided with hydrophilic groups such as-OH and the like, and the carbon fiber is uniformly dispersed in the water.
Preferably, the volume percentage of the carbon fibers in the carbon fiber suspension of step (1) is 1-20%, for example, 2%, 3%, 4%, 5%, 7%, 9%, 10%, 13%, 15%, 17%, 18%, 19% or 20%, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the preparation condition of the carbon fiber suspension in the step (1) is to stir and mix the materials in vacuum;
preferably, the speed of the vacuum stirring and mixing is 1500-2500 rpm, such as 1600rpm, 1700rpm, 1800rpm, 1900rpm, 2000rpm, 2100rpm, 2300rpm, 2400rpm or 2500rpm, and the specific values therebetween are not exhaustive for the sake of brevity and simplicity.
Preferably, the vacuum stirring and mixing time is 10-30 min, such as 12min, 14min, 15min, 17min, 19min, 20min, 22min, 24min, 25min, 27min, 28min or 29min, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the temperature of the freezing in step (1) is 0 to-250 ℃, such as-5 ℃, -10 ℃, -15 ℃, -20 ℃, -30 ℃, -50 ℃, -70 ℃, -100 ℃, -130 ℃, -150 ℃, -180 ℃, -200 ℃, -210 ℃, -230 ℃ or-250 ℃, and the specific values therebetween are limited to space and for the sake of brevity, and the present invention is not exhaustive enumeration of the specific values encompassed by the range.
Preferably, the freezing method in step (1) is liquid nitrogen freezing.
The carbon fiber skeleton in the thermal interface composite material is obtained by freeze-drying a carbon fiber aqueous solution, in the preparation method, the carbon fiber is dispersed in an aqueous solution of a binder at present, the carbon fiber is fully and uniformly mixed to obtain a suspension of the carbon fiber, and then the suspension is cooled and frozen, wherein the cooling and freezing method is preferably liquid nitrogen freezing; water in the carbon fiber suspension is quickly frozen under the low-temperature condition of being lower than 0 ℃, the orientation of the carbon fibers is adjusted by extrusion force generated by the upward growth of ice in the freezing process, and the carbon fibers form vertical single orientation arrangement along the growth direction of the ice under the action of the extrusion force, so that an ordered structure of the carbon fibers in the vertical direction, namely the axial orientation arrangement of the carbon fibers is constructed; meanwhile, the carbon fibers are contacted and connected with each other in the vertical direction to construct a heat conduction channel in the vertical direction. And then drying to remove ice in the system, thereby obtaining the framework structure with the carbon fibers in single orientation arrangement.
Preferably, the drying of step (1) is vacuum freeze-drying;
preferably, the drying time in step (1) is 10-30 h, such as 12h, 14h, 15h, 17h, 20h, 22h, 24h, 26h, 28h or 30h, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the mixing method in step (2) is as follows: completely immersing the carbon fiber skeleton obtained in the step (1) into a liquid polymer;
preferably, the liquid polymer in the step (2) further comprises a curing agent and a catalyst;
preferably, the temperature of the suction filtration in the step (2) is 30-50 ℃, for example, 31 ℃, 33 ℃, 35 ℃, 37 ℃, 39 ℃, 40 ℃, 42 ℃, 44 ℃, 45 ℃, 47 ℃, 48 ℃ or 50 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive list of the specific values included in the range.
Preferably, the suction filtration in the step (2) is vacuum filtration;
preferably, the vacuum filtration time is 2-4 h, such as 2.1h, 2.3h, 2.5h, 2.7h, 2.9h, 3h, 3.3h, 3.5h, 3.8h or 4h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the range.
In the preparation process of the thermal interface composite material, a carbon fiber skeleton structure is obtained by a freeze drying method, then the carbon fiber skeleton structure is immersed in a liquid polymer, the polymer is fully filled in gaps of the carbon fiber skeleton structure and coats the carbon fiber skeleton, and then the polymer matrix is obtained by solidification. After the carbon fiber framework structure is immersed in the liquid polymer, vacuum filtration is carried out, on one hand, the purpose of forming is achieved, on the other hand, the vacuum filtration can enable the polymer to be fully contacted with the carbon fiber framework as far as possible and fill the inside of the whole carbon fiber framework, and the bonding performance between the carbon fiber and the polymer matrix is better on the premise of not damaging the carbon fiber framework structure.
Preferably, the curing method in step (2) is heating curing;
preferably, the temperature for the heat curing is 100-250 ℃, for example, 110 ℃, 130 ℃, 150 ℃, 170 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 240 ℃ or 250 ℃, and the specific values therebetween are limited by the space and the conciseness, and the invention is not exhaustive of the specific values included in the range.
Preferably, the time for the heat curing is 0.5 to 7 hours, such as 0.7 hour, 0.8 hour, 1 hour, 1.3 hour, 1.5 hour, 1.7 hour, 1.9 hour, 2 hour, 2.3 hour, 2.5 hour, 2.8 hour, 3 hour, 4 hour, 5 hour, 6 hour or 6.5 hour, and the specific point values therebetween are limited to the space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the preparation method specifically comprises the following steps:
(1) preparing a carbon fiber framework: mixing the carbon fiber subjected to surface hydrophilic treatment with an aqueous solution of a binder, and mixing the mixture in vacuum for 10-30 min at a rotating speed of 1500-2500 rpm to obtain a carbon fiber suspension with the volume percentage of the carbon fiber being 1-20%; then freezing the carbon fiber suspension liquid by using liquid nitrogen, and drying in vacuum for 10-30 h to obtain the carbon fiber framework with carbon fibers arranged along a single orientation;
(2) preparing a thermal interface composite material: completely immersing the carbon fiber skeleton obtained in the step (1) into a liquid polymer, then placing the carbon fiber skeleton into a vacuum drying oven, and carrying out vacuum filtration for 2-4 h at the temperature of 30-50 ℃; and then heating and curing for 0.5-7 h at the temperature of 100-250 ℃ to obtain the thermal interface composite material.
In another aspect, the present invention provides an electronic component comprising the thermal interface material as described above.
In another aspect, the present invention provides an electronic device including the electronic component described above.
Compared with the prior art, the invention has the following beneficial effects:
the thermal interface composite material provided by the invention comprises a carbon fiber framework and a polymer matrix, wherein carbon fibers in the carbon fiber framework are directionally arranged along a single orientation, a heat conduction channel is established in the vertical direction, and the carbon fibers are mutually contacted and connected in the direction, so that the overall interface thermal resistance of the material is reduced, and the out-of-plane thermal conductivity of the thermal interface composite material is greatly improved; and the carbon fiber framework and the polymer matrix are mutually cooperated, so that the thermal interface composite material has high glass transition temperature and good mechanical properties such as strength, toughness and the like. The thermal interface composite material provided by the invention has excellent heat conduction and mechanical properties, the preparation method is simple and easy to operate, and the thermal interface composite material is a novel heat conduction material with large-scale industrial production prospect.
Drawings
Fig. 1 is a schematic structural diagram of a thermal interface composite material in example 1 of the present invention, in which "heat flow" represents heat transfer in a direction indicated by an arrow, "high temperature" represents a contact surface of the thermal interface composite material with a heat generating device, and "low temperature" represents a surface of the thermal interface composite material away from the heat generating device;
FIG. 2 is a scanning electron micrograph of a carbon fiber skeleton in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of a cross section of the thermal interface composite in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The epoxy resin used in the embodiments 1 to 15 of the invention is TTA 21S of Jiangsu Tetel new material science and technology Limited company, and the epoxy equivalent is 128 to 145; the curing agent is methyl hexahydrophthalic anhydride, the catalyst is N, N-dimethylbenzylamine, and the binder is hydroxyethyl cellulose, which are all purchased from Shanghai Aladdin company; the carbon fiber powder was purchased from Shanghai Limo company, and had an average length of 180 μm and an average diameter of 10 μm, and the surface hydrophilicity treatment method of the carbon fiber was acidification treatment.
Example 1
The embodiment provides a thermal interface composite material, and a specific preparation method comprises the following steps:
(1) preparing a carbon fiber framework: mixing 0.8g of carbon fiber powder subjected to surface hydrophilic treatment with an aqueous solution of a binder, adding a proper amount of water to prepare 3mL of suspension, firstly stirring by using magnetons, and then mixing the suspension in vacuum at a rotating speed of 2000rpm for 20min to obtain a carbon fiber suspension with the volume percentage of carbon fibers being 12%; then freezing the carbon fiber suspension by using liquid nitrogen, and drying in vacuum for 24h to obtain the carbon fiber skeleton with carbon fibers arranged along a single orientation;
(2) preparing a thermal interface composite material: completely immersing the carbon fiber framework obtained in the step (1) into epoxy resin, then placing the carbon fiber framework into a vacuum drying oven, and carrying out vacuum filtration for 3 hours at the temperature of 40 ℃; and then heating and curing in a gradient manner, and heating for 1h, 2h and 2h at the temperature of 120 ℃, 160 ℃ and 200 ℃ respectively in sequence to obtain the thermal interface composite material.
In this embodiment, in step (1), a carbon fiber framework in which carbon fibers are arranged along a single orientation is obtained by a method of freezing with liquid nitrogen and freeze-drying in vacuum, and then in step (2), a polymer is mixed with the carbon fiber framework, and is subjected to suction filtration and solidification, so as to obtain a thermal interface composite material in which a polymer matrix and the carbon fiber framework are composited, for example, a schematic structural diagram of the thermal interface composite material is shown in fig. 1. In fig. 1, "hot flow" represents heat transfer in the direction indicated by the arrows, "high temperature" represents the interface of the thermal interface composite with the heat spreader device, and "low temperature" represents the side of the thermal interface composite away from the heat spreader device.
Testing the carbon fiber skeleton obtained in the step (1) by using a Scanning Electron Microscope (SEM), wherein the obtained scanning electron microscope image is shown in FIG. 2, and as can be seen from FIG. 2, the carbon fibers in the carbon fiber skeleton are orderly arranged along a single orientation; a scanning electron microscope is used for testing the thermal interface composite material, and a scanning electron microscope image of the cross section of the thermal interface composite material is obtained and is shown in fig. 3, and as can be seen from fig. 3, the rod-shaped substance is carbon fibers, an epoxy resin matrix is arranged around the carbon fibers, and the carbon fibers are dispersed in a polymer matrix.
Example 2
The embodiment provides a thermal interface composite material, and a specific preparation method comprises the following steps:
(1) preparing a carbon fiber framework: mixing 0.8g of carbon fiber powder subjected to surface hydrophilic treatment with an aqueous solution of a binder, adding a proper amount of water to prepare 3mL of suspension, firstly stirring by using magnetons, and then mixing the suspension in vacuum at a rotating speed of 1500rpm for 10min to obtain a carbon fiber suspension with the volume percentage of carbon fibers being 12%; then freezing the carbon fiber suspension by using liquid nitrogen, and drying in vacuum for 12h to obtain the carbon fiber skeleton with carbon fibers arranged along a single orientation;
(2) preparing a thermal interface composite material: completely immersing the carbon fiber framework obtained in the step (1) into epoxy resin, then placing the carbon fiber framework into a vacuum drying oven, and carrying out vacuum filtration for 2 hours at the temperature of 30 ℃; and then heating and curing in a gradient manner, and heating for 1h, 2h and 2h at the temperature of 120 ℃, 160 ℃ and 200 ℃ respectively in sequence to obtain the thermal interface composite material.
Example 3
The embodiment provides a thermal interface composite material, and a specific preparation method comprises the following steps:
(1) preparing a carbon fiber framework: mixing 0.8g of carbon fiber powder subjected to surface hydrophilic treatment with an aqueous solution of a binder, adding a proper amount of water to prepare 3mL of suspension, firstly stirring by using magnetons, and then mixing the suspension in vacuum at the rotation speed of 1800rpm for 15min to obtain a carbon fiber suspension with the volume percentage of carbon fibers being 12%; then freezing the carbon fiber suspension by using liquid nitrogen, and drying in vacuum for 20h to obtain the carbon fiber framework with carbon fibers arranged along a single orientation;
(2) preparing a thermal interface composite material: completely immersing the carbon fiber framework obtained in the step (1) into epoxy resin, then placing the carbon fiber framework into a vacuum drying oven, and carrying out vacuum filtration for 2.5h at the temperature of 35 ℃; and then heating and curing in a gradient manner, and heating for 1h, 2h and 2h at the temperature of 120 ℃, 160 ℃ and 200 ℃ respectively in sequence to obtain the thermal interface composite material.
Example 4
The embodiment provides a thermal interface composite material, and a specific preparation method comprises the following steps:
(1) preparing a carbon fiber framework: mixing 0.8g of carbon fiber powder subjected to surface hydrophilic treatment with an aqueous solution of a binder, adding a proper amount of water to prepare 3mL of suspension, firstly stirring by using magnetons, and then mixing the suspension in vacuum at the rotation speed of 2300rpm for 25min to obtain a carbon fiber suspension with the volume percentage of carbon fibers being 12%; then freezing the carbon fiber suspension by using liquid nitrogen, and drying in vacuum for 30h to obtain the carbon fiber framework with carbon fibers arranged along a single orientation;
(2) preparing a thermal interface composite material: completely immersing the carbon fiber framework obtained in the step (1) into epoxy resin, then placing the carbon fiber framework into a vacuum drying oven, and carrying out vacuum filtration for 3.5h at the temperature of 45 ℃; and then heating and curing in a gradient manner, and heating for 1h, 2h and 2h at the temperature of 120 ℃, 160 ℃ and 200 ℃ respectively in sequence to obtain the thermal interface composite material.
Example 5
The embodiment provides a thermal interface composite material, and a specific preparation method comprises the following steps:
(1) preparing a carbon fiber framework: mixing 0.8g of carbon fiber powder subjected to surface hydrophilic treatment with an aqueous solution of a binder, adding a proper amount of water to prepare 3mL of suspension, firstly stirring by using magnetons, and then mixing the suspension in vacuum for 30min at the rotating speed of 2500rpm to obtain a carbon fiber suspension with the volume percentage of carbon fibers of 12%; then freezing the carbon fiber suspension by using liquid nitrogen, and drying in vacuum for 36h to obtain the carbon fiber skeleton with carbon fibers arranged along a single orientation;
(2) preparing a thermal interface composite material: completely immersing the carbon fiber framework obtained in the step (1) into epoxy resin, then placing the carbon fiber framework into a vacuum drying oven, and carrying out vacuum filtration for 4 hours at the temperature of 50 ℃; and then heating and curing in a gradient manner, and heating for 1h, 2h and 2h at the temperature of 120 ℃, 160 ℃ and 200 ℃ respectively in sequence to obtain the thermal interface composite material.
Example 6
The embodiment provides a thermal interface composite material, and a specific preparation method comprises the following steps:
(1) preparing a carbon fiber framework: mixing 0.8g of carbon fiber powder subjected to surface hydrophilic treatment with an aqueous solution of a binder, adding a proper amount of water to prepare 3mL of suspension, firstly stirring by using magnetons, and then mixing the suspension in vacuum at a rotating speed of 2000rpm for 20min to obtain a carbon fiber suspension with the volume percentage of carbon fibers being 12%; then freezing the carbon fiber suspension by using liquid nitrogen, and drying in vacuum for 25h to obtain the carbon fiber framework with carbon fibers arranged along a single orientation;
(2) preparing a thermal interface composite material: completely immersing the carbon fiber skeleton obtained in the step (1) into an alkali-catalyzed phenolic resin prepolymer, then placing the carbon fiber skeleton into a vacuum drying oven, and carrying out vacuum filtration for 3.5h at the temperature of 40 ℃; and then heating and curing for 2h at 180 ℃ to obtain the thermal interface composite material.
Example 7
This example is different from example 1 in that the carbon fiber powder in step (1) was 0.4 g.
Example 8
This example is different from example 1 in that the carbon fiber powder in step (1) was 0.6 g.
Example 9
This example is different from example 1 in that the carbon fiber powder in step (1) was 1.0 g.
Example 10
This example differs from example 1 in that the carbon fiber powder in step (1) was 1.2 g.
Example 11
This example is different from example 1 in that the carbon fiber powder in step (1) was 0.07 g.
Example 12
This example is different from example 1 in that the carbon fiber powder in step (1) was 0.05 g.
Example 13
This example differs from example 1 in that the carbon fiber powder in step (1) was 1.3 g.
Example 14
This example differs from example 1 in that the carbon fiber powder in step (1) was 1.5 g.
Example 15
This example is different from example 1 in that the carbon fiber in step (1) is not subjected to surface hydrophilic treatment.
Example 16
This example differs from example 1 in that the average length of the carbon fibers in step (1) was 500. mu.m.
Comparative example 1
The comparative example provides a thermal interface composite, and the specific preparation method comprises the following steps:
mixing 6g of carbon fiber powder subjected to surface hydrophilic treatment with an aqueous solution of a binder, adding a proper amount of water to prepare 3mL of suspension, firstly stirring by using magnetons, and then mixing the suspension in vacuum for 30min at the rotating speed of 2500rpm to obtain a carbon fiber suspension with the volume percentage of carbon fibers of 12%; and then freezing the carbon fiber suspension by using liquid nitrogen, and drying in vacuum for 36h to obtain the thermal interface composite material.
Comparative example 2
The comparative example provides a thermal interface composite, and the specific preparation method comprises the following steps:
putting the liquid epoxy resin into a vacuum drying oven, and carrying out vacuum filtration for 4h at the temperature of 50 ℃; and then heating and curing for 0.5-3 h at the temperature of 100-250 ℃ to obtain the thermal interface composite material.
Comparative example 3
The difference between the comparative example and the example 1 is that the carbon fiber suspension in the step (1) is heated by a vacuum oven for 1h, 2h and 2h at the temperature of 120 ℃, 160 ℃ and 200 ℃ respectively in sequence to obtain the carbon fiber framework with randomly arranged carbon fibers.
Comparative example 4
This comparative example is distinguished from example 1 in that the carbon fibers in step (1) are replaced with equal-mass carbon nanotubes.
The performance test method comprises the following steps: the performance testing of the thermal interface composites of the present invention is performed with reference to the prior art, for example, Xiaooling Zeng, et al.Small,2015,11(46), 6250-.
(1) And (3) testing the heat conductivity coefficient:
a standard test method for measuring heat conduction in a vertical direction by a steady state method is provided, wherein a test instrument is an LW-9389TIM resistance and conductivity measuring instrument, and the method comprises the following specific steps: placing the thermal interface composite material between the instrument bars, and establishing stable heat flow through the assembly; then monitoring the temperature in the strip at two or more points along its length; the temperature difference across the interface is calculated from the temperature readings obtained and used to determine the thermal conductivity of the interface.
(2) Testing the thermal expansion coefficient:
a thermomechanical analysis method (TMA test) using a thermomechanical analyzer (Model TMA 402F 1 superion, Netzsch) to measure the Coefficient of Thermal Expansion (CTE) of the thermal interface composite at a temperature in the range of 25 to 300 ℃.
(3) Glass transition temperature test:
and (3) a thermomechanical analysis method (TMA test), wherein a testing instrument is a thermomechanical analyzer (Model TMA 402F 1 Hyperion, Netzsch), a thermal expansion curve of the thermal interface composite material is measured within the temperature range of 25-300 ℃, and the glass transition temperature is calculated from an inflection point in the thermal expansion curve.
The thermal conductivity, thermal expansion coefficient and glass transition temperature of the thermal interface composite materials provided in examples 1-15 and comparative examples 1-4 were tested according to the above methods, and the test results are shown in table 1:
TABLE 1
The data in table 1 show that when the volume percentage of the carbon fibers in the thermal interface composite material is within the range of 1-20% defined by the invention, the thermal conductivity efficiency and the glass transition temperature of the thermal interface composite material gradually increase with the increase of the volume percentage of the carbon fibers, and the thermal expansion coefficient gradually decreases with the increase of the volume percentage of the carbon fibers, so that the thermal interface composite material provided by the invention has excellent thermal conductivity and mechanical properties, and particularly has the characteristic of high out-of-plane thermal conductivity. When the volume percentage of the carbon fibers in the thermal interface composite material exceeds the range defined by the invention or the arrangement mode of the carbon fibers is random arrangement, the thermal interface composite material does not have good heat-conducting property; in addition, when the carbon fiber of the present invention is replaced with other two-dimensional carbon materials (such as carbon nanotubes) in the same amount, the process defined in the present invention cannot obtain a carbon heat conductive skeleton arranged in order, and a thermal interface composite material having excellent heat conductive properties cannot be obtained.
The applicant states that the present invention is illustrated by the above examples to provide a thermal interface composite material and a method for preparing and applying the same, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (37)
1. The thermal interface composite material is characterized by comprising a carbon fiber framework and a polymer matrix which is filled and coated with the carbon fiber framework; the carbon fibers in the carbon fiber skeleton are arranged along a single orientation; the length of the carbon fiber is 50-300 mu m, and the diameter of the carbon fiber is 1-15 mu m;
the material of the high polymer matrix is thermosetting polymer; and the volume percentage of the polymer matrix is 80-99% based on 100% of the total volume of the thermal interface composite material.
2. The thermal interface composite of claim 1, wherein the thermosetting polymer is selected from any one of or a combination of at least two of epoxy, phenolic, polyurethane, polyimide, urea formaldehyde, or silicone.
3. The thermal interface composite of claim 1, wherein the thermosetting polymer is an epoxy resin.
4. The thermal interface composite of claim 1, wherein the carbon fibers have a diameter of 9-12 μm.
5. The thermal interface composite of claim 1, wherein the carbon fibers have a length of 150 to 200 μm.
6. The thermal interface composite of claim 1, wherein the carbon fiber is present in an amount of 1 to 20 volume percent, based on 100 volume percent of the total thermal interface composite.
7. The thermal interface composite of claim 1, wherein the carbon fiber is present in an amount of 3 to 15 volume percent, based on 100 volume percent of the total thermal interface composite.
8. The thermal interface composite of claim 1, wherein the carbon fibers are surface functionalized carbon fibers.
9. The thermal interface composite of claim 1, wherein the carbon fibers are surface hydrophilically treated carbon fibers.
10. The thermal interface composite of claim 1, further comprising a binder in the thermal interface composite.
11. The thermal interface composite of claim 10, wherein the binder is a hydrophilic binder.
12. A thermal interface composite as claimed in claim 11 wherein said hydrophilic adhesive is a cellulose adhesive, a polyvinyl alcohol adhesive or a cyanoacrylate adhesive.
13. The thermal interface composite of claim 12, wherein the cellulosic binder is sodium carboxymethylcellulose and/or hydroxyethylcellulose.
14. The thermal interface composite as claimed in claim 10, wherein the mass ratio of the binder to the carbon fibers is (1-5): 1.
15. A method of making a thermal interface composite as claimed in any one of claims 1 to 14, comprising the steps of:
(1) preparing a carbon fiber framework: mixing carbon fibers with an aqueous solution of a binder to obtain a carbon fiber suspension, and then freezing and drying the carbon fiber suspension to obtain the carbon fiber skeleton with the carbon fibers arranged along a single orientation;
(2) preparing a thermal interface composite material: and (3) mixing a liquid polymer with the carbon fiber skeleton obtained in the step (1), and performing suction filtration and curing to obtain the thermal interface composite material.
16. The production method according to claim 15, wherein the carbon fiber of step (1) is a carbon fiber subjected to surface functionalization treatment.
17. The method for producing according to claim 16, wherein the surface functionalization treatment is a hydrophilic treatment.
18. The method of claim 17, wherein the hydrophilic treatment comprises a plasma treatment and/or an acidification treatment.
19. The method according to claim 15, wherein the volume percentage of the carbon fibers in the carbon fiber suspension of step (1) is 1 to 20%.
20. The method according to claim 15, wherein the carbon fiber suspension of step (1) is prepared under vacuum agitation.
21. A preparation method according to claim 20, wherein the rotation speed of the vacuum stirring and mixing material is 1500-2500 rpm.
22. A preparation method according to claim 20, wherein the time for stirring and mixing the materials in vacuum is 10-30 min.
23. The method according to claim 15, wherein the freezing temperature in step (1) is 0 to-250 ℃.
24. The method for preparing the compound of claim 15, wherein the freezing method in step (1) is liquid nitrogen freezing.
25. The method of claim 15, wherein the drying of step (1) is vacuum lyophilization.
26. The preparation method according to claim 15, wherein the drying time in the step (1) is 10-30 h.
27. The method for preparing the compound of claim 15, wherein the mixing in step (2) is performed by: and (2) completely immersing the carbon fiber skeleton obtained in the step (1) into a liquid polymer.
28. The method according to claim 15, wherein the liquid polymer in step (2) further comprises a curing agent and a catalyst.
29. The preparation method according to claim 15, wherein the temperature of the suction filtration in the step (2) is 30-50 ℃.
30. The method according to claim 15, wherein the suction filtration in the step (2) is vacuum filtration.
31. The preparation method of claim 30, wherein the vacuum filtration time is 2-4 h.
32. The method according to claim 15, wherein the curing in step (2) is performed by heating.
33. The method according to claim 32, wherein the temperature for heat curing is 100 to 250 ℃.
34. The preparation method according to claim 32, wherein the heating and curing time is 0.5-7 hours.
35. The method according to claim 15, comprising the steps of:
(1) preparing a carbon fiber framework: mixing the carbon fiber subjected to surface hydrophilic treatment with an aqueous solution of a binder, and mixing the mixture in vacuum for 10-30 min at a rotating speed of 1500-2500 rpm to obtain a carbon fiber suspension with the volume percentage of the carbon fiber being 1-20%; then freezing the carbon fiber suspension liquid by using liquid nitrogen, and drying in vacuum for 10-30 h to obtain the carbon fiber framework with carbon fibers arranged along a single orientation;
(2) preparing a thermal interface composite material: completely immersing the carbon fiber skeleton obtained in the step (1) into a liquid polymer, then placing the carbon fiber skeleton into a vacuum drying oven, and carrying out vacuum filtration for 2-4 h at the temperature of 30-50 ℃; and then heating and curing for 0.5-7 h at the temperature of 100-250 ℃ to obtain the thermal interface composite material.
36. An electronic component comprising the thermal interface composite according to any one of claims 1 to 14.
37. An electronic device characterized by comprising the electronic component according to claim 36.
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