CN109370493B - Thermal interface material and preparation method thereof - Google Patents
Thermal interface material and preparation method thereof Download PDFInfo
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- CN109370493B CN109370493B CN201811086541.5A CN201811086541A CN109370493B CN 109370493 B CN109370493 B CN 109370493B CN 201811086541 A CN201811086541 A CN 201811086541A CN 109370493 B CN109370493 B CN 109370493B
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
Abstract
The invention provides a thermal interface material and a preparation method thereof. The thermal interface material comprises matrix resin and a modified boron nitride nanotube; the modified boron nitride nanotube comprises a boron nitride nanotube and nano cellulose fibers adsorbed on the surface of the boron nitride nanotube; the mass ratio of the nano cellulose fiber to the boron nitride nanotube is 1-5%. The thermal interface material is prepared by firstly modifying a boron nitride nanotube by using nano cellulose fibers to obtain a modified boron nitride nanotube and then dispersing the modified boron nitride nanotube in matrix resin. According to the invention, the boron nitride nanotube is subjected to non-covalent functional modification by adopting the nano cellulose fiber, so that the thermal conductivity coefficient of the thermal interface material is improved and can reach 5-10W/m.K.
Description
Technical Field
The invention belongs to the technical field of heat conduction materials, and particularly relates to a thermal interface material and a preparation method thereof.
Background
With the miniaturization and high integration of electronic devices, the packing density of electronic components continues to increase, providing powerful usage functions, while also leading to a dramatic increase in the operating power consumption and heat generation thereof. CPU failures due to overheating account for up to 55% of the total number of CPU failures. Even for a single communication device or electronic component, the reliability is reduced by 50% for every 10 ℃ increase in operating temperature. Therefore, in order to ensure high reliability while the device exhibits optimum performance, it is necessary to ensure that the heat generated by the heat-generating electronic component can be dissipated in a timely manner. Heat dissipation has become the most critical issue and technical bottleneck that limits the lifetime and performance of electronic devices.
The thermal interface material is also called interface heat conduction material, is a material commonly used for IC packaging and electronic heat dissipation, is mainly used for filling up micro-gaps and holes with uneven surfaces generated when two materials are jointed or contacted, improves the heat dissipation performance of devices, and is considered as an important material for solving the heat dissipation problem of electronic devices. The polymer-based thermal interface material is mainly composed of a polymer and a high thermal conductive inorganic filler. The thermal interface material has the advantages of strong cohesiveness, low price and strong operation performance, and becomes the first choice of the thermal interface material. However, the thermal conductivity of the currently developed polymer-based thermal interface materials is lower than 5W/m · K, mainly because the thermal conductivity of the filler itself is too low and the interfacial thermal resistance between the filler and the polymer matrix is large.
The boron nitride has good thermal conductivity, electrical insulation, oxidation resistance and corrosion resistance, and has good application prospect when being used as a heat-conducting filler of a heat-conducting and insulating polymer composite material. In recent years, nanotubes have received a great deal of attention from scientists and industry. The theoretical value of the thermal conductivity coefficient of the boron nitride nanotube parallel to the tube axis direction can reach 6600W/m.K, and the experimental value is 200-300W/m.K.
Boron nitride nanotubes are used as fillers to be added into various polymer matrixes by the journal of hong Kong City university, and the like, and the change of the thermal conductivity coefficient of the boron nitride nanotubes is contrastingly researched. The results show that the thermal conductivity of the polymer composite material is remarkably improved after the boron nitride nanotubes are doped, particularly the thermal conductivity of the material is improved by more than 20 times after 35 vol% of the boron nitride nanotubes are doped into polystyrene, but the thermal conductivity is still less than 5W/m.K. CN 107779153A discloses a high-thermal-conductivity flame-retardant epoxy resin pouring sealant and a preparation method thereof, wherein the thermal conductivity of the pouring sealant is improved by adding boron nitride nanotubes or boron nitride nanosheets into epoxy resin, but the thermal conductivity of the pouring sealant is below 5W/m.K.
Therefore, how to prepare the polymer thermal interface material with the thermal conductivity larger than 5W/m.K by utilizing the self-high thermal conductivity of the boron nitride nanotube is still a great challenge.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a thermal interface material and a preparation method thereof. Compared with the common boron nitride nanotube filled polymer-based thermal interface material, the thermal interface material provided by the invention has better heat conduction performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a thermal interface material comprising a matrix resin and modified boron nitride nanotubes;
the modified boron nitride nanotube comprises a boron nitride nanotube and nano cellulose fibers adsorbed on the surface of the boron nitride nanotube;
the mass ratio of the nanocellulose fibers to the boron nitride nanotubes is 1-5% (e.g., 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, or 5%, etc.).
According to the invention, the boron nitride nanotube is subjected to non-covalent functional modification by adopting the nano cellulose fiber, so that the dispersibility of the boron nitride nanotube in matrix resin is improved, and the interface interaction of the boron nitride nanotube and the matrix resin is improved, and a heat conduction network can be formed under the condition of low content of the boron nitride nanotube, so that the obtained thermal interface material has high heat conduction performance.
In a preferred embodiment of the present invention, the matrix resin is a cured epoxy resin.
Preferably, the content of the modified boron nitride nanotubes in the thermal interface material is 10-30 wt%; for example, it may be 10 wt%, 12 wt%, 13 wt%, 15 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, 23 wt%, 25 wt%, 26 wt%, 28 wt%, or 30 wt%, etc.
As the preferable technical scheme of the invention, the diameter of the boron nitride nanotube is 10-200 nm; for example, it may be 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm or 200 nm. .
Preferably, the length of the boron nitride nanotube is 2-20 μm; for example, it may be 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, 12 μm, 13 μm, 15 μm, 16 μm, 18 μm or 20 μm.
Preferably, the diameter of the nano cellulose fiber is 20-50 nm; for example, it may be 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50 nm.
Preferably, the length of the nanocellulose fibers is 1-10 μm; for example, it may be 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.
As a preferred technical scheme of the invention, the thermal interface material comprises the following raw material components in percentage by mass:
25-60% of epoxy resin, 10-30% of the modified boron nitride nanotube, 5-40% of curing agent and 0.1-5% of catalyst.
In the present invention, the mass percentage of the epoxy resin may be 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, or the like.
The modified boron nitride nanotube may be 10%, 12%, 13%, 15%, 16%, 18%, 20%, 22%, 23%, 25%, 26%, 28%, 30%, or the like, in mass%.
The mass percentage of the curing agent may be 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, or the like.
The mass percentage of the catalyst may be 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5%, or the like.
As a preferred embodiment of the present invention, the epoxy resin is a liquid epoxy resin.
Preferably, the liquid epoxy resin is selected from one or a combination of at least two of bisphenol A type liquid epoxy resin, bisphenol F type liquid epoxy resin or alicyclic liquid epoxy resin; typical but non-limiting examples of such combinations are: a combination of a bisphenol a type liquid epoxy resin and a bisphenol F type liquid epoxy resin, a combination of a bisphenol a type liquid epoxy resin and an alicyclic liquid epoxy resin, a combination of a bisphenol F type liquid epoxy resin and an alicyclic liquid epoxy resin, and the like.
As a preferred technical scheme of the invention, the curing agent is selected from one or the combination of at least two of methyl hexahydrophthalic anhydride, tetraethylenepentamine or m-phenylenediamine; typical but non-limiting examples of such combinations are: a combination of methylhexahydrophthalic anhydride and tetraethylenepentamine, a combination of methylhexahydrophthalic anhydride and m-phenylenediamine, a combination of tetraethylenepentamine and m-phenylenediamine, and the like.
Preferably, the catalyst is selected from one or a combination of at least two of 2-ethyl-4-methylimidazole, N-dimethylbenzylamine or 2,4, 6-tris (dimethylaminomethyl) phenol; typical but non-limiting examples of such combinations are: a combination of 2-ethyl-4-methylimidazole and N, N-dimethylbenzylamine, a combination of 2-ethyl-4-methylimidazole and 2,4, 6-tris (dimethylaminomethyl) phenol, a combination of N, N-dimethylbenzylamine and 2,4, 6-tris (dimethylaminomethyl) phenol, and the like.
In another aspect, the present invention provides a method for preparing the thermal interface material, including the following steps:
(1) mixing the boron nitride nanotube with a nano cellulose fiber aqueous solution, and removing free nano cellulose fibers to obtain a modified boron nitride nanotube;
(2) and (2) dispersing the modified boron nitride nanotube obtained in the step (1) in matrix resin to obtain the thermal interface material.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing the boron nitride nanotube with a nano cellulose fiber aqueous solution, and removing free nano cellulose fibers to obtain a modified boron nitride nanotube;
(2) mixing epoxy resin, the modified boron nitride nanotube obtained in the step (1), a curing agent and a catalyst to obtain a mixed material;
(3) and (3) curing the mixed material obtained in the step (2) to obtain the thermal interface material.
As a preferable technical scheme of the invention, the concentration of the nano cellulose fiber aqueous solution is 0.1-1 mg/mL; for example, it may be 0.1mg/mL, 0.2mg/mL, 0.3mg/mL, 0.4mg/mL, 0.5mg/mL, 0.6mg/mL, 0.7mg/mL, 0.8mg/mL, 0.9mg/mL, 1mg/mL, or the like.
Preferably, the method of mixing in step (1) is ultrasonic mixing.
Preferably, the time of ultrasonic mixing is 3-12 h; for example, it may be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, or the like.
Preferably, the method for removing the free nano cellulose fiber in the step (1) is centrifugation.
Preferably, step (1) further comprises: after the removal of the free nanocellulose fibers, the obtained solid is dried.
Preferably, the drying temperature is 50-80 deg.C, such as 50 deg.C, 52 deg.C, 53 deg.C, 55 deg.C, 56 deg.C, 58 deg.C, 60 deg.C, 62 deg.C, 63 deg.C, 65 deg.C, 66 deg.C, 68 deg.C, 70 deg.C, 72 deg.C, 73 deg.C, 75 deg.C, 76 deg.C, 78 deg.C or 80 deg; the time is 3 to 12 hours, and may be, for example, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, or 12 hours.
Preferably, the mixing method in step (2) is: firstly, mixing epoxy resin, a curing agent and a catalyst by using a planetary stirrer, and then mixing the epoxy resin, the curing agent and the catalyst with the modified boron nitride nanotube obtained in the step (1) by using a ball mill.
Preferably, the stirring speed of the planetary stirrer is 1000-2000r/min, such as 1000r/min, 1100r/min, 1200r/min, 1300r/min, 1400r/min, 1500r/min, 1600r/min, 1700r/min, 1800r/min, 1900r/min or 2000 r/min; the stirring time is 1-5min, and can be, for example, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min or 5 min.
Preferably, the rotation speed of the ball mill is 200-2000r/min, such as 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min, 900r/min, 1000r/min, 1200r/min, 1300r/min, 1500r/min, 1600r/min, 1800r/min or 2000 r/min; the ball milling time is 1 to 6 hours, and may be, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours.
Preferably, the curing method in step (3) is a stepwise thermal curing process: the first step heat curing treatment temperature is 80-140 deg.C (such as 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C, 120 deg.C, 125 deg.C, 130 deg.C, 135 deg.C or 140 deg.C), and time is 0.5-2h (such as 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.2h, 1.3h, 1.5h, 1.6h, 1.8h or 2 h); the temperature of the second step thermal curing treatment is 140-; the third step heat curing treatment temperature is 160-.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing a boron nitride nanotube with 0.1-1mg/mL of nano cellulose fiber aqueous solution, performing ultrasonic dispersion for 3-12h, centrifuging to remove free nano cellulose fiber, and drying the obtained solid at 50-80 ℃ for 3-12h to obtain a modified boron nitride nanotube;
(2) adding epoxy resin, a curing agent and a catalyst into a planetary stirrer, mixing for 1-5min at the stirring speed of 1000-;
(3) the mixed material obtained in the step (2) is firstly subjected to heat curing treatment at 80-140 ℃ for 0.5-2h, then is subjected to heat curing treatment at 140-160 ℃ for 0.5-2h, and finally is subjected to heat curing treatment at 160-200 ℃ for 0.5-2h, so as to obtain the thermal interface material.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the boron nitride nanotubes are subjected to non-covalent functional modification by adopting the nano cellulose fibers, so that the dispersibility of the boron nitride nanotubes in matrix resin is improved, the interface interaction of the boron nitride nanotubes and the matrix resin is improved, and a heat-conducting network can be formed under the condition of low content of the boron nitride nanotubes. The thermal interface material provided by the invention has the thermal conductivity coefficient of 5-10W/m.K, and the preparation method is simple and can be used for industrial production.
Drawings
Fig. 1 is a scanning electron micrograph of the thermal interface material provided in example 1.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the specific embodiments are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a thermal interface material, which comprises the following raw material components in percentage by mass:
60% of bisphenol A type liquid epoxy resin (epoxy value is 0.44), 10% of modified boron nitride nanotube, 25% of methyl hexahydrophthalic anhydride and 5% of 2-ethyl-4-methylimidazole;
the modified boron nitride nanotube comprises a boron nitride nanotube and nano cellulose fibers adsorbed on the surface of the boron nitride nanotube, and the adsorption amount is 1.6% of the mass of the boron nitride nanotube; the diameter of the boron nitride nanotube is 10nm, and the length of the boron nitride nanotube is 2 microns; the diameter of the nano cellulose fiber is 20nm, and the length of the nano cellulose fiber is 1 mu m.
The preparation method of the thermal interface material comprises the following steps:
(1) mixing a boron nitride nanotube with 0.1mg/mL of nano-cellulose fiber aqueous solution, ultrasonically dispersing for 3h, centrifugally removing free nano-cellulose fibers, and drying the obtained solid at 50 ℃ for 12h to obtain a modified boron nitride nanotube (the adsorption capacity of the nano-cellulose fibers is 1.6 percent of the mass of the boron nitride nanotube);
(2) according to the formula, adding epoxy resin, a curing agent and a catalyst into a planetary stirrer, mixing for 1min at the stirring speed of 1000r/min, then adding the epoxy resin, the curing agent and the catalyst into a ball mill together with the modified boron nitride nanotube obtained in the step (1), and ball-milling for 6h at the rotating speed of 200r/min to obtain a mixed material;
(3) and (3) performing thermal curing treatment on the mixed material obtained in the step (2) at 80 ℃ for 2h, then performing thermal curing treatment at 140 ℃ for 2h, and finally performing thermal curing treatment at 160 ℃ for 2h to obtain the thermal interface material.
The surface topography of the thermal interface material provided in example 1 was characterized using a scanning electron microscope and the results are shown in fig. 1. As can be seen from fig. 1, the boron nitride nanotubes are uniformly dispersed in the cured epoxy resin, no agglomeration phenomenon exists, and a network is formed between the boron nitride nanotubes, thereby realizing the construction of a heat-conducting network.
Example 2
The embodiment provides a thermal interface material, which comprises the following raw material components in percentage by mass:
25% of bisphenol F type liquid epoxy resin (epoxy value is 0.51), 30% of modified boron nitride nanotube, 40% of tetraethylenepentamine and 5% of N, N-dimethylbenzylamine;
the modified boron nitride nanotube comprises a boron nitride nanotube and nano cellulose fibers adsorbed on the surface of the boron nitride nanotube, and the adsorption amount is 5% of the mass of the boron nitride nanotube; the diameter of the boron nitride nanotube is 200nm, and the length of the boron nitride nanotube is 20 microns; the diameter of the nano cellulose fiber is 50nm, and the length of the nano cellulose fiber is 10 mu m.
The preparation method of the thermal interface material comprises the following steps:
(1) mixing a boron nitride nanotube and a 1mg/mL nano-cellulose fiber aqueous solution, ultrasonically dispersing for 12h, centrifugally removing free nano-cellulose fibers, and drying the obtained solid at 80 ℃ for 3h to obtain a modified boron nitride nanotube (the adsorption capacity of the nano-cellulose fibers is 5% of the mass of the boron nitride nanotube);
(2) according to the formula, adding epoxy resin, a curing agent and a catalyst into a planetary stirrer, mixing for 5min at the stirring speed of 2000r/min, then adding the modified boron nitride nanotube obtained in the step (1), and mixing for 20min at the stirring speed of 2000r/min to obtain a mixed material;
(3) and (3) performing thermal curing treatment on the mixed material obtained in the step (2) at 140 ℃ for 0.5h, then at 160 ℃ for 0.5h, and finally at 200 ℃ for 0.5h to obtain the thermal interface material.
Example 3
The embodiment provides a thermal interface material, which comprises the following raw material components in percentage by mass:
50% of alicyclic liquid epoxy resin (epoxy value is 0.54), 20% of modified boron nitride nanotube, 29.9% of m-phenylenediamine and 0.1% of 2,4, 6-tris (dimethylaminomethyl) phenol;
the modified boron nitride nanotube comprises a boron nitride nanotube and nano cellulose fibers adsorbed on the surface of the boron nitride nanotube, and the adsorption amount is 3.5% of the mass of the boron nitride nanotube; the diameter of the boron nitride nanotube is 100nm, and the length of the boron nitride nanotube is 10 microns; the diameter of the nano cellulose fiber is 30nm, and the length is 5 μm.
The preparation method of the thermal interface material comprises the following steps:
(1) mixing a boron nitride nanotube with 0.5mg/mL of nano-cellulose fiber aqueous solution, ultrasonically dispersing for 6h, centrifugally removing free nano-cellulose fibers, and drying the obtained solid at 60 ℃ for 6h to obtain a modified boron nitride nanotube (the adsorption capacity of the nano-cellulose fibers is 3.5 percent of the mass of the boron nitride nanotube);
(2) according to the formula, adding epoxy resin, a curing agent and a catalyst into a planetary stirrer, mixing for 3min at a stirring speed of 1500r/min, then adding the epoxy resin, the curing agent and the catalyst into a ball mill together with the modified boron nitride nanotube obtained in the step (1), and ball-milling for 4h at a rotating speed of 1000r/min to obtain a mixed material;
(3) and (3) performing thermal curing treatment on the mixed material obtained in the step (2) at 120 ℃ for 1h, then performing thermal curing treatment at 150 ℃ for 1h, and finally performing thermal curing treatment at 180 ℃ for 1h to obtain the thermal interface material.
Example 4
The embodiment provides a thermal interface material, which comprises the following raw material components in percentage by mass:
40% of bisphenol A type liquid epoxy resin (epoxy value is 0.44), 25% of modified boron nitride nanotube, 32% of tetraethylenepentamine and 3% of 2-ethyl-4-methylimidazole;
the modified boron nitride nanotube comprises a boron nitride nanotube and nano cellulose fibers adsorbed on the surface of the boron nitride nanotube, and the adsorption amount is 3% of the mass of the boron nitride nanotube; the diameter of the boron nitride nanotube is 100nm, and the length of the boron nitride nanotube is 10 microns; the diameter of the nano cellulose fiber is 30nm, and the length is 5 μm.
The preparation method of the thermal interface material comprises the following steps:
(1) mixing a boron nitride nanotube with 0.5mg/mL of nano-cellulose fiber aqueous solution, ultrasonically dispersing for 9h, centrifugally removing free nano-cellulose fibers, and drying the obtained solid at 70 ℃ for 5h to obtain a modified boron nitride nanotube (the adsorption capacity of the nano-cellulose fibers is 3% of the mass of the boron nitride nanotube);
(2) according to the formula, adding epoxy resin, a curing agent and a catalyst into a planetary stirrer, mixing for 2min at the stirring speed of 1200r/min, then adding the epoxy resin, the curing agent and the catalyst into a ball mill together with the modified boron nitride nanotube obtained in the step (1), and ball-milling for 3h at the rotating speed of 800r/min to obtain a mixed material;
(3) and (3) performing thermal curing treatment on the mixed material obtained in the step (2) at 100 ℃ for 1.5h, then performing thermal curing treatment at 140 ℃ for 1h, and finally performing thermal curing treatment at 170 ℃ for 0.5h to obtain the thermal interface material.
Example 5
The embodiment provides a thermal interface material, which is different from embodiment 1 in that the thermal interface material comprises the following raw material components in percentage by mass:
60% of bisphenol A type liquid epoxy resin (epoxy value is 0.44), 16% of modified boron nitride nanotube, 20% of methyl hexahydrophthalic anhydride and 4% of 2-ethyl-4-methylimidazole; other conditions were the same as in example 1.
Example 6
The embodiment provides a thermal interface material, which is different from embodiment 1 in that the thermal interface material comprises the following raw material components in percentage by mass:
25% of bisphenol A type liquid epoxy resin (epoxy value is 0.44), 30% of modified boron nitride nanotube, 40% of methyl hexahydrophthalic anhydride and 5% of 2-ethyl-4-methylimidazole; other conditions were the same as in example 1.
Example 7
This example provides a thermal interface material, which differs from example 6 in that the boron nitride nanotubes have a diameter of 10nm and a length of 20 μm; other conditions were the same as in example 6.
Example 8
This example provides a thermal interface material, which differs from example 6 in that the boron nitride nanotubes have a diameter of 200nm and a length of 2 μm; other conditions were the same as in example 6.
Comparative example 1
The difference from example 6 is that boron nitride particles having an average particle diameter of 2 μm are used in place of the boron nitride nanotubes; other conditions were the same as in example 6.
Comparative example 2
The difference from the embodiment 6 is that the boron nitride nanotube is not modified, and the boron nitride nanotube is directly used for replacing the modified boron nitride nanotube; other conditions were the same as in example 6.
Comparative example 3
The difference from the example 6 is that in the modified boron nitride nanotube, the mass ratio of the nano cellulose fiber to the boron nitride nanotube is 10%; other conditions were the same as in example 6;
the preparation method of the modified boron nitride nanotube of comparative example 3 is as follows:
mixing a boron nitride nanotube with a 1mg/mL nano-cellulose fiber aqueous solution (the mass ratio of nano-cellulose fibers to the boron nitride nanotube is 10%), ultrasonically dispersing for 3h, filtering, and drying the obtained solid at 50 ℃ for 12 h.
The thermal conductivity of the thermal interface materials provided in examples 1-8 and comparative examples 1-3 was measured according to ASTM E1461-2013 (test method for measuring thermal diffusivity of solid by flash method), and the results are shown in Table 1 below:
TABLE 1
| Item | Coefficient of thermal conductivity (W/m. K) |
| Example 1 | 5.20 |
| Example 2 | 9.56 |
| Example 3 | 7.80 |
| Example 4 | 8.13 |
| Example 5 | 6.75 |
| Example 6 | 8.56 |
| Example 7 | 9.87 |
| Example 8 | 6.53 |
| Comparative example 1 | 3.12 |
| Comparative example 2 | 4.23 |
| Comparative example 3 | 5.34 |
As is clear from the results in Table 1, the present invention utilizes the non-covalent functionalization modification of boron nitride nanotubes with nanocellulose fibers to achieve a thermal conductivity of 5-10W/m.K for the resulting thermal interface material. When boron nitride particles are used instead of boron nitride nanotubes (comparative example 1), it is difficult to form a heat conductive network, and thus the thermal conductivity of the thermal interface material is greatly reduced. When the boron nitride nanotube is not modified by adopting the nano cellulose fiber (comparative example 2), the dispersibility of the boron nitride nanotube in the matrix resin is reduced, the boron nitride nanotube is easy to agglomerate, the formation of a heat conduction network is not facilitated, and the heat conductivity coefficient of the thermal interface material is reduced; when the content of the nanocellulose fiber is excessive (comparative example 3), the water absorption of the modified boron nitride nanotube is increased, the stability of the epoxy resin is reduced, the pores of the thermal interface material are increased, and the thermal conductivity is also reduced.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (22)
1. A thermal interface material, wherein the thermal interface material comprises a matrix resin and modified boron nitride nanotubes;
the modified boron nitride nanotube comprises a boron nitride nanotube and nano cellulose fibers adsorbed on the surface of the boron nitride nanotube;
the mass ratio of the nano cellulose fiber to the boron nitride nanotube is 1-5%;
the diameter of the nano cellulose fiber is 20-45 nm;
the length of the nano cellulose fiber is 1-10 mu m;
the content of the modified boron nitride nanotube in the thermal interface material is 10-30 wt%.
2. The thermal interface material of claim 1, wherein the matrix resin is a cured epoxy resin.
3. The thermal interface material of claim 1, wherein the boron nitride nanotubes have a diameter of 10-200 nm.
4. The thermal interface material of claim 1, wherein the boron nitride nanotubes are 2-20 μ ι η in length.
5. The thermal interface material as claimed in claim 1, comprising the following raw materials in percentage by mass:
25-60% of epoxy resin, 10-30% of the modified boron nitride nanotube, 5-40% of curing agent and 0.1-5% of catalyst.
6. The thermal interface material of claim 5, wherein the epoxy resin is a liquid epoxy resin.
7. A thermal interface material as defined in claim 6, wherein said liquid epoxy resin is selected from one or a combination of at least two of bisphenol A type liquid epoxy resin, bisphenol F type liquid epoxy resin, or cycloaliphatic liquid epoxy resin.
8. The thermal interface material of claim 5, wherein the curing agent is selected from one or a combination of at least two of methyl hexahydrophthalic anhydride, tetraethylene pentamine or metaphenylene diamine.
9. A thermal interface material as claimed in claim 5, wherein the catalyst is selected from one or a combination of at least two of 2-ethyl-4-methylimidazole, N-dimethylbenzylamine or 2,4, 6-tris (dimethylaminomethyl) phenol.
10. A method of making a thermal interface material as defined in claim 1, comprising the steps of:
(1) mixing the boron nitride nanotube with a nano cellulose fiber aqueous solution, and removing free nano cellulose fibers to obtain a modified boron nitride nanotube;
(2) and (2) dispersing the modified boron nitride nanotube obtained in the step (1) in matrix resin to obtain the thermal interface material.
11. The method of claim 10, comprising the steps of:
(1) mixing the boron nitride nanotube with a nano cellulose fiber aqueous solution, and removing free nano cellulose fibers to obtain a modified boron nitride nanotube;
(2) mixing epoxy resin, the modified boron nitride nanotube obtained in the step (1), a curing agent and a catalyst to obtain a mixed material;
(3) and (3) curing the mixed material obtained in the step (2) to obtain the thermal interface material.
12. The method according to claim 11, wherein the concentration of the aqueous solution of nanocellulose fibers is from 0.1 to 1 mg/mL.
13. The method of claim 11, wherein the mixing in step (1) is ultrasonic mixing.
14. The method of claim 13, wherein the ultrasonic mixing is performed for a period of time ranging from 3 to 12 hours.
15. The method for preparing the nano cellulose fiber according to claim 11, wherein the method for removing the free nano cellulose fiber in the step (1) is centrifugation.
16. The method of claim 11, wherein step (1) further comprises: after the removal of the free nanocellulose fibers, the obtained solid is dried.
17. The method according to claim 16, wherein the drying temperature is 50-80 ℃ and the drying time is 3-12 h.
18. The method of claim 11, wherein the mixing in step (2) is performed by: firstly, mixing epoxy resin, a curing agent and a catalyst by using a planetary stirrer, and then mixing the epoxy resin, the curing agent and the catalyst with the modified boron nitride nanotube obtained in the step (1) by using a ball mill.
19. The method as claimed in claim 18, wherein the stirring speed of the planetary stirrer is 1000-2000r/min, and the stirring time is 1-5 min.
20. The preparation method as claimed in claim 18, wherein the rotation speed of the ball mill is 200-2000r/min, and the ball milling time is 1-6 h.
21. The production method according to claim 11, wherein the curing method in step (3) is a stepwise heat curing process: the temperature of the first stage heat curing treatment is 80-140 ℃, and the time is 0.5-2 h; the temperature of the second step thermal curing treatment is 140-160 ℃, and the time is 0.5-2 h; the temperature of the third-step thermal curing treatment is 160-200 ℃, and the time is 0.5-2 h.
22. The method of claim 11, comprising the steps of:
(1) mixing a boron nitride nanotube with 0.1-1mg/mL of nano cellulose fiber aqueous solution, performing ultrasonic dispersion for 3-12h, centrifuging to remove free nano cellulose fiber, and drying the obtained solid at 50-80 ℃ for 3-12h to obtain a modified boron nitride nanotube;
(2) adding epoxy resin, a curing agent and a catalyst into a planetary stirrer, mixing for 1-5min at the stirring speed of 1000-;
(3) the mixed material obtained in the step (2) is firstly subjected to heat curing treatment at 80-140 ℃ for 0.5-2h, then is subjected to heat curing treatment at 140-160 ℃ for 0.5-2h, and finally is subjected to heat curing treatment at 160-200 ℃ for 0.5-2h, so as to obtain the thermal interface material.
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