CN113150557A - Silicon rubber composite material with directional arrangement and three-dimensional structure construction for improving heat conductivity, and preparation method and application thereof - Google Patents
Silicon rubber composite material with directional arrangement and three-dimensional structure construction for improving heat conductivity, and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010276 construction Methods 0.000 title description 3
- 239000000945 filler Substances 0.000 claims abstract description 61
- 239000004945 silicone rubber Substances 0.000 claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 229920001971 elastomer Polymers 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000010008 shearing Methods 0.000 claims abstract description 10
- 238000000748 compression moulding Methods 0.000 claims abstract description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 23
- 229910052582 BN Inorganic materials 0.000 claims description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 20
- 239000002041 carbon nanotube Substances 0.000 claims description 20
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011231 conductive filler Substances 0.000 claims description 4
- -1 methyl phenyl vinyl Chemical group 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
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- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
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- 239000004020 conductor Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 238000009776 industrial production Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007514 turning Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- MOSXLDGILGBOSZ-UHFFFAOYSA-N ethenyl-methyl-phenylsilicon Chemical compound C=C[Si](C)C1=CC=CC=C1 MOSXLDGILGBOSZ-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
- H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
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- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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Abstract
The invention discloses a silicone rubber composite material which is directionally arranged and is used for constructing a three-dimensional structure and improving heat conductivity, and a preparation method and application thereof. The method comprises the following steps: mixing a silicon rubber matrix, a heat-conducting filler and a silane coupling agent, and uniformly mixing to obtain a mixture; adding a vulcanizing agent, and uniformly mixing to obtain a rubber compound; shearing the rubber compound on an open mill along the horizontal plane of the rubber compound to obtain a rubber sheet, stacking the rubber sheets, moving the rubber sheets into a mold, performing compression molding, and curing to obtain the silicone rubber composite material which is directionally arranged, builds a three-dimensional structure and improves the thermal conductivity. According to the invention, the rubber compound is sheared on an open mill along the horizontal plane of the rubber compound to enable the two-dimensional filler to be directionally arranged and form a three-dimensional network structure by combining the functionalized one-dimensional carbon filler, so that the composite material obtains excellent heat-conducting property under the condition of ensuring good insulating property. The invention utilizes a simple mechanical processing method, has simple operation and quick forming, and the obtained sample has excellent heat-conducting property and simultaneously ensures good insulating property.
Description
Technical Field
The invention relates to the technical field of insulating heat-conducting silicone rubber, and discloses a silicone rubber composite material which is directionally arranged, constructs a three-dimensional structure and improves heat-conducting performance, and a preparation method and application thereof.
Background
With the rapid development of aerospace, artificial intelligence, automobile industry and electrics and electronics, the heat dissipation of components has stricter and higher requirements, so that a heat conducting material needs to be added between a heating element and a radiator or the environment to conduct the heat generated by a heating device in time, thereby ensuring the normal operation of the components. The heat conduction material is a thermal interface material which can conduct heat generated by a system out in time according to the heat conduction requirement of equipment so as to ensure the normal operation of the element. In some fields, the thermal interface material not only needs to have excellent heat-conducting property, but also needs to have good flame retardant property, mechanical property, insulating property and the like.
At present, the main heat conduction material is filling type heat conduction material, and the filling type heat conduction material fills high heat conduction and high insulation filler into a high polymer material matrix, so that a heat conduction network is formed inside the filling type heat conduction material, and the heat conduction performance of the composite material is improved. However, maintaining excellent thermal conductivity requires a high loading of the thermal interface material, which often results in poor mechanical properties and flame retardant properties, affecting the service life of the thermal interface material. It is therefore the current aim of research to obtain higher thermal conductivity at low loading, while other properties can be guaranteed. At present, the domestic and foreign research on the heat-conducting composite material mainly focuses on improving the heat conductivity of the composite material by means of surface modification of fillers, compounding and cooperation of various fillers, construction of a three-dimensional network structure, change of a processing technology and the like. For example, the documents Zakaaria M R, Akil H M, Kudus M H A, et al, enhancement of tensile and thermal properties of epoxy nanocomposites through chemical hybridization of carbon nanotubes and aluminum [ J ]. Composites Part A: Applied Science and Manufacturing 2014,66: 109-. And in the research so far, the good heat conducting performance of the heat conducting material is not researched through various ways. Therefore, the technology for preparing the heat-conducting silicone rubber composite material close to industrial production still needs to be improved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a silicone rubber composite material which is directionally arranged, constructs a three-dimensional structure and improves the heat-conducting property, and a preparation method and application thereof.
According to the preparation method provided by the invention, the processing mode is changed and the fillers with different dimensions are filled at the same time, so that the fillers are vertically distributed in the vertical direction and a three-dimensional network structure is constructed on the matrix, and thus the heat-conducting silicone rubber composite material with better heat-conducting property can be obtained at lower content.
The purpose of the invention is realized by at least one of the following technical solutions.
The silicone rubber composite material which is directionally arranged and has a three-dimensional structure and improved thermal conductivity is mainly prepared from silicone rubber, a thermal conductive filler (a two-dimensional layered filler and a one-dimensional carbon filler), a silane coupling agent and a vulcanizing agent.
In the preparation method provided by the invention, the directional arrangement is realized by that the internally mixed rubber compound reaches the result of shearing and pre-orienting the layered filler through a certain roller distance, the rubber compound and the vulcanizing agent are mixed in an open mill, the roller distance of the open mill is adjusted to a certain roller distance after uniform mixing, the rubber compound is put into the open mill for shearing and pre-orienting, the rubber compound is stacked together after shearing, and then the rubber compound is put into a die for compression molding and curing to obtain the final product.
The preparation method of the silicone rubber composite material which is directionally arranged, constructs a three-dimensional structure and improves the heat conductivity comprises the following steps:
(1) mixing a silicon rubber matrix, a heat-conducting filler and a silane coupling agent, and uniformly mixing to obtain a mixture;
(2) mixing the mixture obtained in the step (1) with a vulcanizing agent, and uniformly mixing to obtain a rubber compound;
(3) and (3) shearing the rubber compound obtained in the step (2) on an open mill along a horizontal plane to obtain a rubber sheet, stacking the rubber sheets together, transferring the rubber sheets into a mould, performing compression molding to obtain a plurality of samples, and curing to obtain the silicone rubber composite material which is directionally arranged, constructs a three-dimensional structure and improves the thermal conductivity.
Further, the silicon rubber matrix in the step (1) is more than one of methyl vinyl silicon rubber, dimethyl silicon rubber and methyl phenyl vinyl silicon rubber; the mixing temperature is 40-60 ℃.
Further, the heat-conducting filler of step (1) comprises a two-dimensional layered filler; the two-dimensional layered filler is more than one of aluminum oxide, Boron Nitride (BN) and silicon carbide; the particle size of the heat-conducting filler is 1-50 microns.
Preferably, the thermally conductive filler includes a two-dimensional layered filler and a one-dimensional carbon-based filler; the one-dimensional carbon filler is more than one of carbon nano tube and carbon fiber; the mass ratio of the two-dimensional layered filler to the one-dimensional carbon filler is (10-90): 1.
the one-dimensional carbon filler is a functional group modified filler and is one or a mixture of hydroxyl modification and carboxyl modification.
When the heat-conducting filler in the step (1) is the two-dimensional layered filler and the one-dimensional carbon filler, the mixing temperature is 40-60 ℃.
Further preferably, when the two-dimensional layered filler and the one-dimensional carbon-based filler are simultaneously selected as the heat-conducting filler in the step (1), the two-dimensional layered filler and the silane coupling agent may be added three times, and then the one-dimensional carbon-based filler may be added in batches.
Further, the silane coupling agent in the step (1) is more than one of gamma-methacryloxypropyltrimethoxysilane (KH-570), gamma-aminopropyltriethoxysilane (KH-550), vinyltrimethoxysilane (A-171) and silazane; the vulcanizing agent in the step (2) is more than one of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, bis (2, 4-dichlorobenzoyl) peroxide and a bi-component platinum vulcanizing agent.
Furthermore, according to the mass portion,
preferably, the mass ratio of the vulcanizing agent to the silicone rubber matrix is (1-3): 100.
further, the roll spacing of the open mill in the step (3) is 0.1-0.8 mm; the shearing frequency is more than 10 times; the thickness of the film is 0.1-2 mm.
Preferably, the roll spacing of the open mill in the step (3) is 0.1-0.5 mm.
Preferably, the thickness of the film in the step (3) is 0.2 mm.
Further, the pressure of the compression molding in the step (3) is 10-20 MPa; the curing temperature is 120-180 ℃, and the curing time is 5-10 min.
Preferably, the pressure for curing in the step (3) is 10-20 MPa.
Preferably, after the compression molding in step (3), the multiple samples are turned by 90 degrees along the horizontal plane and then placed into a mold for curing molding.
The invention provides the silicone rubber composite material which is prepared by the preparation method and is directionally arranged, constructs a three-dimensional structure and improves the heat-conducting property.
The silicone rubber composite material which is directionally arranged, constructs a three-dimensional structure and improves the heat conductivity can be applied to the preparation of radiating gaskets of electronic components.
The preparation method provided by the invention can compound the one-dimensional carbon filler and the two-dimensional layered filler at a certain temperature through banburying (mixing), and the two fillers are mutually overlapped in a matrix to construct a three-dimensional network structure through a certain chemical bond bonding.
In the preparation method provided by the invention, Boron Nitride (BN) is used as a two-dimensional layered filler, has excellent heat conductivity in the in-plane direction, and the heat conductivity of the Boron Nitride (BN) can reach 200-400 W.m-1K-1And tend to be horizontally aligned in the matrix. According to the invention, by utilizing the characteristic of the layered filler, the pre-orientation result is achieved by shearing the layered filler through an open mill through mechanical processing, then the composite material with the filler horizontally arranged in the matrix is cut and overturned, so that the horizontally arranged filler is vertically arranged in the matrix after being overturned, the bonding force between the matrix and the filler is improved by utilizing the silane coupling agent, and the thermal contact resistance between the filler and the matrix is reduced, thereby the composite material obtains excellent heat conductivity in the vertical direction. Meanwhile, based on the characteristic that the inherent thermal conductivity of the one-dimensional carbon material is far higher than that of the ceramic filler, a small amount of the hydroxyl modified one-dimensional carbon filler and the two-dimensional layered filler are filled in the matrix and are mutually overlapped to form a three-dimensional network structure, so that a heat conduction path is formed in the matrix more quickly. Because a small amount of carbon fillers are used and the BN fillers are isolated, the insulating property of the composite material is ensured, and meanwhile, the heat conducting property of the composite material is improved to a certain extent. In addition, the rubber compound is used as the combination of the base rubber and the silane coupling agent, so that the mechanical property of the composite material is ensured to a certain extent.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the preparation method provided by the invention, the sample with the filler directionally arranged in the matrix is constructed in a simple processing mode, meanwhile, the one-dimensional carbon material is added to quickly construct the heat conduction network and improve the heat conduction performance, and the insulation performance of the composite material is kept from being lost.
(2) The preparation method provided by the invention adopts a mechanical processing method, is easy to control, safe and pollution-free, is simple to operate, is rapid in forming and is suitable for industrial production.
Drawings
FIG. 1 is a flow chart of the preparation process in the embodiment;
fig. 2a is an SEM image of the silicone rubber composite prepared in comparative example 1;
FIG. 2b is an SEM image of the silicone rubber composite material which is prepared in example 1 and is oriented and constructed in a three-dimensional structure to improve the thermal conductivity;
fig. 2c is an SEM image of the silicone rubber composite prepared in comparative example 2;
FIG. 2d is an SEM image of the silicone rubber composite material which is prepared in example 2 and is oriented and constructed in a three-dimensional structure to improve the thermal conductivity;
fig. 2e is an SEM image of the silicone rubber composite prepared in comparative example 3;
fig. 2f is an SEM image of the silicone rubber composite material with improved thermal conductivity aligned and built up in a three-dimensional structure prepared in example 3.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
In the following examples, the thermal conductivity of the thermally conductive silicone rubber composite was tested in accordance with ISO 22007-22008.
Example 1
(1) Adding 35g of 100phr of methyl vinyl rubber compound (Sanchen organosilicon science and technology Co., Ltd., Dongguan city, trade name: 2051) into a Haake internal mixer (ordinary same experimental analytical instrument Co., Ltd., Guangzhou city, model: RTNI-55/03), adding 28g of heat-conducting filler BN (Tianyuan science and technology group, average particle size: 10 micron, purity: 99.8%) three times, carrying out internal mixing (mixing) for 10min each time at 50 ℃, uniformly mixing, adding 0.28g of silane coupling agent A-171 (Jinan Ring chemical industry Co., Ltd., purity: 99%) during the mixing process, taking out the mixture,
(2) the mixture obtained in step (1) was mixed with 0.756g of a vulcanizing agent (manufactured by Guangzhou trimerization chemical technology Co., Ltd., trade name: C8BS) in an open mill (Dongguan brand Konghong instruments and Equipment Co., Ltd., model: CH-0102).
(3) The roll distance of the open mill is adjusted to 0.2mm, and the mixture is placed in the open mill for shearing for 10 times, so that BN is horizontally distributed in the matrix, the horizontal orientation process is achieved, and the film with the thickness of 0.2mm is obtained. The 0.2mm film was cut into sheets of 100 x 0.2mm, and the sheets were stacked in this order. The stacked rubber sheets were placed in a 120 x 2mm mold, and then placed in a plate press (model: QLB-D, lazhou rubber machinery factory, china) to be pressed at normal temperature and 15MPa for 5min and then formed. Cutting the shaped sample into square strips of 120 x 2mm by using a cut-off knife, preparing 60 square strips according to the method, turning the square strips for 90 degrees along the horizontal direction (enabling the longest edge of each square strip to be vertical to the horizontal plane) and mutually attaching the square strips, so that the BN sheets are arranged from the original horizontal direction to the vertical direction. And finally, curing the attached sample at 175 ℃ and 15MPa for 10min, and then forming to obtain the silicone rubber composite material which is directionally arranged, constructs a three-dimensional structure and improves the heat conductivity.
Example 2
Adding 35g of 100phr of methyl vinyl rubber compound into a Haake mixer, adding 28g of BN three times, carrying out internal mixing for 10min each time, adding 0.28g of silane coupling agent A-171 during the mixing process, uniformly mixing, then adding 0.3166g of carbon nano tubes (OD: 5-15nm, length: 10-30 microns) three times, carrying out internal mixing for 10min each time, and carrying out the mixing at 50 ℃ to obtain a mixture. The subsequent steps are the same as those of the experimental case 1, and the silicone rubber composite material which is directionally arranged, constructs a three-dimensional structure and improves the heat-conducting property is obtained.
Embodiment 3
The preparation procedure was similar to that of example 2, except that 0.6363g of CNT (carbon nanotube) was added to obtain a silicone rubber composite material which was aligned and constructed to have a three-dimensional structure to improve thermal conductivity.
Comparative example 1
35g of a methyl vinyl compound (100 phr) was charged into a Haake internal mixer, 28g of BN was added in three portions, each time for 10 minutes, 0.28g of the silane coupling agent A-171 was added during the mixing, and the mixture 1 was taken out and mixed uniformly with 0.756g of a vulcanizing agent (manufactured by Guangzhou Trimerism technology Co., Ltd., trade name C8BS) in an open mill to obtain a mixture 2. And (3) putting the mixture 2 into a plate press, curing for 10min at 175 ℃ under 15MPa, and directly forming without cutting and turning to obtain the silicone rubber composite material.
Comparative example 2
The preparation procedure was similar to comparative example 1, except that: 0.3166g of CNT (carbon nano tube) was further added during the mixing process in the open mill to obtain a silicone rubber composite material.
Comparative example 3
The preparation procedure was similar to comparative example 1, except that: 0.6363g of CNT (carbon nano tube) was further added during the mixing process in the open mill to obtain a silicone rubber composite material.
Table 1 below is a table of thermal conductivity results for the products prepared in examples and comparative examples.
TABLE 1 thermal conductivity of examples and comparative examples
As can be seen from Table 1, the directionally arranged, thermally conductive silicone rubber composite material prepared by machining has better thermal conductivity, and when 80phr of filler is filled, the thermal conductivity of the embodiment 1 is 1.649 W.m-1K-1The improvement is 44% compared with the comparative example 1.
Fig. 2a is an SEM image of the silicone rubber composite prepared in comparative example 1; FIG. 2b is an SEM image of the silicone rubber composite material which is prepared in example 1 and is oriented and constructed in a three-dimensional structure to improve the thermal conductivity; as can be seen from fig. 2a, the BN of the lamellae tend to be arranged horizontally in the matrix, stacking one on top of the other to form a filler network. However, as can be seen from fig. 2b, after the composite material is prepared by mechanical processing, the BN is clearly exposed on the surface of the brittle-broken composite material in cross section, and the BN is in a vertically aligned state, the BN is vertically aligned and in contact with each other to form a heat conducting network, and only a small part of the BN is in a horizontally aligned state. Meanwhile, after 1 wt% of CNT is added when the addition amount of BN is 80phr, the heat-conducting property of the composite material is improved to a certain extent.
Fig. 2c is an SEM image of the silicone rubber composite prepared in comparative example 2; FIG. 2d is an SEM image of the silicone rubber composite material which is prepared in example 2 and is oriented and constructed in a three-dimensional structure to improve the thermal conductivity; after the CNT is added, as can be seen from fig. 2c, in addition to the surface-to-surface contact of BN, the contact between the dots formed between BN and CNT is also included, which forms a three-dimensional network structure in the matrix, further effectively constructs a filler network, and further improves the thermal conductivity of the composite material. Meanwhile, as can be seen from fig. 2d, after the composite material containing both BN and CNT is mechanically processed to prepare the oriented arrangement, not only the oriented arrangement of BN but also the CNT exists as a bridge between BN in the vertical direction, and the thermal conductivity of the composite material in the vertical direction reaches 1.924W · m-1K-1And is 1.7 times as large as that of comparative example 1.
Fig. 2e is an SEM image of the silicone rubber composite prepared in comparative example 3; fig. 2f is an SEM image of the silicone rubber composite material with improved thermal conductivity aligned and built up in a three-dimensional structure prepared in example 3. When the content of the CNT is further increased, as shown in fig. 2e and fig. 2f, the contact area between BN and the CNT is further increased, which is beneficial to reducing the thermal contact resistance between the filler and the matrix, thereby improving the thermal conductivity of the composite material. Due to the fact that the content of the CNT is low, and the conductive CNT are isolated from each other by the flake BN, the insulating property of the composite material is guaranteed. Even if the content of the CNT is 1 wt%, the volume resistivity of the composite material reaches the power of 12, and the application of the composite material in the field of heat conduction and insulation is effectively ensured.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of silicone rubber composite material which is directionally arranged and has three-dimensional structure and improved thermal conductivity is characterized by comprising the following steps:
(1) mixing a silicon rubber matrix, a heat-conducting filler and a silane coupling agent, and uniformly mixing to obtain a mixture;
(2) mixing the mixture obtained in the step (1) with a vulcanizing agent, and uniformly mixing to obtain a rubber compound;
(3) and (3) shearing the rubber compound in the step (2) on an open mill along the horizontal plane of the rubber compound to obtain a film, stacking the films together, transferring the films into a mould, pressing for forming, and curing to obtain the silicone rubber composite material which is directionally arranged, builds a three-dimensional structure and improves the thermal conductivity.
2. The method for preparing a silicone rubber composite material which is directionally arranged and constructed into a three-dimensional structure to improve the thermal conductivity as claimed in claim 1, wherein the silicone rubber matrix in the step (1) is one or more of methyl vinyl silicone rubber, dimethyl silicone rubber and methyl phenyl vinyl silicone rubber; the mixing temperature is 40-60 ℃.
3. The method for preparing silicone rubber composite material with improved thermal conductivity by orienting and constructing three-dimensional structure according to claim 1, wherein the thermally conductive filler of step (1) comprises two-dimensional layered filler; the two-dimensional layered filler is more than one of aluminum oxide, boron nitride and silicon carbide; the particle size of the heat-conducting filler is 1-50 microns.
4. The method for preparing the silicone rubber composite material which is directionally arranged and has the three-dimensional structure and the improved thermal conductivity as claimed in claim 3, wherein the thermal conductive filler comprises a two-dimensional layered filler and a one-dimensional carbon-based filler; the one-dimensional carbon filler is more than one of carbon nano tube and carbon fiber; the mass ratio of the two-dimensional layered filler to the one-dimensional carbon filler is (10-90): 1.
5. the method for preparing the silicone rubber composite material which is directionally arranged and has the three-dimensional structure and the improved thermal conductivity as claimed in claim 1, wherein the silane coupling agent in the step (1) is one or more of gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, vinyltrimethoxysilane and silazane; the vulcanizing agent in the step (2) is more than one of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, bis (2, 4-dichlorobenzoyl) peroxide and a bi-component platinum vulcanizing agent.
6. The method for preparing the silicone rubber composite material with improved thermal conductivity by directionally arranging and constructing the three-dimensional structure according to claim 1, wherein the silicone rubber composite material comprises, in parts by mass,
7. the method for preparing the silicone rubber composite material with improved thermal conductivity by directionally arranging and constructing a three-dimensional structure according to claim 1, wherein the roll gap of the open mill in the step (3) is 0.1-0.8 mm; the thickness of the film is 0.1-2 mm.
8. The method for preparing the silicone rubber composite material with the improved thermal conductivity by directionally arranging and constructing the three-dimensional structure according to claim 1, wherein the pressure for the compression molding in the step (3) is 10-20 MPa; the shearing frequency is more than 10 times; the curing temperature is 120-180 ℃, and the curing time is 5-10 min.
9. A silicone rubber composite material which is aligned and constructed in a three-dimensional structure to improve thermal conductivity, produced by the production method according to any one of claims 1 to 8.
10. The use of the silicone rubber composite material oriented and structured to provide a three-dimensional structure to improve thermal conductivity of an electronic component as recited in claim 9 in the manufacture of a heat sink for an electronic component.
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