CN113881080A - High-thermal-conductivity low-dielectric film based on sandwich structure and preparation method thereof - Google Patents
High-thermal-conductivity low-dielectric film based on sandwich structure and preparation method thereof Download PDFInfo
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The invention relates to the technical field of polymer composite material processing, in particular to a high-thermal-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof. The invention utilizes a ball milling method to strip and functionalize h-BN to obtain BNNSs-NH2(ii) a The MWCNTs-COOH is connected with a covalent bond, a highly oriented heat conduction path is formed by utilizing spin coating and hot pressing processes, and meanwhile, low dielectric constant and low dielectric loss are kept, so that the high heat conduction low dielectric film based on the sandwich structure is prepared. The preparation method provided by the invention has the advantages of easily obtained raw materials,simple process and low preparation cost.
Description
Technical Field
The invention relates to the technical field of polymer composite material processing, in particular to a high-thermal-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof.
Background
In recent years, miniaturization and integration have become the development trend of electronic devices. As electronic devices continue to increase in power, the amount of heat generated increases dramatically. A large amount of heat may have a certain effect on the stability and the service life of the electronic device. Therefore, the development of high-performance heat management materials is very critical to improving the heat dissipation of electronic equipment, and the heat generated by the electronic equipment is effectively and timely discharged, which obviously becomes an important research direction in the field of heat management.
Thermal interface materials have been widely used in the field of thermal management to fill micro voids and surface irregularities generated when a heat generating element contacts a heat dissipating element, thereby reducing thermal resistance during heat transfer. When the heating element is in direct contact with the heat-dissipating element, only a small portion of the apparent area between them is in actual contact due to the roughness of the surface, which is only about 10% of the area of the heat-dissipating element. The remaining areas are separated by air-filled gaps. Air has poor thermal conductivity, and is a poor conductor with a thermal conductivity of only 0.024 W.m-1K-1. The existence of these air gaps causes the interface thermal resistance at the two interfaces to rise sharply, which severely impedes the heat transfer. A large amount of heat can only be diffused through the actual contact points, but a small number of contact points causes a large amount of heat to be accumulated, thereby creating a serious thermal bottleneck. This will reduce the operating efficiency of the electronic device and affect the reliability, stability and lifetime of the electronic device. The high thermal conductivity thermal interface material is filled between the two interfaces, and can fill the gap between the two interfaces to exhaust air. Thereby increasing the effective contact area and improving the thermal contact between the two interfaces. A large number of effective heat conduction channels are established, the interface thermal resistance is greatly reduced, and the heat is rapidly discharged.
With the development of aviation and aerospace technologies, higher requirements are put forward on advanced resin matrix composite materials, and the materials are required to have high heat resistance, high thermal conductivity and excellent insulation and mechanical properties. Polyimide polymers are attracting attention because of their excellent thermal stability, mechanical properties and dielectric properties. However, the main chain of the aromatic heterocyclic ring in the aromatic heterocyclic ring is in a polar and straight structure, has high symmetry, is obtained by a thermal solid phase imidization process, shows the characteristics of difficult dissolution, difficult melting and the like, and causes difficulty in processing.
Disclosure of Invention
Aiming at the defects of the existing heat-conducting film technology, the invention aims to provide a high-heat-conducting low-dielectric film based on a sandwich structure and a preparation method thereof, namely a high-heat-conducting insulating film based on the cooperation of a sandwich structure and a highly-oriented multidimensional heat-conducting filler and a preparation method thereof. The invention has simple preparation process, common raw materials and low cost.
In the present invention, hexagonal boron nitride is abbreviated as "h-BN", boron nitride nanosheets are abbreviated as "BNNSs", triammonium phosphate, trihydrate or abbreviated as "(NH)3PO4·3H2O ", dichloromethane or simply" DCM ", polyetherimide or simply" PEI ", carboxylated multiwall carbon nanotubes or simply" MWCNTs-COOH ", 1-ethyl-3- (3-dimethylaminopropyl) carbodiimides hydrochloride or simply" EDC ", N-hydroxysuccinimide or simply" NHS ".
The purpose of the invention can be realized by the following technical scheme:
the first purpose of the invention is to provide a preparation method of a high-thermal-conductivity low-dielectric film based on a sandwich structure, which comprises the following steps:
(1) weighing h-BN and (NH)3PO4·3H2O, stripping and functionalizing h-BN to obtain BNNSs-NH2；
(2) Dispersing MWCNTs-COOH, EDC and NHS in DCM, and adding the BNNSs-NH obtained in the step (1) with stirring2Reacting in a nitrogen environment to obtain BNNSs @ MWCNTs;
(3) weighing PEI powder and dissolving the PEI powder in DCM to obtain a PEI solution;
(4) weighing the BNNSs @ MWCNTs obtained in the step (2), and uniformly mixing a PEI solution and the BNNSs @ MWCNTs to obtain a first mixed solution;
(5) weighing the BNNSs-NH2 obtained in the step (1), and uniformly mixing the PEI solution and BNNSs-NH2 to obtain a second mixed solution;
(6) dropwise adding the first mixed solution on a glass sheet of a coating machine, and performing spin coating to form a film; continuously spin-coating the second mixed solution, and alternately and repeatedly forming a thin film similar to a sandwich structure;
(7) and carrying out hot-pressing treatment on the film.
In one embodiment of the invention, in the step (1), the specific steps of peeling and functionalizing the h-BN are as follows:
(11) weighing h-BN and (NH)3PO4·3H2Adding O into a ball milling tank for ball milling;
(12) cleaning the ball milled BNNSs to remove (NH)3PO4·3H2O；
(13) Crushing the solution obtained in the step 2);
(14) centrifuging to obtain supernatant, and removing non-peeled h-BN;
(15) the lower layer was centrifuged again and the pellet was repeated 3 times and finally the dispersion solvent was changed to DCM.
In one embodiment of the present invention, in step 1), the ball milling conditions are: 560-;
preferably, the ball milling conditions are 640 r/min.
In one embodiment of the present invention, in step 1), the ball milling time is 20 h.
In one embodiment of the invention, step 2) the ball-milled BNNSs are washed with deionized water until pH 7.
In one embodiment of the invention, step 3) is performed by using a point-to-point cell disruptor at a power of 500W for 1 hour.
In one embodiment of the present invention, in step 4), the time is 10min during centrifugation, and the rotation speed is 1500-;
preferably, the rotation speed during centrifugation is 2000 rpm.
In one embodiment of the invention, in the step 5), the time is 10min during centrifugation, and the rotation speed is 6000-;
preferably, in the step 5), the rotation speed is 8000rpm during centrifugation.
In one embodiment of the present invention, in step (1), h-BN is reacted with (NH)3PO4·3H2The mass ratio of O is as follows: 1: 25-100 parts of; preferably, h-BN with (NH)3PO4·3H2The mass ratio of O is 1: 25.
in one embodiment of the present invention, in step (2), MWCNTs-COOH and BNNSs-NH2The mass ratio is 1: 1-2; preferably, MWCNTs-COOH and BNNSs-NH2The mass ratio is 1: 2.
in one embodiment of the invention, in step (2), the BNNSs @ MWCNTs are covalently linked.
In one embodiment of the present invention, in the step (3), the mass ratio of PEI to DCM is 1: 10.
in one embodiment of the invention, in the steps (3) to (5), the solution is mixed by ultrasound, and the ultrasound power is 200-;
preferably, the ultrasonic power is 300W.
In one embodiment of the present invention, in the step (6), the spin coating conditions are:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
in one embodiment of the present invention, in step (6), the number of the sandwich layers is 5, and 1.0mL of the spin-coating solution is used.
In one embodiment of the present invention, in step (6), after the sandwich-like structure of the thin film is obtained, the thin film is transferred to an oven to remove the solvent in vacuum.
In one embodiment of the invention, the temperature of the oven is set to 80 ℃, and the time of vacuum solvent removal is 30min-1 h;
preferably, the solvent removal time under vacuum is 1 h.
In one embodiment of the present invention, in the step (7), the hot-pressing condition is 250-280 ℃, 10-20MPa, 10-30 min;
preferably, the hot pressing condition is 280 ℃, 15MPa and 15 min.
The second purpose of the invention is to provide a high thermal conductivity low dielectric film based on a sandwich structure, which has a BNNSs @ MWCNTs highly oriented thermal conduction path structure in the in-plane direction formed by spin coating and hot pressing processes.
The principle of the technical scheme of the invention is as follows:
(1) the principle of BN stripping and functionalization by using physical ball milling is as follows:
the mechanical ball milling stripping method is to strip the h-BN layer by layer through a physical mechanical action. In the ball milling process, the h-BN is subjected to strong shearing force and impact force, and van der Waals force between the sheet layers is destroyed under the action of the shearing force and the impact force, so that the h-BN is stripped. Meanwhile, B atom sites are fully exposed due to strong physical action, so that the functionalization of h-BN is realized. And (NH)3PO4·3H2And O is used as a ball milling auxiliary agent in the ball milling process. The ball milling machine has the functions of buffering and lubricating in the ball milling process, reduces the impact of grinding balls and related abrasion and pollution, avoids BNNSs with smaller size generated under strong shearing force, and minimizes the damage to the crystal structure in the h-BN plane. And an amino group is introduced to realize the functionalization of BNNSs.
(2) The preparation principle of the highly oriented BNNSs @ MWCNTs/PEI high thermal conductive insulating film is as follows:
1) BNNSs-NH after stripping2The MWCNTs-COOH can form a covalent bond, the MWCNTs-COOH has better dispersibility in a matrix and better interface compatibility with the matrix, and the compounding of the multi-dimensional filler enables a heat conduction path to be formed in a system and improves the heat conduction performance.
2) Compared with other film forming methods, the spin coating film forming process can not only take away a part of low-boiling-point organic solvent due to high-speed rotation in the spin coating process, but also can ensure that the heat-conducting filler is uniformly distributed in the matrix.
3) In microelectronic packaging and radio communication technology, the thermal management material is also required to have low dielectric constant and low dielectric loss in order to reduce parasitic capacitance, signal delay and power consumption, and BNNSs-NH in the high thermal conductivity insulating film2the/PEI is used as an insulating layer, and effectively blocks the migration of carriers in BNNSs @ MWCNTs/PEI, so that the BNNSs @ MWCNTs/PEI has the advantages ofHas low dielectric constant and low dielectric loss.
4) Finally, the hot pressing process can enable BNNSs @ MWCNTs to form a highly oriented structure in the in-plane direction, and enable the film to form a stacked structure similar to a cement-brick, so that the interface thermal resistance is reduced, and the heat conducting performance and the mechanical performance are improved.
The molecular main chain of the polyetherimide resin (PEI) contains an ether bond and a meta-substituted structure and also has an isopropyl structure, so that the polyetherimide resin has excellent solubility and film forming property, and a thermoplastic film material prepared based on the polyetherimide resin has wide application prospect.
In the above-mentioned high thermal conductivity low dielectric film based on the sandwich structure and the preparation method thereof, in the first step, BNNSs is in the ball milling aid (NH)3PO4·3H2And (2) carrying out physical ball milling stripping under the action of O, wherein the action is that the BNNSs with the same mass is enabled to exist in a system in more thin layers through stripping, so that the efficiency of the BNNSs for improving the thermal conductivity of the composite material is increased, and the BNNSs is synchronously functionalized by virtue of the synergistic action of the ball milling auxiliary agent, so that the dispersion of the BNNS and the interface compatibility of the BNNS and the matrix are facilitated.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method is simple, the raw materials are easy to obtain, and the production cost is low.
(2) The film prepared by the method has a sandwich structure similar to a sandwich, and effectively maintains excellent low dielectric insulating property.
(3) The film prepared by the method has a structure similar to a cement-brick stacking structure, so that the composite film has high heat conduction and excellent mechanical properties (E' is 2502MPa, T)gAt 229 deg.C).
(4) The film prepared by the method can greatly improve the heat conduction performance of the composite material, and the heat conduction coefficient in the in-plane direction can be improved to 6.88W/mK which is 40.4 times of that of pure PEI.
(5) The multidimensional composite filler highly-oriented structure prepared by the method can avoid mechanical property damage of the composite material caused by excessive addition of inorganic filler.
(6) The filler has low price and small addition amount, and can meet economic benefits.
Drawings
Fig. 1 is an XRD pattern of comparative example 3 and example 2.
FIG. 2 is an infrared thermal image of the BNNSs @ MWCNTs/PEI composite films of comparative example 1 and example 2 and the change of the film surface temperature with time.
FIG. 3 is a schematic diagram showing the dielectric constants of the composite films of comparative examples 1 and 2 and example 2
Fig. 4 is a schematic diagram of dielectric loss of the composite films of comparative examples 1, 2 and example 2.
Detailed Description
The invention provides a preparation method of a high-thermal-conductivity low-dielectric film based on a sandwich structure, which comprises the following steps:
(1) weighing h-BN and (NH)3PO4·3H2O, stripping and functionalizing h-BN to obtain BNNSs-NH2；
(2) Dispersing MWCNTs-COOH, EDC and NHS in DCM, and adding the BNNSs-NH obtained in the step (1) with stirring2Reacting in a nitrogen environment to obtain BNNSs @ MWCNTs;
(3) weighing PEI powder and dissolving the PEI powder in DCM to obtain a PEI solution;
(4) weighing the BNNSs @ MWCNTs obtained in the step (2), and uniformly mixing a PEI solution and the BNNSs @ MWCNTs to obtain a first mixed solution;
(5) weighing the BNNSs-NH obtained in the step (1)2Mixing PEI solution with BNNSs-NH2Uniformly mixing to obtain a second mixed solution;
(6) dropwise adding the first mixed solution on a glass sheet of a coating machine, and performing spin coating to form a film; continuously spin-coating the second mixed solution, and alternately and repeatedly forming a thin film similar to a sandwich structure;
(7) and carrying out hot-pressing treatment on the film.
In one embodiment of the invention, in the step (1), the specific steps of peeling and functionalizing the h-BN are as follows:
(11) weighing h-BN and (NH)3PO4·3H2Adding O into a ball milling tank for ball milling;
(12) cleaning the ball milled BNNSs to remove (NH)3PO4·3H2O；
(13) Crushing the solution obtained in the step (2);
(14) centrifuging to obtain supernatant, and removing non-peeled h-BN;
(15) the lower layer was centrifuged again and the pellet was repeated 3 times and finally the dispersion solvent was changed to DCM.
In one embodiment of the present invention, in step 1), the ball milling conditions are: 560-;
preferably, the ball milling conditions are 640 r/min.
In one embodiment of the present invention, in step 1), the ball milling time is 20 h.
In one embodiment of the invention, step 2) the ball-milled BNNSs are washed with deionized water until pH 7.
In one embodiment of the invention, step 3) is performed by using a point-to-point cell disruptor at a power of 500W for 1 hour.
In one embodiment of the present invention, in step 4), the time is 10min during centrifugation, and the rotation speed is 1500-;
preferably, the rotation speed during centrifugation is 2000 rpm.
In one embodiment of the invention, in the step 5), the time is 10min during centrifugation, and the rotation speed is 6000-;
preferably, in the step 5), the rotation speed is 8000rpm during centrifugation.
In one embodiment of the present invention, in step (1), h-BN is reacted with (NH)3PO4·3H2The mass ratio of O is as follows: 1: 25-100.
Preferably, h-BN with (NH)3PO4·3H2The mass ratio of O is as follows: 1: 25.
in one embodiment of the present invention, in step (2), MWCNTs-COOH and BNNSs-NH2The mass ratio is 1: 1-2;
preferably, MWCNTs-COOH and BNNSs-NH2The mass ratio is 1: 2.
in one embodiment of the invention, in step (2), the BNNSs @ MWCNTs are covalently linked.
In one embodiment of the present invention, in the step (3), the mass ratio of PEI to DCM is 1: 10.
in one embodiment of the invention, in the steps (3) to (5), the solution is mixed by ultrasound, and the ultrasound power is 200-;
preferably, the ultrasonic power is 300W.
In one embodiment of the present invention, in the step (6), the spin coating conditions are:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
in one embodiment of the present invention, in step (6), the number of the sandwich layers is 5, and 1.0mL of the spin-coating solution is used.
In one embodiment of the present invention, in step (6), after the sandwich-like structure of the thin film is obtained, the thin film is transferred to an oven to remove the solvent in vacuum.
In one embodiment of the invention, the temperature of the oven is set to 80 ℃, and the time of vacuum solvent removal is 30min-1 h;
preferably, the solvent removal time under vacuum is 1 h.
In one embodiment of the present invention, in the step (8), the hot-pressing conditions are 250 ℃ and 280 ℃, 10-20MPa and 10-30 min;
preferably, the hot pressing condition is 280 ℃, 15MPa and 15 min.
The invention provides a high-thermal-conductivity low-dielectric film based on a sandwich structure, which is provided with a BNNSs @ MWCNTs highly oriented heat conduction path structure in an in-plane direction formed by spin coating and hot pressing processes.
The invention is described in detail below with reference to the figures and specific embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. Table 1 shows the main reagents and raw materials of the present invention.
TABLE 1 Main reagents and raw materials
Example 1
The embodiment provides a high-thermal-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof, and the preparation method comprises the following steps:
(1) h-BN and (NH)3PO4·3H2And O, stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) weighing the components in a mass ratio of 1: 25 of h-BN with (NH)3PO4·3H2Adding O into a ball milling tank, and ball milling for 20 hours at the rotating speed of 640 r/min;
2) the ball milled BNNSs were dispersed in deionized water and washed several times with deionized water to remove the remaining (NH) in solution3PO4·3H2O until the pH value is 7;
3) further crushing the obtained uniform dispersion solution for 1 hour under the power of 500W by using a point-to-point cell crusher;
4) centrifuging at 2000rpm for 10min, collecting supernatant, and removing un-peeled h-BN;
5) centrifugation was carried out at 8000rpm for 10min and the precipitate was removed, repeated 3 times, and the solvent of the dispersion was changed to DCM.
(2) 1g of MWCNTs-COOH, 0.5g of EDC and 0.3g of NHS were weighed and mixed to disperseThe mixed solution was stirred in a DCM solvent for 30min in a three-necked flask, followed by the addition of 1g of BNNSs-NH in step (1)2And reacting for 12 hours in a nitrogen environment to obtain BNNSs @ MWCNTs connected with covalent bonds.
(3) 4.2g PEI powder was weighed into 42mL DCM solution and sonicated to dissolve completely.
(4) And (3) weighing 0.8g of BNNSs @ MWCNTs obtained in the step (2) and the solution obtained in the step (3), mixing, and performing ultrasonic dispersion and uniform mixing to obtain a first mixed solution.
(5) 3.4g PEI powder was weighed into 34mL DCM solution and sonicated to dissolve completely.
(6) Weighing 1.6g of BNNSs-NH obtained in step (1)2And (5) mixing the solution obtained in the step (5), and performing ultrasonic dispersion and uniform mixing to obtain a second mixed solution.
(7) 1mL of first mixed solution is dripped on a glass sheet of a coating machine once, spin coating is carried out to form a film, 1mL of second mixed solution is further taken for continuous spin coating, a sandwich structure similar to a sandwich is formed alternately and repeatedly in this way, the spin coating is carried out for 5 times in total, and the spin coating conditions are as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
(8) the film was then transferred to an 80 ℃ oven to remove the solvent in vacuo for 1 h.
(9) Finally, the film is hot pressed for 15min at 280 ℃ and 15 MPa.
Example 2
The embodiment provides a high-thermal-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof, and the preparation method comprises the following steps:
(1) h-BN and (NH)3PO4·3H2And O, stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) weighing the components in a mass ratio of 1: 25 of h-BN with (NH)3PO4·3H2Adding O into a ball milling tank, and ball milling for 20 hours at the rotating speed of 640 r/min;
2) dispersing the ball-milled BNNSs in deionized water and using deionized waterWashing with water for several times to remove residual (NH) in solution3PO4·3H2O until the pH value is 7;
3) further crushing the obtained uniform dispersion solution for 1 hour under the power of 500W by using a point-to-point cell crusher;
4) centrifuging at 2000rpm for 10min, collecting supernatant, and removing un-peeled h-BN;
5) centrifugation was carried out at 8000rpm for 10min and the precipitate was removed, repeated 3 times, and the solvent of the dispersion was changed to DCM.
(2) 1g of MWCNTs-COOH, 0.5g of EDC and 0.3g of NHS were weighed out and mixed in DCM solvent, and the mixed solution was stirred in a three-necked flask for 30min, followed by addition of 2g of BNNSs-NH in step (1)2And reacting for 12 hours in a nitrogen environment to obtain BNNSs @ MWCNTs connected with covalent bonds.
(3) 4.2g PEI powder was weighed into 42mL DCM solution and sonicated to dissolve completely.
(4) And (3) weighing 0.8g of BNNSs @ MWCNTs obtained in the step (2) and the solution obtained in the step (3), mixing, and performing ultrasonic dispersion and uniform mixing to obtain a first mixed solution.
(5) 3.4g PEI powder was weighed into 34mL DCM solution and sonicated to dissolve completely.
(6) Weighing 1.6g of BNNSs-NH obtained in step (1)2And (5) mixing the solution obtained in the step (5), and performing ultrasonic dispersion and uniform mixing to obtain a second mixed solution.
(7) 1mL of first mixed solution is dripped on a glass sheet of a coating machine once, spin coating is carried out to form a film, 1mL of second mixed solution is further taken for continuous spin coating, a sandwich structure similar to a sandwich is formed alternately and repeatedly in this way, the spin coating is carried out for 5 times in total, and the spin coating conditions are as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
(8) the film was then transferred to an 80 ℃ oven to remove the solvent in vacuo for 1 h.
(9) Finally, the film is hot pressed for 15min at 280 ℃ and 15 MPa.
Example 3
The embodiment provides a high-thermal-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof, and the preparation method comprises the following steps:
(1) h-BN and (NH)3PO4·3H2And O, stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) weighing the components in a mass ratio of 1: 100 h-BN with (NH)3PO4·3H2Adding O into a ball milling tank, and ball milling for 20 hours at the rotating speed of 640 r/min;
2) the ball milled BNNSs were dispersed in deionized water and washed several times with deionized water to remove the remaining (NH) in solution3PO4·3H2O until the pH value is 7;
3) further crushing the obtained uniform dispersion solution for 1 hour under the power of 500W by using a point-to-point cell crusher;
4) centrifuging at 2000rpm for 10min, collecting supernatant, and removing un-peeled h-BN;
5) centrifugation was carried out at 8000rpm for 10min and the precipitate was removed, repeated 3 times, and the solvent of the dispersion was changed to DCM.
(2) 1g of MWCNTs-COOH, 0.5g of EDC and 0.3g of NHS were weighed out and mixed in DCM solvent, and the mixed solution was stirred in a three-necked flask for 30min, followed by addition of 2g of BNNSs-NH in step (1)2And reacting for 12 hours in a nitrogen environment to obtain BNNSs @ MWCNTs connected with covalent bonds.
(3) 4.2g PEI powder was weighed into 42mL DCM solution and sonicated to dissolve completely.
(4) And (3) weighing 0.8g of BNNSs @ MWCNTs obtained in the step (2) and the solution obtained in the step (3), mixing, and performing ultrasonic dispersion and uniform mixing to obtain a first mixed solution.
(5) 3.4g PEI powder was weighed into 34mL DCM solution and sonicated to dissolve completely.
(6) Weighing 1.6g of BNNSs-NH obtained in step (1)2And (5) mixing the solution obtained in the step (5), and performing ultrasonic dispersion and uniform mixing to obtain a second mixed solution.
(7) 1mL of first mixed solution is dripped on a glass sheet of a coating machine once, spin coating is carried out to form a film, 1mL of second mixed solution is further taken for continuous spin coating, a sandwich structure similar to a sandwich is formed alternately and repeatedly in this way, the spin coating is carried out for 5 times in total, and the spin coating conditions are as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
(8) the film was then transferred to an 80 ℃ oven to remove the solvent in vacuo for 1 h.
(9) Finally, the film is hot pressed for 15min at 280 ℃ and 15 MPa.
Example 4
The embodiment provides a high-thermal-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof, and the preparation method comprises the following steps:
(1) h-BN and (NH)3PO4·3H2And O, stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) weighing the components in a mass ratio of 1: 25 of h-BN with (NH)3PO4·3H2Adding O into a ball milling tank, and ball milling for 20 hours at the rotating speed of 640 r/min;
2) the ball milled BNNSs were dispersed in deionized water and washed several times with deionized water to remove the remaining (NH) in solution3PO4·3H2O until the pH value is 7;
3) further crushing the obtained uniform dispersion solution for 1 hour under the power of 500W by using a point-to-point cell crusher;
4) centrifuging at 2000rpm for 10min, collecting supernatant, and removing un-peeled h-BN;
5) centrifugation was carried out at 8000rpm for 10min and the precipitate was removed, repeated 3 times, and the solvent of the dispersion was changed to DCM.
(2) 1g of MWCNTs-COOH, 0.5g of EDC and 0.3g of NHS were weighed out and mixed in DCM solvent, and the mixed solution was stirred in a three-necked flask for 30min, followed by addition of 2g of BNNSs-NH in step (1)2And reacting for 12 hours in a nitrogen environment to obtain BNNSs @ MWCNTs connected with covalent bonds.
(3) 4.2g PEI powder was weighed into 42mL DCM solution and sonicated to dissolve completely.
(4) And (3) weighing 0.8g of BNNSs @ MWCNTs obtained in the step (2) and the solution obtained in the step (3), mixing, and performing ultrasonic dispersion and uniform mixing to obtain a first mixed solution.
(5) 3.4g PEI powder was weighed into 34mL DCM solution and sonicated to dissolve completely.
(6) Weighing 1.6g of BNNSs-NH obtained in step (1)2And (5) mixing the solution obtained in the step (5), and performing ultrasonic dispersion and uniform mixing to obtain a second mixed solution.
(7) 1mL of first mixed solution is dripped on a glass sheet of a coating machine once, spin coating is carried out to form a film, 1mL of second mixed solution is further taken for continuous spin coating, a sandwich structure similar to a sandwich is formed alternately and repeatedly in this way, the spin coating is carried out for 5 times in total, and the spin coating conditions are as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
(8) the film was then transferred to an 80 ℃ oven to remove the solvent in vacuo for 1 h.
(9) Finally, the film is hot pressed for 15min at 250 ℃ and 15 MPa.
Comparative example 1
The embodiment provides a high-thermal-conductivity low-dielectric film based on a sandwich structure and a preparation method thereof, and the preparation method comprises the following steps:
(1) 5g PEI powder was weighed into 50mL DCM solution and sonicated to dissolve completely.
(2) 1mL of the mixed solution was dropped onto a glass plate of a coater, and spin-coated to form a film, and this was repeated 5 times. The spin coating conditions were as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
(3) the film was then transferred to an 80 ℃ oven to remove the solvent in vacuo for 1 h.
(4) Finally, the film is hot pressed for 15min at 280 ℃ and 15 MPa.
Comparative example 2
The present comparative example provides a composite material and a method of making the same, comprising the steps of:
(1) h-BN and (NH)3PO4·3H2And O, stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) weighing the components in a mass ratio of 1: 25 of h-BN with (NH)3PO4·3H2Adding O into a ball milling tank, and ball milling for 20 hours at the rotating speed of 640 r/min;
2) the ball milled BNNSs were dispersed in deionized water and washed several times with deionized water to remove the remaining (NH) in solution3PO4·3H2O until the pH value is 7;
3) further crushing the obtained uniform dispersion solution for 1 hour under the power of 500W by using a point-to-point cell crusher;
4) centrifuging at 2000rpm for 10min, collecting supernatant, and removing un-peeled h-BN;
5) centrifugation was carried out at 8000rpm for 10min and the precipitate was removed, repeated 3 times, and the solvent of the dispersion was changed to DCM.
(2) 7.6g of PEI powder was weighed into 76mL of DCM solution and sonicated to dissolve it completely.
(3) Weighing 2g of BNNSs-NH obtained in the step (1)20.4g of MWCNTs-COOH, and the solution obtained in the step (2) are mixed, ultrasonically dispersed and uniformly mixed.
(4) 1mL of mixed solution is dripped on a glass sheet of a coating machine at a time, and spin coating is carried out for 5 times in total, wherein the spin coating conditions are as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
(5) the film was then transferred to an 80 ℃ oven to remove the solvent in vacuo for 1 h.
(6) Finally, the film is hot pressed for 15min at 280 ℃ and 15 MPa.
Comparative example 3
The composite material and the preparation method thereof provided by the comparative example comprise the following steps:
(1) h-BN and (NH)3PO4·3H2And O, stripping and functionalizing the h-BN by using a physical ball milling method. The method comprises the following specific steps:
1) weighing the components in a mass ratio of 1: 25 of h-BN with (NH)3PO4·3H2Adding O into a ball milling tank, and ball milling for 20 hours at the rotating speed of 640 r/min;
2) the ball milled BNNSs were dispersed in deionized water and washed several times with deionized water to remove the remaining (NH) in solution3PO4·3H2O until the pH value is 7;
3) further crushing the obtained uniform dispersion solution for 1 hour under the power of 500W by using a point-to-point cell crusher;
4) centrifuging at 2000rpm for 10min, collecting supernatant, and removing un-peeled h-BN;
5) centrifugation was carried out at 8000rpm for 10min and the precipitate was removed, repeated 3 times, and the solvent of the dispersion was changed to DCM.
(2) 7.6g of PEI powder was weighed into 76mL of DCM solution and sonicated to dissolve it completely.
(3) Weighing 2g of BNNSs-NH obtained in the step (1)20.4g of MWCNTs-COOH, and the solution obtained in the step (2) are mixed, ultrasonically dispersed and uniformly mixed.
(4) And (4) forming a film by a casting method.
(5) The film was then transferred to an 80 ℃ oven to remove the solvent in vacuo for 1 h.
The centrifugal times, centrifugal speed, ultrasonic power and ball milling speed have little influence on the final experimental result, and although only the optimal conditions are embodied in the embodiment, the high-thermal-conductivity low-dielectric film based on the sandwich structure with obvious effect can be obtained within the protection range of the invention, so the description of the invention on the values within the condition range is included in the protection range of the invention.
And (3) analyzing an experimental result:
the thermal conductivity of the composite films of examples 1, 2, 3 and 4 and comparative examples 1, 2 and 3 were 3.36W/mK,6.88W/mK,2.86W/mK,2.54W/mK,0.17W/mK,1.08W/mK and 1.17W/mK, respectively. By comparing examples 1 and 2, while MWCNTThe reaction ratio of s to BNNSs is controlled to be 1: 2, the composite material has the highest heat conductivity coefficient, which indicates that the ratio of the two is 1: 2, the reaction is optimized and a more efficient phonon transport channel can be provided. By comparing examples 2 and 3, when the ball milling ratio is 1: 25 of h-BN with (NH)3PO4·3H2And when O is used, the BNNSs has better stripping effect and is more uniformly dispersed in the matrix. Meanwhile, the example 2 shows excellent mechanical property, and E' reaches 2502MPa and Tg229 c is reached. Comparative examples 2 and 4 show that when the hot pressing temperature is 280 ℃, the thermal conductivity coefficient of the composite material is the highest, and the higher temperature can fully improve the orientation degree of the matrix and the filler, form a heat conduction path in the in-plane direction and improve the heat conduction performance.
Fig. 1 is an XRD pattern of comparative example 3 and example 2. Wherein in example 2I002/I100152, comparative example 3, I002/I100By comparing the two sets of data, the spin coating method realizes the orientation structure of the heat-conducting filler in the in-plane direction, namely 10.
FIG. 2 is an infrared thermal image of the BNNSs @ MWCNTs/PEI composite films of comparative example 1 and example 2 and the change of the film surface temperature with time. It can be visually observed that the surface temperature of example 2 reaches 82 ℃ at 6.9s, and the heat transmission rate is fastest.
Fig. 3 and 4 are dielectric properties of the composite films of comparative examples 1, 2 and example 2. Comparison shows that the heat-conducting film material with the sandwich structure constructed by the invention has low dielectric constant and low dielectric loss, and meets the requirement of the thermal interface material on the insulating property.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a high-thermal-conductivity low-dielectric film based on a sandwich structure is characterized by comprising the following steps:
(1) weighing h-BN and (NH)3PO4·3H2O, stripping and functionalizing h-BN to obtain BNNSs-NH2；
(2) Dispersing MWCNTs-COOH, EDC and NHS in DCM, and adding the BNNSs-NH obtained in the step (1) with stirring2Reacting in a nitrogen environment to obtain BNNSs @ MWCNTs;
(3) weighing PEI powder and dissolving the PEI powder in DCM to obtain a PEI solution;
(4) weighing the BNNSs @ MWCNTs obtained in the step (2), and uniformly mixing a PEI solution and the BNNSs @ MWCNTs to obtain a first mixed solution;
(5) weighing the BNNSs-NH obtained in the step (1)2Mixing PEI solution with BNNSs-NH2Uniformly mixing to obtain a second mixed solution;
(6) dropwise adding the first mixed solution on a glass sheet of a coating machine, and performing spin coating to form a film; continuously spin-coating the second mixed solution, and alternately and repeatedly forming a thin film similar to a sandwich structure;
(7) and carrying out hot-pressing treatment on the film.
2. The preparation method of the high-thermal-conductivity low-dielectric film based on the sandwich structure as claimed in claim 1, wherein in the step (1), the specific steps of peeling and functionalizing the h-BN are as follows:
(11) weighing h-BN and (NH)3PO4·3H2Adding O into a ball milling tank for ball milling;
(12) cleaning the ball milled BNNSs to remove (NH)3PO4·3H2O；
(13) Crushing the solution obtained in the step (12);
(14) centrifuging to obtain supernatant, and removing non-peeled h-BN;
(15) the lower layer was centrifuged again and the pellet was repeated 3-5 times and finally the dispersion solvent was changed to DCM.
3. The method as claimed in claim 2, wherein the rotation speed during centrifugation in step (14) is 2000-4000 rpm;
in the step (15), the rotation speed is 6000-8000rpm during centrifugation.
4. The method for preparing a high thermal conductivity low dielectric film based on a sandwich structure according to claim 1, wherein in the step (1), h-BN and (NH) are added3PO4·3H2The mass ratio of O is as follows: 1: 25-100 parts of; preferably, h-BN with (NH)3PO4·3H2The mass ratio of O is 1: 25.
5. the method for preparing a high thermal conductivity low dielectric film based on a sandwich structure of claim 1, wherein in the step (2), MWCNTs-COOH and BNNSs-NH are added2The mass ratio is 1: 1-2;
preferably, MWCNTs-COOH and BNNSs-NH2The mass ratio is 1: 2.
6. the method for preparing a high thermal conductivity low dielectric film based on a sandwich structure according to claim 1, wherein in the step (3), the mass ratio of PEI to DCM is 1: 10.
7. the method for preparing a high thermal conductivity low dielectric film based on a sandwich structure according to claim 1, wherein in the step (6), the spin coating conditions are as follows:
1)1000rpm，20s；
2)3000rpm，20s；
3)7000rpm，10s。
8. the method for preparing a high thermal conductivity low dielectric film based on a sandwich structure according to claim 1, wherein in the step (6), the number of the sandwich layers is 5; after a sandwich-like film was obtained, the film was transferred to an oven to remove the solvent in vacuo.
9. The method as claimed in claim 1, wherein the step (7) includes a hot pressing at 280 ℃ and 10-20MPa for 10-30min, preferably at 280 ℃ and 15MPa for 15 min.
10. The sandwich structure based high thermal conductivity low dielectric film as claimed in any one of claims 1-9, which has a BNNSs @ MWCNTs highly oriented thermal conductive via structure in the in-plane direction formed by spin coating and hot pressing processes.
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