CN118241379A - Preparation method of composite film, composite film and application of composite film - Google Patents
Preparation method of composite film, composite film and application of composite film Download PDFInfo
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Abstract
The embodiment of the application relates to the technical field of polymer-based heat-conducting composite materials, in particular to a preparation method of a composite film, the composite film and application thereof. In the method, BNNS@PDA has better dispersibility in a PI matrix, and is beneficial to improving the thermal conductivity of the composite film. In addition, the composite film is prepared by adopting a method combining in-situ polymerization, electrostatic spinning and compression molding, so that BNNS@PDA is uniformly dispersed and directionally arranged in a PI matrix, and the heat conductivity of the composite film is improved. Meanwhile, the s-CNT with larger length-diameter ratio can be lapped between BNNS@PDA and BNNS@PDA, so that a continuous heat conduction network passage is built in the PI substrate, and the heat conduction coefficient of the composite film is further improved. And the strong viscosity of the polydopamine ensures that the composite film maintains good breakdown strength. The composite film prepared by the method has excellent heat conduction performance and insulating performance; wherein, the heat conductivity coefficient of the composite film can be 0.574W/mK-0.703W/mK, and the volume resistivity can reach more than 10 15 Ω & cm.
Description
Technical Field
The embodiment of the application relates to the technical field of polymer-based heat-conducting composite materials, in particular to a preparation method of a composite film, the composite film and application thereof.
Background
In recent years, as electronic devices are rapidly developed toward higher power, integration, and multifunction, the operating frequency and packing density of the electronic devices are increasing, resulting in an increasing problem of overheating of the electronic devices. The large amount of heat generated and accumulated by the electronic device during operation not only reduces the working efficiency, stability and service life of the device, but also brings about great potential safety hazards. Therefore, the heat dissipation efficiency of the electronic device is improved, and the heat dissipation device has great significance for promoting the development of the electronic industry and guaranteeing the production safety.
Currently, the main approach to solve the problem of heat accumulation in electronic devices is to conduct the excess heat in the electronic device to the external environment through a heat sink material. The polymer-based heat conductive thin film material is widely used as a heat dissipation material for electronic devices due to its ultra-high in-plane heat conductivity and excellent flexibility.
Polyimide (PI) has excellent high temperature resistance, low temperature resistance, chemical corrosion resistance, electrical insulation properties, dimensional stability and the like, and is often used as a base material of a heat conductive composite film. However, the dispersibility of the heat conducting filler in the PI matrix is poor, which is unfavorable for improving the heat conducting performance of the PI-based heat conducting composite material.
Disclosure of Invention
In order to further improve the heat conduction performance of the PI-based composite material, the embodiment of the application provides a preparation method of a composite film, the composite film and application thereof, and a heat conduction double network can be constructed in a PI matrix by utilizing carboxylated carbon nanotubes and modified boron nitride nanosheets so as to improve the heat conduction performance of the composite film.
In order to solve the technical problems, the embodiment of the application provides the following technical scheme:
In a first aspect of the present application, there is provided a method of preparing a composite film, the method comprising the steps of: preparing a spinning solution, wherein the spinning solution comprises a polyamic acid solution, and carboxylated carbon nanotubes and polydopamine modified boron nitride nano-sheets dispersed in the polyamic acid solution; carrying out electrostatic spinning by using the spinning solution to obtain a first fiber felt; performing thermal imidization treatment on the first fiber felt to obtain a second fiber felt; the second fiber felt is molded to prepare a composite film; the first fiber felt is used for representing carboxylated carbon nano tube/polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt, and the second fiber felt is used for representing carboxylated carbon nano tube/polydopamine modified boron nitride nano sheet/polyimide composite fiber felt.
In the embodiment of the application, the polydopamine modified boron nitride nano-sheet (BNNS@PDA) has better dispersibility in the PI matrix, is beneficial to increasing the contact area between BNNS@PDA and between BNNS@PDA and the PI matrix, thereby reducing interface defects and heat transfer resistance between the PI matrix and the BNNS@PDA, reducing phonon scattering in the diffusion process and improving the heat conductivity of the composite film. In addition, the composite film is prepared by adopting a method combining in-situ polymerization, electrostatic spinning and compression molding, so that BNNS@PDA is uniformly dispersed and directionally arranged in a PI matrix, and the heat conductivity of the composite film is improved. Meanwhile, carboxylated carbon nanotubes (s-CNTs) with larger length-diameter ratio can be lapped between BNNS@PDA and BNNS@PDA, so that a continuous heat conduction network passage is built in a PI matrix, and the heat conduction coefficient of the composite film is further improved. And the strong viscosity of the polydopamine ensures that the composite film maintains good breakdown strength. The composite film prepared by the method has excellent heat conduction performance and insulating performance; wherein, the heat conductivity coefficient of the composite film can be 0.574W/mK-0.703W/mK, and the volume resistivity can reach more than 10 15 Ω & cm.
In some embodiments, the carboxylated carbon nanotubes comprise 0.1% -0.5% of the mass of the polyamic acid, and the polydopamine modified boron nitride nanoplatelets comprise 10% of the mass of the polyamic acid.
In some embodiments, the polydopamine modified boron nitride nanoplatelets comprise: the boron nitride nano-sheet and polydopamine distributed on the surface of the boron nitride nano-sheet, wherein the mass of polydopamine accounts for 20% -40% of the mass of the boron nitride nano-sheet.
In some embodiments, the configuring the dope includes: and adding the carboxylated carbon nano tube and the polydopamine modified boron nitride nano sheet into a polyamic acid solution, and stirring the polyamic acid solution to obtain the spinning solution.
In some embodiments, prior to the configuring the dope, the method further comprises: preparing polydopamine modified boron nitride nanosheets; the preparation of the polydopamine modified boron nitride nanosheets comprises the following steps: adding tris (hydroxymethyl) aminomethane into a mixed solution of deionized water and ethanol to prepare a buffer solution, wherein the pH value of the buffer solution is 8.5; adding the boron nitride nanosheets into the buffer solution, and performing ultrasonic treatment on the buffer solution; and adding dopamine into the buffer solution, stirring the buffer solution at room temperature, and removing supernatant after the buffer solution is gray black and a reaction product in the buffer solution is precipitated to obtain the polydopamine modified boron nitride nanosheets.
In some embodiments, prior to the configuring the dope, the method further comprises: preparing polyamide acid; the preparation of the polyamic acid comprises the following steps: under the ice water bath condition, 4' -diaminodiphenyl ether monomer and benzene tetra-acetic anhydride monomer are dissolved in N, N-dimethylformamide for polycondensation reaction to prepare polyamide acid; wherein the mass ratio of the 4,4' -diaminodiphenyl ether monomer to the pyromellitic anhydride monomer is 1.15:1.
In some embodiments, the temperature of the compression molding is 290 ℃ to 320 ℃, the pressure of the compression molding is 5MPa to 10MPa, and the time of the compression molding is 10min to 15min.
In some embodiments, the first fiber bond comprises a carboxylated carbon nanotube/polydopamine modified boron nitride nanoplatelet/polyamic acid composite fiber, and the arrangement of the carboxylated carbon nanotube/polydopamine modified boron nitride nanoplatelet/polyamic acid composite fiber comprises a zigzagged arrangement.
In a second aspect of the application there is also provided a composite film prepared according to the method of the first aspect.
In a third aspect of the present application, there is also provided an application of the composite film prepared by the method according to the first aspect in the field of electronic packaging.
It should be understood that the description in this summary is not intended to limit the critical or essential features of the disclosure, nor is it intended to limit the scope of the disclosure. Other features of the present disclosure will become apparent from the following description.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present invention, the drawings that are required to be used in the embodiments of the present invention will be briefly described below. It is evident that the drawings described below are only some embodiments of the present invention and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a schematic flow chart of a method for preparing a composite film according to some embodiments of the present application;
FIG. 2 is a schematic flow chart of a method for preparing a composite film according to other embodiments of the present application;
FIG. 3 is an SEM image of a composite film provided by some examples and comparative examples of the application;
FIG. 4 is a graph showing the results of thermal conductivity testing of the composite films provided by some examples and comparative examples of the present application, wherein (a) in FIG. 4 is the thermal conductivity of the composite films provided by some examples and comparative examples of the present application, and (b) in FIG. 4 is the rate of increase in the thermal conductivity of the composite films provided by some examples of the present application relative to the thermal conductivity of the composite film of comparative example 1;
fig. 5 is a graph of the volume resistivity of composite films provided by some examples of the application and comparative examples.
Detailed Description
The principles and spirit of the present disclosure will be described below with reference to several exemplary embodiments shown in the drawings. It should be understood that these specific embodiments are described merely to enable those skilled in the art to better understand and practice the present disclosure and are not intended to limit the scope of the present disclosure in any way. In the following description and claims, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.
As used herein, the term "comprising" and the like should be understood to be open-ended, i.e., including, but not limited to. The term "one embodiment" or "the embodiment" should be understood as "at least one embodiment". The terms "first," "second," and the like, may refer to different or the same object and are used solely to distinguish one from another without implying a particular spatial order, temporal order, order of importance, etc. of the referenced objects.
The polymer matrix generally has a low intrinsic thermal conductivity, and the addition of fillers with high thermal conductivity to the polymer matrix is a common method of increasing its thermal conductivity. For polymer-based thermally conductive composites, interfacial thermal resistance and phonon scattering at the filler/polymer and filler/filler interface are major factors that prevent further increases in their thermal conductivity. When the filler content is low, the main factor influencing the heat conductivity coefficient of the polymer matrix composite is the interfacial thermal resistance of the filler/polymer interface; and when the filler forms a heat conduction network structure, the main factor influencing the heat conduction coefficient of the polymer matrix composite is the interface thermal resistance between the filler and the filler. Effective strategies for reducing interface thermal resistance include: chemical modification of the filler surface, covalent bond connection between the filler and the polymer, coating of the polymer layer on the filler surface, construction of a 'bridge' structure by using high-heat-conductivity nano particles, and the like.
In addition to high thermal conductivity, other properties of heat dissipating materials are being developed by the modern, highly developed microelectronics industry, such as: the light and thin property, flatness, resistivity, mechanical property, thermal stability and the like are all put forward higher requirements. The light and thin heat conducting material can avoid increasing the volume of the microelectronic device; the good flatness can reduce the influence of the heat conduction material on the precision of the microelectronic device; the high resistivity can effectively avoid the short circuit of the electronic device caused by the heat conducting material; the excellent mechanical property and thermal stability can make the heat conducting material work stably under various extreme environments. Therefore, it is becoming more and more important to improve the overall properties of the thermally conductive material.
Based on the above, the embodiment of the application provides a preparation method of a composite film, the composite film and application thereof, wherein PI is used as a matrix material of the composite film, carboxylated carbon nanotubes and polydopamine modified boron nitride nanosheets are used as fillers, and the composite film with excellent comprehensive performance is prepared by using an electrostatic spinning process and a hot press forming process. In order to facilitate the reader's understanding of the application, a description is provided below in connection with specific examples.
The embodiment of the application provides a preparation method of a composite film. Fig. 1 and 2 show a schematic flow chart of a method for producing a composite film. Referring to fig. 1 and 2, the method includes the steps of:
And 11, preparing a spinning solution, wherein the spinning solution comprises a polyamic acid solution, and carboxylated carbon nanotubes and modified boron nitride nano-sheets dispersed in the polyamic acid solution.
In an embodiment of the present application, carboxylated carbon nanotubes (s-CNT) and polydopamine modified boron nitride nanoplatelets (bnns@pda) may be dispersed in a polyamic acid (PAA) solution to obtain a spinning solution. For example, the s-CNT, bnns@pda, and PAA solution may be mixed (e.g., s-CNT and bnns@pda are added to the PAA solution), and then the s-CNT and bnns@pda are uniformly dispersed in the PAA solution by stirring to obtain the spinning solution. In some embodiments, a mixture of BNNS@PDA and PAA solution may be prepared and then the s-CNT is added to the mixture of BNNS@PDA and PAA solution in portions. In the embodiment, the BNNS@PDA and the s-CNT are added into the PAA solution and uniformly dispersed, so that the dispersibility of the BNNS@PDA and the s-CNT in the PAA solution can be improved, and the preparation of the composite film with more uniform performance is facilitated. In other embodiments, s-CNT and bnns@pda may be added to DMF solution to perform ultrasonic dispersion, and the prepared PAA powder may be dissolved in the dispersion, and stirred at a low temperature to obtain a spinning solution.
In some embodiments, to improve the overall properties of the composite film, such as thermal conductivity, insulation, mechanical properties, etc., the mass of s-CNT is 0.1% -0.5% of the mass of PAA, and the mass of bnns@pda is 10% of the mass of PAA.
Boron nitride nano-sheets (BNNS) are widely applied to the fields of electronic packaging and insulating materials because of the advantages of high heat conductivity coefficient (lambda), low dielectric constant (epsilon), dielectric loss tangent value (tan delta), excellent oxidation resistance, corrosion resistance and the like. However, BNNS has difficulty in good bonding to most polymer matrices due to its low solubility, low functionality, and chemical inertness. The bnns@pda in the examples of the present application had better dispersibility relative to the unmodified boron nitride nanoplatelets. Therefore, BNNS@PDA is used as the filler, so that the contact area between the filler and the contact area between the filler and the PI matrix can be increased, the interface defect and the heat transfer resistance between the matrix and the filler are reduced, the scattering of phonons in the diffusion process is reduced, and the heat conductivity of the composite material is further improved. In addition, the strong viscosity of the polydopamine can also ensure that the composite film maintains good breakdown strength.
Specifically, in some embodiments, step 11 is preceded by the further step of: BNNS@PDA was prepared. The preparation method of BNNS@PDA comprises the following steps: adding boron nitride nano-sheets (BNNS) and dopamine into a mixed solution of Tris (hydroxymethyl) aminomethane (Tris), deionized water and ethanol, and reacting to obtain BNNS@PDA. BNNS@PDA comprises BNNS and PDAs distributed on the surface of the BNNS; wherein the mass of PDA accounts for 20% -40% of the mass of BNNS.
In some embodiments, the preparation method of the BNNS@PDA comprises the following steps: first, a buffer solution is prepared, which includes a mixed solution of Tris, deionized water and ethanol. For example, tris powder may be added to a mixed solution of deionized water and ethanol, and Tris may be sufficiently dissolved in the mixed solution of deionized water and ethanol by stirring to prepare a buffer. Secondly, BNNS powder is firstly added into a buffer solution, the BNNS powder is uniformly dispersed in the buffer solution in an ultrasonic dispersion mode, then dopamine is added, the mixture is stirred until the mixture solution is grey black, and after the mixture solution is placed for a period of time (or centrifugal treatment) at room temperature, the supernatant is removed, so that BNNS@PDA is obtained. In some embodiments, the volume ratio of deionized water to ethanol may be 3:1. In order to make the heat conducting property of the composite film better, the pH value of the buffer solution is 8.5.
In some embodiments, the mass of PDA in BNNS@PDA is 20% -40% of the mass of BNNS.
In the embodiment of the application, dopamine (DA) is oxidized and self-polymerized under the weak base condition formed by tris (hydroxymethyl) aminomethane to form Polydopamine (PDA) with strong adhesiveness, and the surface modification is carried out on the boron nitride nano-sheet (BNNS) through the PDA to obtain the polydopamine modified boron nitride nano-sheet (BNNS@PDA) with a large number of active groups (-NH and-OH). The inorganic filler BNNS is subjected to surface activation modification treatment, so that the dispersibility of BNNS can be effectively improved, the contact area between BNNS@PDA and between BNNS@PDA and a PI matrix is increased, interface defects and heat transfer resistance between the PI matrix and the BNNS@PDA are reduced, the scattering of phonons in the diffusion process is reduced, and the heat conductivity of the composite film is further improved.
In some embodiments, it is also desirable to dry the BNNS@PDA prior to the spin pack. The drying treatment mode specifically can be as follows: and (3) drying BNNS@PDA at 60-80 ℃ for 12-24 hours. Since PAA is easily polymerized and precipitated in water, mixing the aqueous dispersion of bnns@pda with the PAA solution results in precipitation of PAA, which reduces the yield of the target product. Therefore, in order to improve the dispersibility of bnns@pda in PAA solution, bnns@pda may be added to the PAA solution in the form of a dry powder during the preparation of the dope.
In some embodiments, step 11 is preceded by the further step of: PAA is prepared. The method for preparing PAA is as follows: under the ice water bath condition, 4' -diaminodiphenyl ether monomer and benzene tetra-acetic anhydride monomer are dissolved in N, N-dimethylformamide for polycondensation reaction to obtain polyamide acid. For example, the method for preparing PAA may specifically be as follows: under the ice water bath condition, adding 4,4' -diaminodiphenyl ether (ODA) monomer into N, N-Dimethylformamide (DMF) solution, stirring to completely dissolve the ODA monomer in DMF, adding pyromellitic anhydride (PMDA) monomer, and continuously stirring until the polymerization reaction is complete to obtain PAA solution. In order to further improve the heat conducting property of the composite film, the mass ratio of PMDA monomer to ODA monomer can be 1.15:1.
Specifically, in some embodiments, PMDA may be added to ODA-dissolved DMF in several batches during the preparation of PAA solution; after each addition of pyromellitic anhydride, the PMDA was dissolved in DMF with stirring and reacted completely, and then the next batch of PMDA was added. Specifically, in some embodiments, the weight of PMDA added in each batch is no more than 0.2g. By adding PMDA in batches, the heat generated in the dissolution process of PMDA can be effectively reduced, and the self-polymerization process of PMDA is avoided, so that the occurrence of side reaction is reduced, and the yield of the target product PAA is improved.
In some embodiments, step 11 specifically includes the steps of: adding ODA into a reaction vessel, adding DMF under the condition of ice water bath, adding PMDA in batches after the ODA is completely dissolved, adding BNNS@PDA and s-CNT after the PMDA is completely added and dissolved, and obtaining spinning solution after the reactants in the reaction vessel are subjected to polycondensation reaction.
The s-CNTs in the embodiments of the present application may be commercially available s-CNTs or self-made s-CNTs. The preparation method of the s-CNT is the prior art, and the embodiment of the application is not repeated.
And step 12, carrying out electrostatic spinning by using the spinning solution to obtain the first fiber felt.
Electrostatic spinning is a process of spinning by using spinning solution under high-voltage electrostatic condition. In some embodiments, the voltage of the high-voltage power supply is 15 kV-25 kV in the electrostatic spinning process. Specifically, the spinning solution can be added into an electrostatic spinning instrument to carry out electrostatic spinning, so that the s-CNT/BNNS@PDA/PAA solution is prepared into the s-CNT/BNNS@PDA/PAA composite fiber felt. The electrostatic spinning apparatus comprises an injection needle tube with a metal needle. The spinning solution was charged into an injection needle tube, and electrospinning was performed under conditions of an applied voltage of 18kV, a collection distance of 15cm, and a flow rate of the spinning solution of 0.017 mL/min.
In some embodiments, the arrangement of the s-CNT/bnns@pda/PAA composite fibers in the first fiber paste comprises a zig-zag arrangement. Compared with other arrangement modes, such as random arrangement or vertical arrangement, the zigzag arrangement mode is more beneficial to improving the heat conduction of the fiber-based material. The composite film prepared by using the S-CNT/BNNS@PDA/PAA composite fibers which are arranged in a zigzag manner has better heat conduction performance. Specifically, the s-CNT/bnns@pda/PAA composite fibers may be alternately arranged along the bending direction of the first fiber mat. For example, each time 1mL of the dope s-CNT/BNNS@PDA/PAA composite fiber is ejected, the fibers are alternately arranged. The electrostatic spinning can be carried out by using the method in the embodiment, so that the spinning solution can be continuously spun, and the s-CNT/BNNS@PDA/PAA composite fiber has the advantages of large length-diameter ratio, good appearance, no bonding phenomenon and non-spindle structure.
In the embodiment of the application, the composite fiber prepared by using the electrostatic spinning process has higher porosity, good interconnectivity, micron-sized gaps and larger surface volume ratio, and can be used as an excellent material for heat conduction of electronic elements. The s-CNT/BNNS@PDA/PAA solution is prepared into the s-CNT/BNNS@PDA/PAA composite fiber felt by adopting an electrostatic spinning process, so that the distribution uniformity of the s-CNT and the BNNS@PDA in a PI fiber matrix can be effectively improved, and the heat conducting property of the composite film is improved.
Step 13, performing thermal imidization treatment on the first fiber felt to obtain a second fiber felt;
in this embodiment, the first fiber mat may be subjected to a stepped thermal imidization treatment using a tube furnace in a nitrogen atmosphere to produce a second fiber mat. The heating rate of the thermal imidization treatment is 5 ℃/min, and the temperature of the thermal imidization treatment is 120 ℃ to 250 ℃.
In some embodiments, the imidization process is specifically as follows: (a) Heating the first fiber mat to 120 ℃ at a heating rate of 5 ℃/min, and annealing for 1 hour to remove the DMF solvent remained in the first fiber mat; (b) Heating the first fiber mat to 200 ℃ at a heating rate of 5 ℃/min, and annealing for 1 hour; (c) The first fiber mat was heated to 250 c at a ramp rate of 5 c/min and annealed for an additional 1h.
In some embodiments, step 13 is preceded by the further step of: the first fiber mat is placed in a vacuum environment for vacuum treatment. Specifically, the vacuum degree of the vacuum environment is 0.08-0.1 MPa, the temperature of the vacuum environment is 60-80 ℃, and the vacuum treatment time is 4-6 hours. In this embodiment, the organic solvent, such as DMF, in the first fiber mat may be removed by vacuum treating the first fiber mat. In some embodiments, to improve the removal efficiency of the organic solvent, the vacuum degree of the vacuum environment is 0.1MPa, the temperature of the vacuum environment is 60 ℃, and the time of the vacuum treatment is 4 hours.
And 14, performing compression molding on the second fiber felt to obtain the composite film.
In this embodiment, a plurality of layers of the second fiber mat may be compression molded to obtain a composite film. The shape and the size of each layer of the second fiber felt can be prepared according to actual needs; for example, each layer of second fibrous paper may be square in shape. For example, 2g of the second fiber mat may be weighed, cut into a sample of 20mm by 20mm size, placed in a mold, and compression molded on a small platen vulcanizer.
Specifically, in some embodiments, in order to improve the comprehensive performance of the composite film, the temperature of compression molding is 290 ℃ to 320 ℃, the pressure of compression molding is 5MPa to 10MPa, and the time of compression molding is 10min to 15min.
In the embodiment of the application, the polydopamine modified structure constructed on the boron nitride nanosheets can be effectively bonded with polyimide, so that the dispersibility of the boron nitride nanosheets in the polyimide film is effectively improved; in addition, the polyimide-based composite film is prepared by adopting an electrostatic spinning process, so that the dispersibility of the boron nitride nano-sheet in the polyimide film can be further improved while the mechanical strength of the polyimide film is ensured. Meanwhile, the method prepares the polydopamine modified boron nitride nano-sheet/polyimide composite fiber heat conduction film by compression molding a plurality of layers of carboxylated carbon nano-tubes/polydopamine modified boron nitride nano-sheet/polyimide composite fiber felt, and further effectively improves the mechanical strength of the composite film. The composite film can meet the requirements of the electronic device on electrical insulation performance, transverse heat transfer performance, high strength, light weight and the like, and reduce the risks of thermal management failure and the like of the electronic device.
The embodiment of the application also provides a composite film, namely the carboxylated carbon nano tube/modified boron nitride nano sheet/polyimide composite film, which is prepared by the method provided by the embodiment of the method.
In some embodiments, the carboxylated carbon nanotubes/modified boron nitride nanoplatelets/polyimide composite film has a thermal conductivity of 0.574W/mK to 0.703W/mK and a volume resistivity exceeding 10 15 Ω cm. The composite film has good heat conduction performance and insulating performance.
The embodiment of the application also provides an application of the composite film prepared by the method provided by the embodiment in the field of electronic packaging.
The composite film provided by the embodiment of the application can be filled in the gap between the heating device and the radiating fin or the metal base. The flexible characteristic that the composite film possesses makes it can laminate in the device surface that generates heat to the heat can be conducted from the device that generates heat (such as PCB etc.) to metal casing or fin on, is favorable to improving the radiating efficiency and the life of the device that generates heat. For example, the composite film may be disposed between the heat sink cold plate and the heat-generating chip to conduct heat generated by the chip into the heat sink cold plate, thereby reducing the temperature of the chip.
In the embodiment of the application, the polydopamine modified boron nitride nano-sheet (BNNS@PDA) has better dispersibility in the PI matrix, is beneficial to increasing the contact area between BNNS@PDA and between BNNS@PDA and the PI matrix, thereby reducing interface defects and heat transfer resistance between the PI matrix and the BNNS@PDA, reducing phonon scattering in the diffusion process and improving the heat conductivity of the composite film. In addition, the composite film is prepared by adopting a method combining in-situ polymerization, electrostatic spinning and compression molding, so that BNNS@PDA is uniformly dispersed and directionally arranged in a PI matrix, and the heat conductivity of the composite film is improved. Meanwhile, carboxylated carbon nanotubes (s-CNTs) with larger length-diameter ratio can be lapped between BNNS@PDA and BNNS@PDA, so that a continuous heat conduction network passage is built in a PI matrix, and the heat conduction coefficient of the composite film is further improved. And the strong viscosity of the polydopamine ensures that the composite film maintains good breakdown strength. The composite film prepared by the method has excellent heat conduction performance and insulating performance; wherein, the heat conductivity coefficient of the composite film can be 0.574W/mK-0.703W/mK, and the volume resistivity can reach more than 10 15 Ω & cm.
Several embodiments of the application are provided below.
Example 1
Step one: preparing spinning solution.
1.08G of ODA was added to a three-necked flask; 19g of DMF was added to a three-necked flask under ice-water bath conditions; after the ODA was completely dissolved in DMF, 1.244g of PMDA was added in portions to the three-necked flask, with the mass of PMDA added in each portion being 0.15g; after PMDA is completely added into the three-neck flask and dissolved, stirring the liquid in the three-neck flask for 30min by a mechanical stirring mode, adding 0.38g BNNS@PDA and 0.0076g s-CNT, and continuing stirring for 30min to obtain a mixed liquid of the s-CNT, the BNNS@PDA and PAA, namely a spinning solution. In the spinning solution, BNNS@PDA accounts for 10% of the mass of the PAA, and s-CNT accounts for 0.1% of the mass of the PAA; in BNNS@PDA, the mass of PDA accounts for 40% of the mass of BNNS.
And secondly, carrying out electrostatic spinning by using the spinning solution to obtain the first fiber felt.
And (3) filling the spinning solution obtained in the step (A) into an injection needle tube of an electrostatic spinning instrument, carrying out electrostatic spinning under the conditions of 18kV applied voltage, 15cm collecting distance and 0.017mL/min flow rate of the spinning solution, and collecting the first fiber adhesive on a roller with the rotating speed of 120 rpm. The humidity of the electrostatic spinning environment is (50+/-5)%, and the temperature of the electrostatic spinning environment is (25+/-3) °c. The inner diameter of the needle point of the injection needle tube is 0.41mm. The fiber collection method is a zigzag arrangement.
And thirdly, performing thermal imidization treatment on the first fiber felt to obtain a second fiber felt.
And (3) drying the first fiber mat in vacuum at 60 ℃ for 4 hours, and then placing the first fiber mat in a high-temperature oven to perform thermal imidization treatment in an atmosphere of N 2 to obtain a second fiber mat. The imidization treatment process specifically comprises the following steps: (a) Heating the first fiber mat to 120 ℃ at a heating rate of 5 ℃/min, and annealing for 1 hour to remove residual DMF solvent; (b) Heating the first fiber mat to 200 ℃ at a heating rate of 5 ℃/min, and annealing for 1h; (c) The first fiber mat was heated to 250 c at a ramp rate of 5 c/min and annealed for 1h.
And fourthly, performing compression molding on the second fiber felt to obtain the composite film.
2G of a second fiber mat was cut into a 20mm by 20mm sample, and the sample was placed in a mold, and compression molded on a small press vulcanizer to obtain a composite film. Wherein, the temperature of compression molding is 320 ℃, the pressure of compression molding is 10MPa, and the time of compression molding is 10min.
Example 2
This embodiment differs from embodiment 1 in that: in the spinning solution, the mass of s-CNT accounts for 0.2% of the mass of PAA.
Example 3
This embodiment differs from embodiment 1 in that: in the spinning solution, the mass of s-CNT accounts for 0.3% of the mass of PAA.
Example 4
This embodiment differs from embodiment 1 in that: in the spinning solution, the mass of s-CNT accounts for 0.4% of the mass of PAA.
Example 5
This embodiment differs from embodiment 1 in that: in the spinning solution, the mass of s-CNT accounts for 0.5% of the mass of PAA.
Comparative example 1
This embodiment differs from embodiment 1 in that: the spinning solution comprises unmodified CNTs and unmodified BNNS; and the mass of unmodified CNT in the spinning solution is 0.3% of the mass of PAA.
The results of the performance tests of examples 1-5 and comparative example 1 are provided below.
FIG. 3 shows a scanning electron microscope (SEARCH ENGINE MARKETING, SEM) image of the composite film provided in comparative example 1 and examples 1 to 5. Wherein (a) in fig. 3 is an SEM image of the composite film provided in comparative example 1, and (b) - (f) in fig. 3 are SEM images of the composite films provided in examples 1-5, respectively. As can be seen from fig. 3 (a), unmodified CNTs and unmodified BNNS are prone to agglomeration in PI matrix. As can be seen from FIGS. 3 (b) - (f), in the composite film prepared by using the modified s-CNTs and BNNS@PDA, the s-CNTs and BNNS@PDA are uniformly dispersed, and the s-CNTs are overlapped between the BNNS@PDA and the BNNS@PDA.
As can be seen from (a) in fig. 3 and (d) in fig. 3, the s-CNT in (d) in fig. 3 is more uniformly dispersed in the PI matrix than the unmodified CNT in (a) in fig. 3, with the same addition amount of s-CNT and unmodified CNT. This phenomenon is attributed to the covalent bond formed by the s-CNTs and the PI chains during in situ polymerization, which promotes interfacial bonding between the s-CNTs and the PI matrix.
The thermal conductivity magnitudes (λ, units of W/mK) of the composite films provided in comparative example 1 and examples 1 to 5 are shown in (a) and table one in fig. 4. As can be seen from (a) and Table one of FIG. 4, the thermal conductivity of the composite film is significantly improved as the s-CNT content is increased. As can be seen from (b) of fig. 4, in the spinning solution, when s-CNT accounts for 0.5% of PAA mass, the thermal conductivity of the composite material is improved by 25.6% with respect to comparative example 1.
List one
FIG. 5 shows the volume resistivity of the composite films provided in examples 1-5. As can be seen from FIG. 5, the volume resistivity of the composite films provided in examples 1-5 were all greater than 10 15 Ω & cm, far exceeding the volume resistivity required for electrical insulation (10 9 Ω & cm). Thus, the composite films provided in examples 1-5 are suitable for insulation performance requirements in electronic devices.
The thermal conductivity of the heat conducting filler is far higher than that of the polymer matrix, but under the condition that a single filler is added and the filler amount is low, gaps often appear in adjacent fillers, so that a heat conducting passage is discontinuous, and the heat conducting improvement of the material is limited. However, too large a filler amount reduces the mechanical properties of the material. Therefore, the embodiment of the application combines the two fillers of the s-CNT and the BNNS@PDA, plays the respective advantages of the two fillers, simultaneously shows good synergistic effect, forms a more effective heat conduction path, and can more effectively improve the heat conduction efficiency of the composite film even under the condition of smaller addition amount of the fillers.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; the technical features of the above embodiments or in the different embodiments may also be combined within the idea of the invention, the steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A method of preparing a composite film, the method comprising:
Preparing a spinning solution, wherein the spinning solution comprises a polyamic acid solution, and carboxylated carbon nanotubes and polydopamine modified boron nitride nano-sheets dispersed in the polyamic acid solution;
carrying out electrostatic spinning by using the spinning solution to obtain a first fiber felt;
Performing thermal imidization treatment on the first fiber felt to obtain a second fiber felt;
The second fiber felt is molded to prepare a composite film;
The first fiber felt is used for representing carboxylated carbon nano tube/polydopamine modified boron nitride nano sheet/polyamide acid composite fiber felt, and the second fiber felt is used for representing carboxylated carbon nano tube/polydopamine modified boron nitride nano sheet/polyimide composite fiber felt.
2. The method of claim 1, wherein the carboxylated carbon nanotubes are present in an amount of 0.1% to 0.5% by mass of the polyamic acid, and the polydopamine modified boron nitride nanoplatelets are present in an amount of 10% by mass of the polyamic acid.
3. The method of claim 2, wherein the polydopamine modified boron nitride nanoplatelets comprise: the boron nitride nano-sheet and polydopamine distributed on the surface of the boron nitride nano-sheet, wherein the mass of polydopamine accounts for 20% -40% of the mass of the boron nitride nano-sheet.
4. The method of claim 1, wherein said configuring the dope comprises:
and adding the carboxylated carbon nano tube and the polydopamine modified boron nitride nano sheet into a polyamic acid solution, and stirring the polyamic acid solution to obtain the spinning solution.
5. The method of claim 4, wherein prior to said configuring the dope, the method further comprises: preparing polydopamine modified boron nitride nanosheets;
The preparation of the polydopamine modified boron nitride nanosheets comprises the following steps:
adding tris (hydroxymethyl) aminomethane into a mixed solution of deionized water and ethanol to prepare a buffer solution, wherein the pH value of the buffer solution is 8.5;
adding the boron nitride nanosheets into the buffer solution, and performing ultrasonic treatment on the buffer solution;
And adding dopamine into the buffer solution, stirring the buffer solution at room temperature, and removing supernatant after the buffer solution is gray black and a reaction product in the buffer solution is precipitated to obtain the polydopamine modified boron nitride nanosheets.
6. The method of claim 4, wherein prior to said configuring the dope, the method further comprises: preparing polyamide acid;
The preparation of the polyamic acid comprises the following steps:
under the ice water bath condition, 4' -diaminodiphenyl ether monomer and benzene tetra-acetic anhydride monomer are dissolved in N, N-dimethylformamide for polycondensation reaction to prepare polyamide acid;
Wherein the mass ratio of the 4,4' -diaminodiphenyl ether monomer to the pyromellitic anhydride monomer is 1.15:1.
7. The method according to any one of claims 1 to 6, wherein the temperature of the compression molding is 290 ℃ to 320 ℃, the pressure of the compression molding is 5mpa to 10mpa, and the time of the compression molding is 10min to 15min.
8. The method of any one of claims 1-6, wherein the first fiber bond comprises a carboxylated carbon nanotube/polydopamine modified boron nitride nanoplatelet/polyamic acid composite fiber, and wherein the arrangement of the carboxylated carbon nanotube/polydopamine modified boron nitride nanoplatelet/polyamic acid composite fiber comprises a zig-zag arrangement.
9. A composite film prepared according to the method of any one of claims 1-8.
10. Use of a composite film prepared according to the method of any one of claims 1-8 in the field of electronic packaging.
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