CN117603506B - Boron nitride heat conduction material with three-dimensional network structure and preparation and application thereof - Google Patents
Boron nitride heat conduction material with three-dimensional network structure and preparation and application thereof Download PDFInfo
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- 229910052582 BN Inorganic materials 0.000 title claims abstract description 99
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims abstract description 17
- 239000000017 hydrogel Substances 0.000 claims abstract description 44
- 229920001661 Chitosan Polymers 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 29
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 28
- 239000004020 conductor Substances 0.000 claims abstract description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 238000010257 thawing Methods 0.000 claims abstract description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 45
- 239000002131 composite material Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 14
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- 239000006185 dispersion Substances 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 2
- 239000000945 filler Substances 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract 1
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- 101710149792 Triosephosphate isomerase, chloroplastic Proteins 0.000 description 4
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000004100 electronic packaging Methods 0.000 description 2
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- 229940005550 sodium alginate Drugs 0.000 description 2
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000005266 casting Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
Abstract
The invention relates to a boron nitride heat conduction material with a three-dimensional network structure, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Dropwise adding chitosan and polyacrylic acid solution into the boron nitride solution, stirring for 30-60 min at 85 ℃ in an oil bath, and stirring for 3-4 h in a normal temperature water bath; (2) And (3) placing the hydrogel in a planetary dispersing machine for dispersing treatment, placing the hydrogel in an ultrasonic cleaning machine for ultrasonic treatment for 20-30 min, uniformly extruding the hydrogel by using extrusion equipment, placing the hydrogel in a freezer of a refrigerator for ice assembly for 10-20 min at 18 ℃ below zero to 22 ℃ below zero, thawing the film in ethanol, performing solvent exchange in acetone, and finally taking the film out and placing the film in an oven for drying at 65 ℃ under normal pressure. The boron nitride heat-conducting material has a three-dimensional network structure, has excellent heat conductivity in the transverse direction and the longitudinal direction, has excellent resistivity and excellent flexibility, and can be applied to electronic devices with different shapes. And the preparation process is simple, no modification treatment is required to be carried out on the filler, the preparation period is shorter, and the repetition rate is higher.
Description
Technical Field
The invention belongs to the technical field of heat-conducting composite materials, and particularly relates to a boron nitride heat-conducting material with a three-dimensional network structure, and preparation and application thereof.
Background
With the continuous development of integration and miniaturization of electronic devices, efficient heat dissipation in the field of electronic packaging is a key issue. The use of a thermal interface material (THERMAL INTERFACE MATERIAL, TIM) between the heat source (i.e., the work equipment unit) and the heat sink can reduce or prevent overheating of the system. Therefore, TIMs with high thermal conductivity are critical for reliable and long-life operation of microelectronic products. The addition of fillers having higher thermal conductivity to the polymer matrix allows for the preparation of high performance polymer-based TIMs that achieve adequate thermal conductivity while allowing the mechanical properties of the composite to be compatible with the thermal expansion and contraction of the individual components. Boron nitride is widely used as a filler for TIMs in the field of electronic packaging because it itself has a relatively high thermal conductivity while also having good insulation. In order to effectively improve the heat conductivity of the composite material, the fillers are directionally arranged in the matrix to form a heat conducting channel, so that the heat conducting property of the composite material can be greatly improved.
Chinese patent CN113214583a discloses a thermal interface material with a vertical sandwich structure and a method for preparing the same by preparing a polymer gel mixed solution containing a thermally conductive filler and dripping the same onto a flat substrate. And (3) forming a film by using an ice casting gel solution containing calcium ions, freezing, and performing solvent exchange and normal-pressure drying on the frozen gel film to obtain the composite film with the vertical sandwich structure. The disclosed technology shows that the thermal interface material with the vertical sandwich structure has the advantages of bidirectional high thermal conductivity and excellent mechanical property, and can effectively improve the heat dissipation performance, but the method has the defects of low preparation yield, long period and the like because boron nitride needs to be peeled off in a mixed solvent in an ultrasonic manner and then centrifugally separated.
Disclosure of Invention
The invention aims to provide a boron nitride heat conduction material with a three-dimensional network structure and preparation and application thereof, so as to solve the problems of low preparation yield, long period and the like of the existing boron nitride.
A preparation method of a boron nitride heat conduction material with a three-dimensional network structure comprises the following steps:
(1) Preparing boron nitride, chitosan aqueous solution and polyacrylic acid aqueous solution, gradually dripping chitosan and polyacrylic acid solution into the boron nitride aqueous solution in the stirring process of the boron nitride aqueous solution, stirring for 30-60 min in an oil bath at 85 ℃ after all dripping is finished, and stirring for 3-4 h in a normal-temperature water bath to obtain boron nitride heat-conducting composite material hydrogel;
(2) And (3) putting the hydrogel obtained in the step (1) into a planetary disperser for dispersion treatment, putting the planetary disperser into an ultrasonic cleaner for ultrasonic treatment for 20-30 min, extruding the hydrogel onto a glass culture dish by using extrusion equipment, putting the glass culture dish into a refrigerator freezing chamber for ice assembly for 10-20 min at the temperature of 18 ℃ below zero to 22 ℃ below zero, thawing the film in ethanol, exchanging solvents in acetone, and finally taking out the film and putting the film into an oven for drying at the temperature of 65 ℃ under normal pressure to obtain the boron nitride heat-conducting material with the three-dimensional network structure.
In the invention, the chitosan and the polyacrylic acid solution are gradually dripped into the stirring process of the boron nitride solution, so that the chitosan and the polyacrylic acid solution are fully contacted at first, the time for forming a uniform hydrogel system is shortened, the boron nitride can be uniformly adsorbed and wrapped by the hydrogel, and the uniform hydrogel system is formed. Secondly, in the process of ice self-assembly of the hydrogel, the filler is induced by a temperature gradient, and a three-dimensional network structure is spontaneously constructed in a matrix.
The hydrogel is placed in the planetary disperser for dispersion treatment, so that boron nitride is uniformly distributed in the hydrogel, in the process, the boron nitride is more uniformly distributed in the hydrogel, and meanwhile, bubbles generated in the stirring process of the hydrogel are completely removed, so that the three are combined more tightly, and the formation of a three-dimensional structure in the ice assembling process is facilitated.
And then the hydrogel is placed in an ultrasonic cleaner for ultrasonic treatment, so that the boron nitride is favorably arranged in the hydrogel in a transverse orientation. The hydrogel is uniformly extruded by the extrusion equipment, so that the longitudinal orientation arrangement of the boron nitride in the ice assembly process is facilitated, and the combination of the two can greatly improve the repetition rate of the three-dimensional network structure.
Further, the mass ratio of the chitosan to the polyacrylic acid is 2: 1-1: 2. the chitosan is favorable for the boron nitride to form a three-dimensional network structure in the ice self-assembly process of the hydrogel at 18 ℃ below zero to 22 ℃ below zero. Polyacrylic acid can improve the flexibility of the film. When the chitosan content is too high, the three-dimensional network structure formed by the boron nitride is too loose; when the chitosan content is too low, the boron nitride is unfavorable to form a three-dimensional network structure.
Further, the mass fraction of the boron nitride in the boron nitride heat conduction material with the three-dimensional network structure is 20% -50%.
Further, in the step (1), the morphology of the boron nitride is sheet-shaped, and the median diameter D50 is 5-10 mu m. The flaky boron nitride has ultrahigh in-plane thermal conductivity and good electrical insulation property.
Further, in the step (2), the dispersing treatment time of the planet dispersing machine is 2-4 min, and the dispersing speed is 800-1000 r/min.
Further, the mass fraction of chitosan in the chitosan aqueous solution is 1-5%.
Further, the mass fraction of polyacrylic acid in the polyacrylic acid aqueous solution is 1-5%.
The boron nitride heat conduction material with the three-dimensional network structure is prepared by the method. The boron nitride heat conducting material has excellent heat conductivity in the transverse direction and the longitudinal direction, and is especially suitable for electronic devices such as display panels, chips and the like which need to have excellent heat conductivity in the transverse direction and the longitudinal direction.
The boron nitride heat conduction material with the three-dimensional network structure can be used in the field of electronic devices, and is particularly suitable for the fields such as display panels, chips and the like.
Compared with the prior art, the invention has the following advantages:
(1) The boron nitride can be directly used without long-time pretreatment such as ultrasonic treatment, so that the agglomeration phenomenon is avoided, and the boron nitride can be uniformly dispersed in a matrix; the whole manufacturing process is simpler, the manufacturing period is shorter, and the repetition rate is higher; cost can be saved and efficiency can be improved at the same time; is beneficial to large-scale production and application in industry.
(2) According to the invention, the boron nitride heat-conducting material with a three-dimensional network structure is obtained through vacuum defoamation of a planetary disperser, ice self-assembly at 18 ℃ below zero to 22 ℃ below zero and orientation means such as ultrasonic orientation, extrusion orientation and the like, has excellent heat conductivity in the transverse direction and the longitudinal direction, has excellent resistivity, and is favorable for supporting and being applied to the field of electronic devices.
(3) The invention has the advantages of short experimental period, simple experimental operation, no need of expensive equipment, no pollution to the environment in the experimental process and contribution to industrial large-scale application.
(4) The boron nitride heat-conducting composite material prepared by the invention has good flexibility and foldability, can be applied to electronic devices with different shapes, and has a very wide application range.
Drawings
Fig. 1 is an SEM image of the boron nitride heat conductive material having a three-dimensional network structure prepared in example 1.
Fig. 2 is an SEM image of the boron nitride heat conductive material with three-dimensional network structure prepared in example 2.
Fig. 3 is an SEM image of the boron nitride heat conductive material with three-dimensional network structure prepared in example 3.
Fig. 4 is an SEM image of the boron nitride heat conductive material without the three-dimensional network structure prepared in comparative example 1.
Fig. 5 is an SEM image of the boron nitride heat conductive material without the three-dimensional network structure prepared in comparative example 2.
Fig. 6 is an SEM image of the boron nitride heat conductive material having a three-dimensional network structure prepared in comparative example 3.
Fig. 7 is an SEM image of the boron nitride heat conductive material having a three-dimensional network structure prepared in comparative example 4.
Fig. 8 is a graph showing the comparison of the thermal conductivity of the boron nitride thermal conductive material with three-dimensional network structure and pure chitosan and polyacrylic acid polymer prepared in example 1.
Fig. 9 is a resistivity comparison graph of the boron nitride heat conductive material having a three-dimensional network structure prepared in example 1 and the polymer/BN composite film prepared in comparative example 7.
Fig. 10 is a diagram showing flexibility of the boron nitride heat conductive material having the three-dimensional network structure prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Example 1
A preparation method of a boron nitride heat conduction material with a three-dimensional network structure comprises the following steps:
(1) Respectively dispersing 1.25g of flaky boron nitride with the median diameter D50 of 5-10 mu m, 2.5g of chitosan and 2.5g of polyacrylic acid into 100g of ultrapure water to prepare three solutions, gradually dripping the chitosan and the polyacrylic acid solution into the three solutions in the stirring process of the boron nitride solution, stirring the solution for 30min in an oil bath at 85 ℃ after all dripping is finished, and stirring the solution in a normal-temperature water bath for 3-4 h to obtain the boron nitride heat-conducting composite material hydrogel;
(2) And (3) putting the hydrogel in the step into a planetary disperser to carry out dispersing treatment at the speed of 800r/min for 2-4 min, then putting the hydrogel into an ultrasonic cleaner to carry out ultrasonic treatment for 20-30 min, uniformly extruding the hydrogel onto a glass culture dish by using extrusion equipment, putting the glass culture dish into a refrigerator refrigerating chamber to carry out ice assembly at about 18 ℃ below zero for 10-20 min, thawing the film in ethanol, carrying out solvent exchange in acetone, and finally taking out the film and putting the film into an oven to carry out drying at the normal pressure of 65 ℃ to obtain the boron nitride heat-conducting material with the three-dimensional network structure.
As shown in FIG. 1, the cross section of the boron nitride heat-conducting composite material prepared by the invention has a three-dimensional network structure.
As shown in FIG. 8, the thermal conductivity of the boron nitride thermal conductive composite material prepared by the invention is far higher than that of the polymer film of pure chitosan and polyacrylic acid, and the three-dimensional network structure is proved to form a thermal conductive channel inside the composite material, so that the thermal conductivity is improved.
As shown in fig. 9, the resistivity of the boron nitride heat conductive material prepared in example 1 was 20 times that of the polymer/BN composite film prepared in comparative example 7. The boron nitride heat-conducting composite material has the advantages of remarkably improved resistivity and very good insulating property.
As shown in FIG. 10, the prepared boron nitride heat-conducting composite material has good flexibility and foldability, can be applied to electronic devices with different shapes, and has a very wide application range.
Example 2
(1) Respectively dispersing 2.14g of flaky boron nitride with the median diameter D50 of 5-10 mu m, 2.3g of chitosan and 2.7g of polyacrylic acid into 100g of ultrapure water to prepare three solutions, gradually dripping the chitosan and the polyacrylic acid solution into the three solutions in the stirring process of the boron nitride solution, stirring the solution for 30min in an oil bath at 85 ℃ after all dripping is finished, and stirring the solution in a normal-temperature water bath for 3-4 h to obtain the boron nitride heat-conducting composite material hydrogel;
(2) And (3) putting the hydrogel in the step into a planetary disperser to carry out dispersing treatment at the speed of 900r/min for 2-4 min, then putting the hydrogel into an ultrasonic cleaner to carry out ultrasonic treatment for 20-30 min, uniformly extruding the hydrogel onto a glass culture dish by using extrusion equipment, putting the glass culture dish into a refrigerator refrigerating chamber to carry out ice assembly at about 18 ℃ below zero for 10-20 min, thawing the film in ethanol, carrying out solvent exchange in acetone, and finally taking out the film and putting the film into an oven to carry out drying at the normal pressure of 65 ℃ to obtain the boron nitride heat-conducting material with the three-dimensional network structure.
As shown in FIG. 2, the cross section of the prepared boron nitride heat-conducting composite material has a three-dimensional network structure.
Example 3
(1) Respectively dispersing 1.25g of flaky boron nitride with the median diameter D50 of 5-10 mu m, 2.5g of chitosan and 2.0g of polyacrylic acid into 100g of ultrapure water to prepare three solutions, gradually dripping the chitosan and the polyacrylic acid solution into the three solutions in the stirring process of the boron nitride solution, stirring the solution for 30min in an oil bath at 85 ℃ after all dripping is finished, and stirring the solution in a normal-temperature water bath for 3-4 h to obtain the boron nitride heat-conducting composite material hydrogel;
(2) And (3) putting the hydrogel in the step into a planetary disperser to carry out dispersing treatment at the speed of 1000r/min for 2-4 min, then putting the hydrogel into an ultrasonic cleaner to carry out ultrasonic treatment for 20-30 min, uniformly extruding the hydrogel onto a glass culture dish by using extrusion equipment, putting the glass culture dish into a refrigerator refrigerating chamber to carry out ice assembly at about 18 ℃ below zero for 10-20 min, thawing the film in ethanol, carrying out solvent exchange in acetone, and finally taking out the film and putting the film into an oven to carry out drying at the normal pressure of 65 ℃ to obtain the boron nitride heat-conducting material with the three-dimensional network structure.
As shown in FIG. 3, the cross section of the prepared boron nitride heat-conducting composite material has a three-dimensional network structure.
Comparative example 1
(1) Respectively dispersing 1.25g of flaky boron nitride with the median diameter D50 of 5-10 mu m, 2.5g of chitosan and 2.5g of polyacrylic acid into 100g of ultrapure water to prepare three solutions, gradually dripping the chitosan and the polyacrylic acid solution into the three solutions in the stirring process of the boron nitride solution, stirring the solution for 30min in an oil bath at 85 ℃ after all dripping is finished, and stirring the solution in a normal-temperature water bath for 3-4 h to obtain the boron nitride heat-conducting composite material hydrogel;
(2) And directly placing the hydrogel in the steps into a refrigerating chamber of a refrigerator to be subjected to ice assembly for 10-20 min at about minus 18 ℃, thawing the film in ethanol, performing solvent exchange in acetone, and finally taking out the film, and placing the film in an oven to be dried at the normal pressure of 65 ℃ to obtain the boron nitride heat-conducting material.
As shown in FIG. 4, the cross section of the prepared boron nitride heat conduction composite material has no three-dimensional network structure, and the phenomenon of boron nitride agglomeration is serious.
Comparative example 2
(1) Respectively dispersing 1.25g of flaky boron nitride with the median diameter D50 of 5-10 mu m, 2.5g of chitosan and 2.5g of polyacrylic acid into 100g of ultrapure water to prepare three solutions, gradually dripping the chitosan and the polyacrylic acid solution into the three solutions in the stirring process of the boron nitride solution, stirring the solution for 30min in an oil bath at 85 ℃ after all dripping is finished, and stirring the solution in a normal-temperature water bath for 3-4 h to obtain the boron nitride heat-conducting composite material hydrogel;
(2) And (3) placing the hydrogel in a planetary disperser for dispersing for 2-4 min at the speed of 800r/min, uniformly spreading the hydrogel on a glass culture dish, placing the glass culture dish in a refrigerator refrigerating chamber for ice assembly at about 18 ℃ below zero for 10-20 min, thawing the film in ethanol, performing solvent exchange in acetone, and finally taking out the film and drying the film in an oven at the normal pressure of 65 ℃ to obtain the boron nitride heat-conducting composite material.
As shown in FIG. 5, the cross section of the prepared boron nitride heat conduction composite material has no three-dimensional network structure, but the boron nitride is uniformly dispersed in the film, so that the agglomeration phenomenon does not exist.
Comparative example 3
(1) Respectively dispersing 1.25g of flaky boron nitride with the median diameter D50 of 5-10 mu m, 2.5g of sodium alginate and 2.5g of polyvinyl alcohol in 100g of ultrapure water to prepare three solutions, gradually dripping sodium alginate and polyvinyl alcohol solutions into the three solutions in the stirring process of the boron nitride solution, stirring the three solutions for 30min in an oil bath at 85 ℃ after all dripping is finished, and stirring the three solutions in a normal-temperature water bath for 3-4 h to obtain the boron nitride heat-conducting composite hydrogel;
(2) And (3) putting the hydrogel in the step into a planetary disperser to carry out dispersing treatment at the speed of 800r/min for 2-4 min, then putting the hydrogel into an ultrasonic cleaner to carry out ultrasonic treatment for 20-30 min, uniformly extruding the hydrogel onto a glass culture dish by using extrusion equipment, putting the glass culture dish into a refrigerator refrigerating chamber to carry out ice assembly at about 18 ℃ below zero for 10-20 min, thawing the film in ethanol, carrying out solvent exchange in acetone, and finally taking out the film and putting the film into an oven to carry out drying at the normal pressure of 65 ℃ to obtain the boron nitride heat-conducting material with the three-dimensional network structure.
As shown in FIG. 6, the boron nitride heat-conducting composite material prepared by the invention has a three-dimensional network structure, but the structure is not compact and regular enough.
Comparative example 4 the procedure of the experiment implementation in example 1 was changed to that of first stirring chitosan and polyacrylic acid solution at 85 ℃ for 30min in an oil bath, cooling, then adding boron nitride solution, and placing in a normal temperature water bath for stirring for 3-4 h to obtain boron nitride heat-conducting composite material hydrogel, and the other materials are unchanged.
As shown in FIG. 7, the prepared boron nitride heat-conducting composite material has a three-dimensional network structure, but has larger pores and is not tightly connected.
Comparative example 5
The ratio of chitosan to polyacrylic acid in example 1 was changed to 3:1, the others were unchanged. The three-dimensional network structure of the prepared boron nitride heat-conducting composite material is too loose.
Comparative example 6
The ratio of chitosan to polyacrylic acid in example 1 was changed to 0.5:2, the others being unchanged. The prepared boron nitride heat-conducting composite material does not form a three-dimensional network structure.
Comparative example 7
The polymer/BN composite film with vertical sandwich structure prepared by the method disclosed in example 1 of CN113214583a (a thermal interface material with vertical sandwich structure and method of preparing the same).
Claims (8)
1. The preparation method of the boron nitride heat conduction material with the three-dimensional network structure is characterized by comprising the following steps of:
(1) Preparing flaky boron nitride, chitosan aqueous solution and polyacrylic acid aqueous solution, gradually dripping chitosan and polyacrylic acid solution into the flaky boron nitride aqueous solution in the stirring process of the flaky boron nitride aqueous solution, stirring the mixture for 30 to 60 minutes in an oil bath at the temperature of 85 ℃ after all dripping is finished, and stirring the mixture in a water bath at normal temperature for 3 to 4 hours to obtain boron nitride heat-conducting composite material hydrogel;
(2) Placing the hydrogel obtained in the step (1) in a planetary disperser for dispersion treatment, placing the planetary disperser in an ultrasonic cleaner for ultrasonic treatment for 20-30 min, uniformly extruding the hydrogel onto a glass culture dish by using extrusion equipment, placing the glass culture dish in a refrigerator freezing chamber for ice assembly for 10-20 min at the temperature of 18 ℃ below zero to 22 ℃ below zero, thawing the film in ethanol, exchanging solvents in acetone, taking out the film, placing the film in an oven for drying at the temperature of 65 ℃ at normal pressure to obtain the boron nitride heat-conducting material with a three-dimensional network structure,
Wherein the mass ratio of the chitosan to the polyacrylic acid is 2: 1-1: 2.
2. The preparation method of claim 1, wherein the mass fraction of the boron nitride in the boron nitride heat conduction material with the three-dimensional network structure is 20% -50%.
3. The method according to claim 1, wherein in the step (1), the morphology of the boron nitride is in the form of a sheet and the median diameter D50 is 5 μm to 10 μm.
4. The preparation method of claim 1, wherein the dispersion treatment time of the planetary disperser in the step (2) is 2-4 min, and the dispersion rate is 800-1000 r/min.
5. The preparation method of claim 1, wherein the mass fraction of chitosan in the chitosan aqueous solution is 1-5%.
6. The preparation method of claim 1, wherein the polyacrylic acid aqueous solution comprises 1-5% of polyacrylic acid by mass.
7. The boron nitride heat-conducting material with a three-dimensional network structure prepared by the method according to any one of claims 1-6.
8. The use of a boron nitride thermally conductive material having a three-dimensional network structure according to claim 7, for use in the field of electronic devices.
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