CN109666263A - The preparation method and product of a kind of boron nitride/epoxy resin composite material and application - Google Patents
The preparation method and product of a kind of boron nitride/epoxy resin composite material and application Download PDFInfo
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- CN109666263A CN109666263A CN201910006616.2A CN201910006616A CN109666263A CN 109666263 A CN109666263 A CN 109666263A CN 201910006616 A CN201910006616 A CN 201910006616A CN 109666263 A CN109666263 A CN 109666263A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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- C08K2003/382—Boron-containing compounds and nitrogen
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Abstract
The present invention relates to a kind of preparation method of boron nitride/epoxy resin composite material and product and application, preparation method includes: 1) to be dispersed in water boron nitride nanosheet with binder, forms mixed solution；2) mixed solution carries out two-way freezing, and then freeze-drying removal ice crystal, obtains the boron nitride aeroge with lamellar orientation structure；3) cured epoxy resin is filled in the lamellar orientation structure of boron nitride aeroge, obtains boron nitride/epoxy resin composite material.This method is easy to operate, can continuous large scale preparation, be suitble to industry amplification application.
Description
Technical field
The present invention relates to the preparation fields of thermal interfacial material, and in particular to a kind of boron nitride/epoxy resin composite material
Preparation method and product and application.
Background technique
With the raising at full speed of electronic device degree of integration and packing density, generated in electronic device operational process excessive
Heat can generate harmful influence in stability, reliability and service life on device, and for example excessively high temperature can jeopardize semiconductor
Node damages the linkage interface of circuit, increases the resistance value of conductor and mechanical stress is caused to damage, therefore heat dissipation has become entire electricity
One of sub- device and the key problem of encapsulation field.
Thermal interfacial material is between radiating element and heating device, reducing between them used in thermal contact resistance
The general name of material.Can all there be roughness on all surfaces, so when two surfaces contact, it is impossible to completely attach to
Together, some air-gaps are always had to be mingled with wherein, and the thermal coefficient of air is very small, therefore has resulted in bigger
Thermal contact resistance.And this air-gap can be filled using thermal interfacial material, thermal contact resistance can be thus reduced, improves and dissipates
Hot property.
At present polymer matrix thermal interfacial material because its outstanding electrical insulation capability, it is low in cost, prepare the features such as simple quilt
It is widely used in Electronic Packaging field, most representative is epoxy resin, has the following characteristics that wide variety, and solidification is convenient, glues
Attached power is strong, and shrinkage is low, excellent mechanical property and high dielectric property, excellent corrosion resistance etc..But polymer is lower to lead
Thermal energy power limits its further development as thermal interfacial material.
The heat filling of traditional promotion polymer matrix thermal interfacial material has: metal nanoparticle, metal oxide, metal
Nitride, graphene, carbon nanotube etc., wherein boron nitride is with its outstanding heating conduction, outstanding thermal insulation properties and cost
The features such as cheap, is widely used in promoting the heating conduction of polymer matrix thermal interfacial material.
However, boron nitride doses the conventional method in polymer matrix thermal interfacial material due to can not shape as heat filling
At efficient thermal conducting path, the final thermal interfacial material capacity of heat transmission is caused to be promoted not fairly obvious.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of boron nitride/epoxy resin composite material
Preparation method is obtained the boron nitride aeroge with lamellar orientation structure by two-way freezing, forms efficient thermal conducting path.
Technical solution provided by the present invention are as follows:
A kind of preparation method of boron nitride/epoxy resin composite material, comprising:
1) boron nitride nanosheet is dispersed in water with binder, forms mixed solution；
2) mixed solution carries out two-way freezing, and then freeze-drying removal ice crystal, obtains the nitrogen with lamellar orientation structure
Change boron aeroge；
3) cured epoxy resin is filled in the lamellar orientation structure of boron nitride aeroge, obtains boron nitride/asphalt mixtures modified by epoxy resin
Resin composite material.
Two-way freezing discloses in 108840671 A of CN 105692598 A and CN.
Boron nitride aeroge is prepared using two-way freezing in the present invention, there is temperature gradient, nitrogen due to horizontal and vertical
Change among the gap that boron nanometer sheet is compressed between ice crystal by ice crystal exclusion, the lamellar orientation structure of formation rule.It is to be frozen complete
Quan Hou, then ice crystal is removed by freeze-drying, just obtain the boron nitride using ice crystal as template, with lamellar orientation structure
Aeroge fills cured epoxy resin in lamellar orientation structure later, ultimately forms the nitridation with high-efficiency heat conduction access
Boron/epoxy resin composite material has the characteristics that high thermal conductivity, high anisotropy.
Preferably, the two-way freezing includes: that mixed solution is added to bottom to have in the mold of silicon rubber block, silicon
The contact surface of rubber block and mixed solution is inclined-plane, and cold source setting is 5~20 ° in silicon rubber block lower part, the gradient of silicon rubber block,
The temperature of cold source is -120~-30 DEG C.
Further preferably, the gradient of the silicon rubber block is 15~20 °, conducive to better lamellar orientation structure is formed.
Further preferably, the temperature of the cold source is -90~-30 DEG C, and the temperature of cold source is the reaction temperature of two-way freezing
Degree.Above-mentioned temperature makes ice crystal be easily formed template, and cryogenic temperature has influence to the lamellar orientation structure of formation.Temperature is too low
When, temperature gradient is larger, ice-crystal growth fast speed, and the interlamellar spacing of the lamellar orientation structure of formation is smaller, and the number of plies is more, nitridation
Interface cohesion is more between boron thermal conducting path and epoxy resin, and when heat transfer loses more.When temperature is higher, temperature gradient compared with
Small, ice-crystal growth speed is slower, and the interlamellar spacing of the lamellar orientation structure of formation is larger, and the number of plies is less, in boron nitride thermal conducting path
Portion's defect is more, and phon scattering is stronger, and when heat transfer loses more.
The volume fraction of binder is 2~4% in heretofore described mixed solution；Boron nitride is received in the mixed solution
The volume fraction of rice piece is 2.5~20%.Preferably, the volume fraction of the binder is 2~2.5%, the boron nitride
The volume fraction of nanometer sheet is 15~20%, conducive to more effective thermal conducting path is formed.
Heretofore described boron nitride nanosheet is removed to obtain using boron nitride powder；The piece diameter of the boron nitride nanosheet
For 400~800nm.
Preferably, the boron nitride powder removing includes: that the boron nitride powder is dissolved in the aqueous solution of isopropanol
Ball milling is carried out, ultrasound, centrifugation and freeze-drying obtain.
Heretofore described binder is hydroxypropyl cellulose, hydroxymethyl cellulose or polyvinyl alcohol.Preferably, described
Binder is polyvinyl alcohol, conducive to the stability for effectively increasing mixed solution.
The cured epoxy resin of heretofore described filling include: by boron nitride aeroge be immersed in epoxy monomer with
In the mixture of curing agent, solidify under vacuum condition.
The cured epoxy resin of heretofore described filling include: by boron nitride aeroge be immersed in epoxy monomer,
In the mixture of curing agent and catalyst, solidify under vacuum condition.
Preferably, the epoxy monomer is selected from bisphenol F type epoxy prepolymer, bisphenol type epoxy prepolymer, bis-phenol
S type prepolymer.
Preferably, curing agent is selected from methylhexahydrophthalic anhydride, m-xylene diamine, methylnadic anhydride.
Preferably, catalyst is selected from 2,4,6- tri- (dimethylamino methyl) phenol, 2-ethyl-4-methylimidazole.
Preferably as one of which, the cured epoxy resin of filling includes: that boron nitride aeroge is immersed in Bisphenol F
Type epoxy prepolymer, methylhexahydrophthalic anhydride and 2, in the mixture of 4,6- tri- (dimethylamino methyl) phenol, very
It is heating and curing under empty condition.Further preferably, described to be heating and curing using step heating, 75~85 DEG C of heating 1~4h, 125~
135 DEG C of 1~4h of heating.
Preferably as one of which, the cured epoxy resin of filling includes: that boron nitride aeroge is immersed in Bisphenol F
Type epoxy prepolymer, m-xylene diamine mixture in, normal temperature cure under vacuum condition.
Preferably as one of which, the cured epoxy resin of filling includes: that boron nitride aeroge is immersed in Bisphenol F
In the mixture of type epoxy prepolymer, methylhexahydrophthalic anhydride and 2-ethyl-4-methylimidazole, add under vacuum condition
Heat cure.Further preferably, described to be heating and curing using step heating, 65~75 DEG C of 1~3h of heating, 110~130 DEG C of heating 1
~3h.
Preferably as one of which, the cured epoxy resin of filling includes: that boron nitride aeroge is immersed in Bisphenol F
Type epoxy prepolymer, methylnadic anhydride, 2-ethyl-4-methylimidazole mixture in, heated under vacuum solidification.Into
One step is preferred, described to be heating and curing using step heating, 75-85 DEG C of heating 1~3h, 120~135 DEG C of 1~3h of heating.
Preferably as one of which, the cured epoxy resin of filling includes: that boron nitride aeroge is immersed in Bisphenol F
Type epoxy prepolymer, methylnadic anhydride, 2, in the mixture of 4,6- tri- (dimethylamino methyl) phenol, under vacuum condition plus
Heat cure.Further preferably, described to be heating and curing using step heating, 75~85 DEG C of 1~3h of heating, 120~135 DEG C of heating 1
~3h.
Preferably as one of which, the cured epoxy resin of filling includes: that boron nitride aeroge is immersed in bisphenol-A
Type epoxy prepolymer, m-xylene diamine mixture in, normal temperature cure under vacuum condition.
Preferably as one of which, the cured epoxy resin of filling includes: that boron nitride aeroge is immersed in bisphenol-A
In the mixture of type epoxy prepolymer, methylhexahydrophthalic anhydride and 2-ethyl-4-methylimidazole, add under vacuum condition
Heat cure.Further preferably, described to be heating and curing using step heating, 65~75 DEG C of 1~3h of heating, 115~125 DEG C of heating 1
~3h.
Preferably as one of which, the cured epoxy resin of filling includes: that boron nitride aeroge is immersed in bisphenol S
Type epoxy prepolymer, m-xylene diamine mixture in, normal temperature cure under vacuum condition.
Preferably as one of which, the cured epoxy resin of filling includes: that boron nitride aeroge is immersed in bisphenol S
Type epoxy prepolymer, methylnadic anhydride, 2-ethyl-4-methylimidazole mixture in, heated under vacuum solidification.Into
One step is preferred, described to be heating and curing using step heating, 75~85 DEG C of heating 1~3h, 125~135 DEG C of 1~3h of heating.
The present invention also provides a kind of boron nitride/epoxy resin composite materials, including the boron nitride with lamellar orientation structure
Aeroge, and it is filled in cured epoxy resin in lamellar orientation structure.
The present invention also provides a kind of such as application of the above-mentioned boron nitride/epoxy resin composite material as thermal interfacial material,
For being mounted between radiating element and heating device.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) preparation method of the invention is easy to operate, can continuous large scale preparation, be suitble to industry amplification application.
(2) the of the invention raw material for preparing is boron nitride and epoxy resin, environmental-friendly, from a wealth of sources, low in cost, is suitble to
It is widely used in industrial use.
(3) preparation method of the invention can be made by parameters such as the temperature of the two-way freezing of adjusting and mixed solution concentration
It is standby to obtain boron nitride/epoxy resin composite material of different interlamellar spacings, thickness degree.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of two-way refrigerating plant in the embodiment of the present invention；
Fig. 2 is the SEM photograph of the boron nitride aeroge prepared in embodiment 1；
Fig. 3 is the boron nitride/epoxy resin composite material SEM photograph prepared in embodiment 1；
Fig. 4 is the SEM photograph of the boron nitride aeroge prepared in embodiment 2；
Fig. 5 is the boron nitride/epoxy resin composite material SEM photograph prepared in embodiment 2；
Fig. 6 is the SEM photograph of the boron nitride aeroge prepared in embodiment 3；
Fig. 7 is the boron nitride/epoxy resin composite material SEM photograph prepared in embodiment 3；
Fig. 8 is the SEM photograph of the boron nitride aeroge prepared in embodiment 4；
Fig. 9 is the boron nitride/epoxy resin composite material SEM photograph prepared in embodiment 4；
Figure 10 is the boron nitride/epoxy resin composite material SEM photograph prepared in embodiment 5；
Figure 11 is the boron nitride/epoxy resin composite material SEM photograph prepared in embodiment 6；
Figure 12 is the SEM photograph of the boron nitride aeroge prepared in comparative example 1；
Figure 13 be boron nitride/epoxy resin composite material as thermal interfacial material when the infrared figure of LED surface temperature change；
Figure 14 be commercial silica gel heat conductive pad as thermal interfacial material when the infrared figure of LED surface temperature change.
Specific embodiment
The present invention is further explained in the light of specific embodiments:
For two-way refrigerating plant used in embodiment as shown in Figure 1,1 be wherein cold ethanol, 2 be copper post, and 3 be copper sheet, 4
It is Teflon mould for silicon rubber block, 5,6 be mixed solution.Cold ethanol 1, copper post 2 and copper sheet 3 form cold source, low temperature
The temperature of ethyl alcohol 1 is controlled at -120~-30 DEG C；The gradient of silicon rubber block 4 is 15 °.
Embodiment 1
(1) solution is prepared: 6.87g boron nitride powder being taken to be scattered in 200mL isopropanol and deionized water (volume at room temperature
Than 1:1) in mixed solution, ball milling 12h or more makes it be uniformly dispersed, and ultrasonic 1h, 2000r/min are centrifuged 5min, takes supernatant
9000r/min is centrifuged 5min again, removes supernatant, and bottom solid is freeze-dried to obtain boron nitride nanosheet.
Take 0.27g polyvinyl alcohol, 17mL deionized water, 90 DEG C of heating 30min make polyvinyl alcohol be dissolved completely in from
In sub- water, 6.87g boron nitride nanosheet is added, stirs evenly, ultrasonic 1h, obtains more stable mixed solution after vacuum degassing bubble,
Wherein boron nitride nanosheet volume fraction is 15vol%, and polyvinyl alcohol volume fraction is 2vol%.
(2) two-way frost: the mixed solution that step (1) obtains is placed in the mold of two-way refrigerating plant carry out it is two-way cold
Freeze, cryogenic temperature is -90 DEG C.
(3) be freeze-dried: by the two-way frozen product that step (2) obtains be freeze-dried at -80 DEG C, 5Pa more than for 24 hours with
Sufficiently removal ice crystal, obtains the boron nitride aeroge with lamellar orientation structure, SEM photograph is as shown in Figure 2.
(4) the resulting boron nitride aeroge of step (3) curable epoxide: is immersed into (wherein epoxy monomer in mixture
For bisphenol f type epoxy resin 20g, curing agent methylhexahydrophthalic anhydride 20g, catalyst 2,4, (the dimethylamino first of 6- tri-
Base) phenol 0.1g), 30min is vacuumized, solidifies 2h at 80 DEG C, the secondary curing 2h at 120 DEG C obtains boron nitride/asphalt mixtures modified by epoxy resin
Resin composite material, SEM photograph are as shown in Figure 3.
Embodiment 2
(1) solution is prepared: 6.87g boron nitride powder being taken to be scattered in 200mL isopropanol and deionized water (volume at room temperature
Than 1:1) in mixed solution, ball milling 12h or more makes it be uniformly dispersed, and ultrasonic 1h, 2000r/min are centrifuged 5min, takes supernatant
9000r/min is centrifuged 5min again, removes supernatant, and bottom solid is freeze-dried to obtain boron nitride nanosheet.
Take 0.27g polyvinyl alcohol, 17mL deionized water, 90 DEG C of heating 30min make polyvinyl alcohol be dissolved completely in from
In sub- water, 6.87g boron nitride nanosheet is added, stirs evenly, ultrasonic 1h, obtains more stable mixed solution after vacuum degassing bubble,
Wherein boron nitride nanosheet volume fraction is 15vol%, and polyvinyl alcohol volume fraction is 2vol%.
(2) two-way frost: the mixed solution that step (1) obtains is placed in the mold of two-way refrigerating plant carry out it is two-way cold
Freeze, cryogenic temperature is -40 DEG C.
(3) be freeze-dried: by the two-way frozen product that step (2) obtains be freeze-dried at -80 DEG C, 5Pa more than for 24 hours with
Sufficiently removal ice crystal, obtains the boron nitride aeroge with lamellar orientation structure, SEM photograph is as shown in Figure 4.
(4) the resulting boron nitride aeroge of step (3) curable epoxide: is immersed into (wherein epoxy monomer in mixture
For bisphenol f type epoxy resin 20g, curing agent methylhexahydrophthalic anhydride 20g, catalyst 2,4, (the dimethylamino first of 6- tri-
Base) phenol 0.1g), 30min is vacuumized, solidifies 2h at 80 DEG C, the secondary curing 2h at 120 DEG C obtains boron nitride/asphalt mixtures modified by epoxy resin
Resin composite material, SEM photograph are as shown in Figure 5.
Embodiment 3
(1) solution is prepared: 6.87g boron nitride powder being taken to be scattered in 200mL isopropanol and deionized water (volume at room temperature
Than 1:1) in mixed solution, ball milling 12h or more makes it be uniformly dispersed, and ultrasonic 1h, 2000r/min are centrifuged 5min, takes supernatant
9000r/min is centrifuged 5min again, removes supernatant, and bottom solid is freeze-dried to obtain boron nitride nanosheet.
Take 0.27g polyvinyl alcohol, 17mL deionized water, 90 DEG C of heating 30min make polyvinyl alcohol be dissolved completely in from
In sub- water, 6.87g boron nitride nanosheet is added, stirs evenly, ultrasonic 1h, obtains more stable mixed solution after vacuum degassing bubble,
Wherein boron nitride nanosheet volume fraction is 15vol%, and polyvinyl alcohol volume fraction is 2vol%.
(2) two-way frost: the mixed solution that step (1) obtains is placed in the mold of two-way refrigerating plant carry out it is two-way cold
Freeze, cryogenic temperature is -120 DEG C.
(3) be freeze-dried: by the two-way frozen product that step (2) obtains be freeze-dried at -80 DEG C, 5Pa more than for 24 hours with
Sufficiently removal ice crystal, obtains the boron nitride aeroge with lamellar orientation structure, SEM photograph is as shown in Figure 6.
(4) the resulting boron nitride aeroge of step (3) curable epoxide: is immersed into (wherein epoxy monomer in mixture
For bisphenol f type epoxy resin 20g, curing agent methylhexahydrophthalic anhydride 20g, catalyst 2,4, (the dimethylamino first of 6- tri-
Base) phenol 0.1g), 30min is vacuumized, solidifies 2h at 80 DEG C, the secondary curing 2h at 120 DEG C obtains boron nitride/asphalt mixtures modified by epoxy resin
Resin composite material, SEM photograph are as shown in Figure 7.
Embodiment 4
(1) solution is prepared: 3.44g boron nitride powder being taken to be scattered in 200mL isopropanol and deionized water (volume at room temperature
Than 1:1) in mixed solution, ball milling 12h or more makes it be uniformly dispersed, and ultrasonic 1h, 2000r/min are centrifuged 5min, takes supernatant
9000r/min is centrifuged 5min again, removes supernatant, and bottom solid is freeze-dried to obtain boron nitride nanosheet.
0.16g polyvinyl alcohol, 18.5mL deionized water are taken, 90 DEG C of heating 30min are dissolved completely in polyvinyl alcohol
In ionized water, 3.44g boron nitride nanosheet is added, stirs evenly, ultrasonic 1h, it is molten that more stable mixing is obtained after vacuum degassing bubble
Liquid, wherein boron nitride nanosheet volume fraction is 7.5vol%, and polyvinyl alcohol volume fraction is 4vol%.
(2) two-way frost: the mixed solution that step (1) obtains is placed in the mold of two-way refrigerating plant carry out it is two-way cold
Freeze, cryogenic temperature is -90 DEG C.
(3) be freeze-dried: by the two-way frozen product that step (2) obtains be freeze-dried at -80 DEG C, 5Pa more than for 24 hours with
Sufficiently removal ice crystal, obtains the boron nitride aeroge with lamellar orientation structure, SEM photograph is as shown in Figure 8.
(4) the resulting boron nitride aeroge of step (3) curable epoxide: is immersed into (wherein epoxy monomer in mixture
For bisphenol f type epoxy resin 20g, curing agent methylhexahydrophthalic anhydride 20g, catalyst 2,4, (the dimethylamino first of 6- tri-
Base) phenol 0.1g), 30min is vacuumized, solidifies 2h at 80 DEG C, the secondary curing 2h at 120 DEG C obtains boron nitride/asphalt mixtures modified by epoxy resin
Resin composite material, SEM photograph are as shown in Figure 9.
Embodiment 5
(1) solution is prepared: 6.87g boron nitride powder being taken to be scattered in 200mL isopropanol and deionized water (volume at room temperature
Than 1:1) in mixed solution, ball milling 12h or more makes it be uniformly dispersed, and ultrasonic 1h, 2000r/min are centrifuged 5min, takes supernatant
9000r/min is centrifuged 5min again, removes supernatant, and bottom solid is freeze-dried to obtain boron nitride nanosheet.
Take 0.27g polyvinyl alcohol, 17mL deionized water, 90 DEG C of heating 30min make polyvinyl alcohol be dissolved completely in from
In sub- water, 6.87g boron nitride nanosheet is added, stirs evenly, ultrasonic 1h, obtains more stable mixed solution after vacuum degassing bubble,
Wherein boron nitride nanosheet volume fraction is 15vol%, and polyvinyl alcohol volume fraction is 2vol%.
(2) two-way frost: the mixed solution that step (1) obtains is placed in the mold of two-way refrigerating plant carry out it is two-way cold
Freeze, cryogenic temperature is -90 DEG C.
(3) be freeze-dried: by the two-way frozen product that step (2) obtains be freeze-dried at -80 DEG C, 5Pa more than for 24 hours with
Sufficiently removal ice crystal, obtains the boron nitride aeroge with lamellar orientation structure, SEM photograph is as shown in Figure 2.
(4) the resulting boron nitride aeroge of step (3) curable epoxide: is immersed into (wherein epoxy monomer in mixture
30min is vacuumized, solidifies 6h at room temperature, is nitrogenized for bisphenol f type epoxy resin 20g, curing agent m-xylene diamine 5g
Boron/epoxy resin composite material, SEM photograph are as shown in Figure 10.
Embodiment 6
(1) solution is prepared: 6.87g boron nitride powder being taken to be scattered in 200mL isopropanol and deionized water (volume at room temperature
Than 1:1) in mixed solution, ball milling 12h or more makes it be uniformly dispersed, and ultrasonic 1h, 2000r/min are centrifuged 5min, takes supernatant
9000r/min is centrifuged 5min again, removes supernatant, and bottom solid is freeze-dried to obtain boron nitride nanosheet.
Take 0.27g polyvinyl alcohol, 17mL deionized water, 90 DEG C of heating 30min make polyvinyl alcohol be dissolved completely in from
In sub- water, 6.87g boron nitride nanosheet is added, stirs evenly, ultrasonic 1h, obtains more stable mixed solution after vacuum degassing bubble,
Wherein boron nitride nanosheet volume fraction is 15vol%, and polyvinyl alcohol volume fraction is 2vol%.
(2) two-way frost: the mixed solution that step (1) obtains is placed in the mold of two-way refrigerating plant carry out it is two-way cold
Freeze, cryogenic temperature is -120 DEG C.
(3) be freeze-dried: by the two-way frozen product that step (2) obtains be freeze-dried at -80 DEG C, 5Pa more than for 24 hours with
Sufficiently removal ice crystal, obtains the boron nitride aeroge with lamellar orientation structure, SEM photograph is as shown in Figure 6.
(4) the resulting boron nitride aeroge of step (3) curable epoxide: is immersed into (wherein epoxy monomer in mixture
For bisphenol f type epoxy resin 20g, curing agent is methylnadic anhydride 18g, catalyst is 2-ethyl-4-methylimidazole 0.2g,
30min is vacuumized, solidifies 2h at 80 DEG C, the secondary curing 2h at 130 DEG C obtains boron nitride/epoxy resin composite material,
SEM photograph is as shown in figure 11.
Comparative example 1
(1) solution is prepared: 6.87g boron nitride powder being taken to be scattered in 200mL isopropanol and deionized water (volume at room temperature
Than 1:1) in mixed solution, ball milling 12h or more makes it be uniformly dispersed, and ultrasonic 1h, 2000r/min are centrifuged 5min, takes supernatant
9000r/min is centrifuged 5min again, removes supernatant, and bottom solid is freeze-dried to obtain boron nitride nanosheet.
Take 0.27g polyvinyl alcohol, 17mL deionized water, 90 DEG C of heating 30min make polyvinyl alcohol be dissolved completely in from
In sub- water, 6.87g boron nitride nanosheet is added, stirs evenly, ultrasonic 1h, obtains more stable mixed solution after vacuum degassing bubble,
Wherein boron nitride nanosheet volume fraction is 15vol%, and polyvinyl alcohol volume fraction is 2vol%.
(2) orientation frost: the mixed solution that step (1) obtains is placed in the not mold of silicon rubber block be oriented it is cold
Freeze, the gradient for being equivalent to silicon rubber block is 0 °, and cryogenic temperature is -90 DEG C.
(3) be freeze-dried: by the orientation frozen product that step (2) obtains be freeze-dried at -80 DEG C, 5Pa more than for 24 hours with
Sufficiently removal ice crystal, obtains boron nitride aeroge, and SEM photograph is as shown in figure 12, does not have lamellar orientation structure.
(4) the resulting boron nitride aeroge of step (3) curable epoxide: is immersed into (wherein epoxy monomer in mixture
For bisphenol f type epoxy resin 20g, curing agent methylhexahydrophthalic anhydride 20g, catalyst 2,4, (the dimethylamino first of 6- tri-
Base) phenol 0.1g), 30min is vacuumized, solidifies 2h at 80 DEG C, the secondary curing 2h at 120 DEG C obtains boron nitride/asphalt mixtures modified by epoxy resin
Resin composite material.
Performance test
(1) boron nitride/epoxy resin composite material (BNNS/epoxy) prepared by testing example 1 is used as thermal interfacial material
Performance
Composite material in embodiment 1 is cut into 40 × 40 × 2mm size, with a 20W LED light and copper billet radiate trap into
Row assembling.The temperature of copper billet heat dissipation trap is by cold and hot constant control at 10 DEG C.LED is recorded from start-up operation by infrared camera
To temperature change during 260s, as shown in figure 13.
(2) performance of the commercial silica gel heat conductive pad (Silicone) as thermal interfacial material is tested
Commercial silica gel heat conductive pad is cut into 40 × 40 × 2mm size, carries out group with a 20W LED light and copper billet heat dissipation trap
Dress.The temperature of copper billet heat dissipation trap is by cold and hot constant control at 10 DEG C.By infrared camera record LED from start to work to
Temperature change during 260s, as shown in figure 14.
The two compares it is found that temperature after LED operation 260s when boron nitride/epoxy resin composite material is as thermal interfacial material
Rising degree than commercial silicagel pad as thermal interfacial material when it is 10 DEG C low, it was demonstrated that boron nitride/epoxy resin composite material conduct
Excellent heat dissipation performance when thermal interfacial material.
Claims (10)
1. a kind of preparation method of boron nitride/epoxy resin composite material characterized by comprising
1) boron nitride nanosheet is dispersed in water with binder, forms mixed solution；
2) mixed solution carries out two-way freezing, and then freeze-drying removal ice crystal, obtains the boron nitride with lamellar orientation structure
Aeroge；
3) cured epoxy resin is filled in the lamellar orientation structure of boron nitride aeroge, it is multiple obtains boron nitride/epoxy resin
Condensation material.
2. the preparation method of boron nitride/epoxy resin composite material according to claim 1, which is characterized in that described double
It include: that mixed solution is added in the mold that bottom has silicon rubber block to freezing, contact of the silicon rubber block with mixed solution
Face is inclined-plane, and cold source setting is 5~20 ° in silicon rubber block lower part, the gradient of silicon rubber block, and the temperature of cold source is -120~-30
℃。
3. the preparation method of boron nitride/epoxy resin composite material according to claim 1, which is characterized in that described mixed
The volume fraction for closing binder in solution is 2~4%；In the mixed solution volume fraction of boron nitride nanosheet be 2.5~
20%.
4. the preparation method of boron nitride/epoxy resin composite material according to claim 1, which is characterized in that the nitrogen
Change boron nanometer sheet to remove to obtain using boron nitride powder；The piece diameter of the boron nitride nanosheet is 400~800nm.
5. the preparation method of boron nitride/epoxy resin composite material according to claim 4, which is characterized in that the nitrogen
Changing boron powder removing includes: that the boron nitride powder is dissolved in the aqueous solution of isopropanol to carry out ball milling, ultrasound, centrifugation and freezing
It is dried to obtain.
6. the preparation method of boron nitride/epoxy resin composite material according to claim 1, which is characterized in that described viscous
Knot agent is hydroxypropyl cellulose, hydroxymethyl cellulose or polyvinyl alcohol.
7. the preparation method of boron nitride/epoxy resin composite material according to claim 1, which is characterized in that described to fill out
Filling cured epoxy resin includes: to be immersed in boron nitride aeroge in the mixture of epoxy monomer and curing agent, vacuum
Under the conditions of solidify.
8. the preparation method of boron nitride/epoxy resin composite material according to claim 1, which is characterized in that described to fill out
Filling cured epoxy resin includes: the mixing that boron nitride aeroge is immersed in epoxy monomer, curing agent and catalyst
In object, solidify under vacuum condition.
9. a kind of boron nitride/epoxy resin composite material, which is characterized in that including the boron nitride airsetting with lamellar orientation structure
Glue, and it is filled in cured epoxy resin in lamellar orientation structure.
10. a kind of application of boron nitride/epoxy resin composite material as claimed in claim 9 as thermal interfacial material.
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