CN108715671A - A kind of high heat conducting nano heat conducting film and preparation method thereof - Google Patents
A kind of high heat conducting nano heat conducting film and preparation method thereof Download PDFInfo
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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
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- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The present invention provides a kind of high heat conducting nano heat conducting films and preparation method thereof, are prepared by the raw material of following parts by weight：15-40 parts of modifying epoxy resin by organosilicon, 30-60 parts of denatured conductive filler, 4-9 parts of curing agent, 4-9 parts of dispersant, 8-16 parts of stabilizer, 25-50 parts of solvent；The denatured conductive filler is the mixture of AlN, SiN and graphene.The present invention, as bonding matrix material, improves the mechanical performance of epoxy resin and the binding ability with substrate using organosilicon epoxy resin.It is obtained by test result, heat conducting film shear strength produced by the present invention reaches 83MPa, and peel strength reaches 14.2N/mm, thermal coefficient reaches 1738W/m K, therefore there is heat conducting film produced by the present invention excellent heat conductivility, good mechanical property to be suitable for the commonly used of heat conduction membrane material.
Description
Technical field
The present invention relates to a kind of heat conducting films, and in particular to a kind of high heat conducting nano heat conducting film and preparation method thereof.
Background technology
Currently, electronic product just develops towards high-density wiring direction, and high-density wiring must take into consideration printed circuit board
With the heat dissipation problem of component, how in a limited space the copper-clad plates such as conventional FR-4, CEM-3 are all the non-conductor of heat,
The heat generated when inside electronic component working as much as possible quickly sheds, it has also become the important research class of industry in recent years
Topic.
Metal-based copper-clad plate especially aluminum-based copper-clad plate due to excellent heat conductivility, good processing performance and compared with
High cost performance is widely used in LED heat radiating circuit design.LED heat dissipations quality directly affects LED life, and LED is special
It is not the LEDbulb lamp lighting angle such as lighting angle for needing to reach similar incandescent light bulb, needs using with certain flexure
Property can 3D encapsulation aluminum substrate, thermally conductive insulating layer therein needs to have that good heat dissipation is better, however existing heat conducting film makes
Heat filling is more single, and heat conductivility cannot be significantly improved, and therefore, studies the high thermal conductivity of heat conducting film always
It is the key that research.
Invention content
Above of the existing technology in order to solve the problems, such as, the purpose of the present invention is to provide a kind of high heat conducting nano heat conduction
Film and preparation method thereof.
To achieve the goals above, the present invention provides following technical scheme：
A kind of high heat conducting nano heat conducting film, is prepared by the raw material of following parts by weight：Modifying epoxy resin by organosilicon 15-40
Part, 30-60 parts of denatured conductive filler, 4-9 parts of curing agent, 4-9 parts of dispersant, 8-16 parts of stabilizer, 25-50 parts of solvent；
The denatured conductive filler is the mixture of AlN, SiN and graphene,
The preparation method of the denatured conductive filler is：（1）By 100 parts of graphenes under atmosphere of inert gases first with 1-2 DEG C/
The rate of min is warming up to 400-600 DEG C, keeps the temperature 0.5-1h, then be warming up under the same conditions with the rate of 3-5 DEG C/min
1000-1200 DEG C, after keeping the temperature 1-2h, it is down to room temperature naturally；
（2）By step（1）Treated graphene, 50 parts of AlN, 50 parts of SiN and to be added to the 30-50 parts of ethyl alcohol containing 10%DMF molten
In liquid, 5-10 parts of dispersing aid is added thereto, 20-40min is stirred at room temperature, temperature is risen to 40-60 DEG C, is added
3-8 parts of gamma-aminopropyl-triethoxy-silanes continue after stirring 1-2h, and supernatant is removed by centrifugation, and it is heavy to collect lower layer graphene
It forms sediment, is placed in baking oven and dries to get denatured conductive filler.
Preferably, the modifying epoxy resin by organosilicon be polymethylphenylsiloxane be modified bisphenol A type epoxy resin,
The one of 4,5 dioctyl phthalate epoxy resin of glycerol epoxy resin, 4,5 dioctyl phthalate epoxy resin of 2- epoxy-cyclohexanes or 2- epoxy-cyclohexanes
Kind or a variety of arbitrary combinations.
Preferably, the mass ratio of AlN, SiN and graphene is 3 in the denatured conductive filler:1:2.5.
Preferably, the curing agent is 4,4 diaminodiphenyl ethers or 4,4 diaminodiphenylmethane.
Preferably, the dispersant is carmethose, sulfonated polyaniline, dodecyl sodium sulfate, cetyl three
Methyl bromide ammonium, sodium polymethacrylate or sodium taurocholate it is one or more.
Preferably, the stabilizer be epoxidized soybean oil, pentaerythrite, barium laurate or 2,6- d-tert-butyl-p-cresols
One or more combinations.
Preferably, the solvent is methyl ethyl ketone, isopropanol, butanol, ethyl acetate, cyclohexanone, glycol monoethyl ether or first
Ethoxy-ethanol.
Preferably, the dispersing aid is the one or more of polyvinylpyrrolidone, polyethylene glycol or calgon
Combination.
The preparation method of heat conducting film of the present invention, includes the following steps：
（1）Modifying epoxy resin by organosilicon is added in solution, 0.5-1h is stirred at a temperature of 80-120 DEG C, it then will be warm
Degree is down to 60-70 DEG C, and denatured conductive filler, curing agent, dispersant, stabilizer are added in reaction system, this temperature is kept
Then the reaction was continued 1-2h handles 40-60min through ultrasonic disperse again, premixed liquid is made；
（2）By step（1）Premixed liquid obtained is cast in preheated mold, 80 DEG C of vacuumizing and defoaming 10-20min, then will be warm
Gradient increased temperature is spent to 120-130 DEG C, and keeps this temperature-curable 2-3h, it is last to be down to room temperature demoulding naturally to get heat conducting film.
Advantageous effect：The present invention provides a kind of high heat conducting nano heat conducting film and preparation method thereof, the present invention is using organic
Epoxy silicone is as bonding matrix material, and organosilicon has the advantages that good thermal stability, resistance to oxidation, weather-proof, surface energy is low etc., adopts
Epoxy resin is modified with organosilicon, improves the mechanical performance of epoxy resin and the binding ability with substrate, simultaneously
The internal stress of modified epoxy resin reduces, and filler is easier to be filled into resin, the adhesive force of filler is improved, to heat conducting film
The raising of mechanical performance and heat conductivility all has important role.It is obtained by test result, heat conduction produced by the present invention
Film shear strength reaches 83MPa, and peel strength reaches 14.2N/mm, and thermal coefficient reaches 1738W/m K, therefore the present invention is made
Heat conducting film have excellent heat conductivility, good mechanical property, be suitable for heat conduction membrane material it is commonly used.
Specific implementation mode
The invention will now be further described with reference to specific embodiments, but examples are merely exemplary, not to this hair
Bright range constitutes any restrictions.It will be understood by those skilled in the art that without departing from the spirit and scope of the invention
Can the details and form of technical solution of the present invention be modified or be replaced, but these modifications and replacement each fall within the present invention's
In protection domain.
Embodiment 1
A kind of high heat conducting nano heat conducting film, is prepared by the raw material of following parts by weight：28 parts of modifying epoxy resin by organosilicon changes
45 parts of conductive filler of property, 6.5 parts of curing agent, 7 parts of dispersant, 12 parts of stabilizer, 38 parts of solvent；
The denatured conductive filler is the mixture of AlN, SiN and graphene, mass ratio 1：2.5：3.5.
The preparation method of the denatured conductive filler is：（1）By 100 parts of graphenes first with 1-2 under atmosphere of inert gases
DEG C/rate of min is warming up to 500 DEG C, 0.8h is kept the temperature, then be warming up to 1100 under the same conditions with the rate of 3-5 DEG C/min
DEG C, after keeping the temperature 1.5h, it is down to room temperature naturally；
（2）By step（1）Treated graphene, 50 parts of AlN, 50 parts of SiN and it is added to 40 parts of ethanol solutions containing 10%DMF
In, 7.5 parts of dispersing aid is added thereto, and 30min is stirred at room temperature, temperature is risen to 50 DEG C, adds 5.5 parts of γ-
Aminopropyl triethoxysilane continues after stirring 1.5h, and supernatant is removed by centrifugation, collects lower layer graphene precipitation, is placed in
Drying is to get denatured conductive filler in baking oven.
The modifying epoxy resin by organosilicon is the bisphenol A type epoxy resin that polymethylphenylsiloxane is modified.
The mass ratio of AlN, SiN and graphene is 3 in the denatured conductive filler:1:2.5.
The curing agent is 4,4 diaminodiphenyl ethers.
The dispersant is carmethose.
The stabilizer is that mass ratio is 1:1 epoxidized soybean oil and pentaerythrite.
The solvent is mass ratio 1:3 for methyl ethyl ketone and isopropanol with.
The dispersing aid is polyvinylpyrrolidone.
The preparation method of heat conducting film of the present invention, includes the following steps：
（1）Modifying epoxy resin by organosilicon is added in solution, 0.8h is stirred at a temperature of 100 DEG C, then drops temperature
To 65 DEG C, denatured conductive filler, curing agent, dispersant, stabilizer are added in reaction system, keeping this temperature, the reaction was continued
Then 1.5h handles 50min through ultrasonic disperse again, premixed liquid is made；
（2）By step（1）Premixed liquid obtained is cast in preheated mold, 80 DEG C of vacuumizing and defoaming 15min, then by temperature ladder
Degree is warming up to 125 DEG C, and keeps this temperature-curable 2.5h, last to be down to room temperature demoulding naturally to get heat conducting film.
Embodiment 2
A kind of high heat conducting nano heat conducting film, is prepared by the raw material of following parts by weight：15 parts of modifying epoxy resin by organosilicon changes
30 parts of conductive filler of property, 4 parts of curing agent, 4 parts of dispersant, 8 parts of stabilizer, 25 parts of solvent；
The denatured conductive filler is the mixture of AlN, SiN and graphene, mass ratio 1：1：2.
The preparation method of the denatured conductive filler is：（1）By 100 parts of graphenes first with 1-2 under atmosphere of inert gases
DEG C/rate of min is warming up to 400 DEG C, 0.5h is kept the temperature, then be warming up to 1000 under the same conditions with the rate of 3-5 DEG C/min
DEG C, after keeping the temperature 1h, it is down to room temperature naturally；
（2）By step（1）Treated graphene, 50 parts of AlN, 50 parts of SiN and it is added to 30 parts of ethanol solutions containing 10%DMF
In, 5 parts of dispersing aid is added thereto, and 20min is stirred at room temperature, temperature is risen to 40 DEG C, adds 3 parts of γ-ammonia third
Ethyl triethoxy silicane alkane continues after stirring 1h, and supernatant is removed by centrifugation, collects lower layer graphene precipitation, is placed in baking oven
Drying is to get denatured conductive filler.
The modifying epoxy resin by organosilicon is the 4,5 dioctyl phthalate ring of 2- epoxy-cyclohexanes that polymethylphenylsiloxane is modified
Oxygen resin.
The mass ratio of AlN, SiN and graphene is 3 in the denatured conductive filler:1:2.5.
The curing agent is 4,4 diaminodiphenylmethane.
The dispersant is that mass ratio is 1:1 dodecyl sodium sulfate and cetyl trimethylammonium bromide.
The stabilizer is pentaerythrite.
The solvent is mass ratio 1:2 cyclohexanone and glycol monoethyl ether.
The dispersing aid is polyethylene glycol 400.
The preparation method of heat conducting film of the present invention, includes the following steps：
（1）Modifying epoxy resin by organosilicon is added in solution, 0.5h is stirred at a temperature of 80 DEG C, then cools the temperature to
60 DEG C, denatured conductive filler, curing agent, dispersant, stabilizer are added in reaction system, keeping this temperature, the reaction was continued
Then 1h handles 40min through ultrasonic disperse again, premixed liquid is made；
（2）By step（1）Premixed liquid obtained is cast in preheated mold, 80 DEG C of vacuumizing and defoaming 10min, then by temperature ladder
Degree is warming up to 120 DEG C, and keeps this temperature-curable 2h, last to be down to room temperature demoulding naturally to get heat conducting film.
Embodiment 3
A kind of high heat conducting nano heat conducting film, is prepared by the raw material of following parts by weight：20 parts of modifying epoxy resin by organosilicon changes
40 parts of conductive filler of property, 5 parts of curing agent, 5 parts of dispersant, 10 parts of stabilizer, 30 parts of solvent；
The denatured conductive filler is the mixture of AlN, SiN and graphene, mass ratio 1：2：3.
The preparation method of the denatured conductive filler is：（1）By 100 parts of graphenes first with 1-2 under atmosphere of inert gases
DEG C/rate of min is warming up to 450 DEG C, 0.6h is kept the temperature, then be warming up to 1050 under the same conditions with the rate of 3-5 DEG C/min
DEG C, after keeping the temperature 1.2h, it is down to room temperature naturally；
（2）By step（1）Treated graphene, 50 parts of AlN, 50 parts of SiN and it is added to 35 parts of ethanol solutions containing 10%DMF
In, 6 parts of dispersing aid is added thereto, and 25min is stirred at room temperature, temperature is risen to 45 DEG C, adds 4 parts of γ-ammonia third
Ethyl triethoxy silicane alkane continues after stirring 1.2h, and supernatant is removed by centrifugation, collects lower layer graphene precipitation, is placed in baking oven
Middle drying is to get denatured conductive filler.
The modifying epoxy resin by organosilicon is the 4,5 dioctyl phthalate ring of 2- epoxy-cyclohexanes that polymethylphenylsiloxane is modified
Oxygen resin.
The mass ratio of AlN, SiN and graphene is 3 in the denatured conductive filler:1:2.5.
The curing agent is 4,4 diaminodiphenyl ethers.
The dispersant is sodium polymethacrylate.
The stabilizer is that mass ratio is 2:3 barium laurate and 2,6- d-tert-butyl-p-cresols.
The solvent is methyl cellosolve.
The dispersing aid is polyethylene glycol.
The preparation method of heat conducting film of the present invention, includes the following steps：
（1）Modifying epoxy resin by organosilicon is added in solution, 0.6h is stirred at a temperature of 90 DEG C, then cools the temperature to
62 DEG C, denatured conductive filler, curing agent, dispersant, stabilizer are added in reaction system, keeping this temperature, the reaction was continued
Then 1.3h handles 45min through ultrasonic disperse again, premixed liquid is made；
（2）By step（1）Premixed liquid obtained is cast in preheated mold, 80 DEG C of vacuumizing and defoaming 12min, then by temperature ladder
Degree is warming up to 123 DEG C, and keeps this temperature-curable 2.3h, last to be down to room temperature demoulding naturally to get heat conducting film.
Embodiment 4
A kind of high heat conducting nano heat conducting film, is prepared by the raw material of following parts by weight：40 parts of modifying epoxy resin by organosilicon changes
60 parts of conductive filler of property, 9 parts of curing agent, 9 parts of dispersant, 16 parts of stabilizer, 50 parts of solvent；
The denatured conductive filler is the mixture of AlN, SiN and graphene, mass ratio 1：4：5.
The preparation method of the denatured conductive filler is：（1）By 100 parts of graphenes first with 1-2 under atmosphere of inert gases
DEG C/rate of min is warming up to 600 DEG C, 1h is kept the temperature, then be warming up to 1200 DEG C under the same conditions with the rate of 3-5 DEG C/min,
After keeping the temperature 2h, it is down to room temperature naturally；
（2）By step（1）Treated graphene, 50 parts of AlN, 50 parts of SiN and it is added to 50 parts of ethanol solutions containing 10%DMF
In, 5-10 parts of dispersing aid is added thereto, and 40min is stirred at room temperature, temperature is risen to 60 DEG C, adds 8 parts of γ-ammonia
Propyl-triethoxysilicane continues after stirring 2h, and supernatant is removed by centrifugation, collects lower layer graphene precipitation, is placed in baking oven
Middle drying is to get denatured conductive filler.
The modifying epoxy resin by organosilicon is bisphenol A type epoxy resin, the glycerine ring that polymethylphenylsiloxane is modified
One kind or more of 4,5 dioctyl phthalate epoxy resin of oxygen resin, 4,5 dioctyl phthalate epoxy resin of 2- epoxy-cyclohexanes or 2- epoxy-cyclohexanes
The arbitrary combination of kind.
The mass ratio of AlN, SiN and graphene is 3 in the denatured conductive filler:1:2.5.
The curing agent is 4,4 diaminodiphenylmethane.
The dispersant is that mass ratio is 1:1 carmethose and dodecyl sodium sulfate.
The stabilizer is 2,6- d-tert-butyl-p-cresols.
The solvent is that mass ratio is 3:2 butanol and cyclohexanone.
The dispersing aid is calgon.
The preparation method of heat conducting film of the present invention, includes the following steps：
（1）Modifying epoxy resin by organosilicon is added in solution, 0.5-1h is stirred at a temperature of 80-120 DEG C, it then will be warm
Degree is down to 60-70 DEG C, and denatured conductive filler, curing agent, dispersant, stabilizer are added in reaction system, this temperature is kept
Then the reaction was continued 1-2h handles 40-60min through ultrasonic disperse again, premixed liquid is made；
（2）By step（1）Premixed liquid obtained is cast in preheated mold, 80 DEG C of vacuumizing and defoaming 10-20min, then will be warm
Gradient increased temperature is spent to 120-130 DEG C, and keeps this temperature-curable 2-3h, it is last to be down to room temperature demoulding naturally to get heat conducting film.
Comparative example 1
Difference lies in the filler in comparative example 1 carries out comparative example 1 without gamma-aminopropyl-triethoxy-silane with embodiment 1
Modification.
Comparative example 2
Difference lies in the epoxy resin in comparative example 2 is without modification with embodiment 1 for comparative example 2.
The technical solution of embodiment 1-4 and comparative example 1-2 is subjected to following performance test, test result is as shown in table 1：
It is obtained by test result, heat conducting film shear strength produced by the present invention reaches 83MPa, and peel strength reaches 14.2N/
Mm, thermal coefficient reaches 1738W/m K, therefore heat conducting film produced by the present invention has excellent heat conductivility, good mechanics
Performance is suitable for the commonly used of heat conduction membrane material.
Table 1
Claims (9)
1. a kind of high heat conducting nano heat conducting film, which is characterized in that be prepared by the raw material of following parts by weight：Organic silicon modified epoxy
15-40 parts of oxygen resin, 30-60 parts of denatured conductive filler, 4-9 parts of curing agent, 4-9 parts of dispersant, 8-16 parts of stabilizer, solvent
25-50 parts；
The denatured conductive filler is the mixture of AlN, SiN and graphene,
The preparation method of the denatured conductive filler is：（1）By 100 parts of graphenes under atmosphere of inert gases first with 1-2 DEG C/
The rate of min is warming up to 400-600 DEG C, keeps the temperature 0.5-1h, then be warming up under the same conditions with the rate of 3-5 DEG C/min
1000-1200 DEG C, after keeping the temperature 1-2h, it is down to room temperature naturally；
（2）By step（1）Treated graphene, 50 parts of AlN, 50 parts of SiN and to be added to the 30-50 parts of ethyl alcohol containing 10%DMF molten
In liquid, 5-10 parts of dispersing aid is added thereto, 20-40min is stirred at room temperature, temperature is risen to 40-60 DEG C, is added
3-8 parts of gamma-aminopropyl-triethoxy-silanes continue after stirring 1-2h, and supernatant is removed by centrifugation, and it is heavy to collect lower layer graphene
It forms sediment, is placed in baking oven and dries to get denatured conductive filler.
2. a kind of high heat conducting nano heat conducting film according to claim 1, which is characterized in that the silicon-modified epoxy tree
Fat is bisphenol A type epoxy resin, glycerol epoxy resin, 4,5 dioctyl phthalate of 2- epoxy-cyclohexanes that polymethylphenylsiloxane is modified
One or more arbitrary combinations of 4,5 dioctyl phthalate epoxy resin of epoxy resin or 2- epoxy-cyclohexanes.
3. a kind of high heat conducting nano heat conducting film according to claim 1, which is characterized in that in the denatured conductive filler
The mass ratio of AlN, SiN and graphene is 3:1:2.5.
4. a kind of high heat conducting nano heat conducting film according to claim 1, which is characterized in that the curing agent is 4,4 diaminos
Yl diphenyl ether or 4,4 diaminodiphenylmethane.
5. a kind of high heat conducting nano heat conducting film according to claim 1, which is characterized in that the dispersant is carboxylic first fiber
Plain sodium, sulfonated polyaniline, dodecyl sodium sulfate, cetyl trimethylammonium bromide, sodium polymethacrylate or sodium taurocholate
It is one or more.
6. a kind of high heat conducting nano heat conducting film according to claim 1, which is characterized in that the stabilizer is epoxy soybean
One or more combinations of oil, pentaerythrite, barium laurate or 2,6- d-tert-butyl-p-cresols.
7. a kind of high heat conducting nano heat conducting film according to claim 1, which is characterized in that the solvent is methyl ethyl ketone, different
Propyl alcohol, butanol, ethyl acetate, cyclohexanone, glycol monoethyl ether or methyl cellosolve.
8. a kind of high heat conducting nano heat conducting film according to claim 1, which is characterized in that the dispersing aid is polyethylene
One or more combinations of pyrrolidones, polyethylene glycol or calgon.
9. the preparation method of the heat conducting film described in claim 1-8, which is characterized in that include the following steps：
（1）Modifying epoxy resin by organosilicon is added in solution, 0.5-1h is stirred at a temperature of 80-120 DEG C, it then will be warm
Degree is down to 60-70 DEG C, and denatured conductive filler, curing agent, dispersant, stabilizer are added in reaction system, this temperature is kept
Then the reaction was continued 1-2h handles 40-60min through ultrasonic disperse again, premixed liquid is made；
（2）By step（1）Premixed liquid obtained is cast in preheated mold, 80 DEG C of vacuumizing and defoaming 10-20min, then will be warm
Gradient increased temperature is spent to 120-130 DEG C, and keeps this temperature-curable 2-3h, it is last to be down to room temperature demoulding naturally to get heat conducting film.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109972398A (en) * | 2019-04-16 | 2019-07-05 | 清华大学 | A kind of high thermal conductivity flexible-epoxy insulating materials and the preparation method and application thereof |
| CN113088037A (en) * | 2021-04-13 | 2021-07-09 | 珠海昌意新材料科技有限公司 | Heat dissipation material with high heat conductivity coefficient and high radiation coefficient and preparation method thereof |
| CN113290999A (en) * | 2021-02-19 | 2021-08-24 | 哈工大机器人集团(无锡)科创基地研究院 | Soft-surface composite heat conduction material with gridding distribution and preparation method thereof |
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| CN113290999A (en) * | 2021-02-19 | 2021-08-24 | 哈工大机器人集团(无锡)科创基地研究院 | Soft-surface composite heat conduction material with gridding distribution and preparation method thereof |
| CN113088037A (en) * | 2021-04-13 | 2021-07-09 | 珠海昌意新材料科技有限公司 | Heat dissipation material with high heat conductivity coefficient and high radiation coefficient and preparation method thereof |
| CN113088037B (en) * | 2021-04-13 | 2022-11-11 | 珠海昌意新材料科技有限公司 | Heat dissipation material with high heat conductivity coefficient and high radiation coefficient and preparation method thereof |
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Application publication date: 20181030 |