CN110759750A - Preparation method of high-thermal-conductivity ceramic material for LED - Google Patents
Preparation method of high-thermal-conductivity ceramic material for LED Download PDFInfo
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- CN110759750A CN110759750A CN201911061128.8A CN201911061128A CN110759750A CN 110759750 A CN110759750 A CN 110759750A CN 201911061128 A CN201911061128 A CN 201911061128A CN 110759750 A CN110759750 A CN 110759750A
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- aluminum nitride
- normal temperature
- weight
- stirring
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 57
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000000919 ceramic Substances 0.000 claims abstract description 36
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims abstract description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 67
- 238000003756 stirring Methods 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 53
- 239000000843 powder Substances 0.000 claims description 49
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- 239000008103 glucose Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 26
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 18
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 14
- 239000000395 magnesium oxide Substances 0.000 claims description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 14
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 239000011268 mixed slurry Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 13
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 13
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 12
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 12
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- 238000007731 hot pressing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000005262 decarbonization Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 11
- 229910052709 silver Inorganic materials 0.000 abstract description 11
- 239000004332 silver Substances 0.000 abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 9
- 230000017525 heat dissipation Effects 0.000 abstract description 7
- 238000007747 plating Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000010355 oscillation Effects 0.000 abstract description 2
- -1 silver ions Chemical class 0.000 abstract description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000015895 biscuits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- UWTNZVZEAHSTRO-UHFFFAOYSA-N azane;ethane-1,2-diamine Chemical compound N.NCCN UWTNZVZEAHSTRO-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/581—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on aluminium nitride
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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Abstract
The invention relates to a preparation method of a high-thermal-conductivity ceramic material for an LED, belonging to the technical field of LEDs. The invention takes aluminum nitride ceramic as a substrate, prepares a high-thermal-conductivity ceramic material for an LED through a chemical silver plating process, the aluminum nitride ceramic is a ceramic material with excellent comprehensive performance, the aluminum nitride has the characteristics of low atomic weight, strong interatomic bonding, simple crystal structure, high lattice oscillation harmony and the like, so that the aluminum nitride ceramic has extremely high thermal conductivity, the aluminum nitride ceramic substrate is subjected to surface chemical silver plating, ammonia water and silver ions are used for forming silver-ammonia complex ion solution, and potassium hydroxide is used as a speed regulator and a pH regulator, so that the deposition rate can be increased, the silver plating rate can be effectively improved, and the heat dissipation performance of the material is improved.
Description
Technical Field
The invention relates to a preparation method of a high-thermal-conductivity ceramic material for an LED, belonging to the technical field of LEDs.
Background
The LED structure composition can be simply summarized into three main parts, namely a heat dissipation substrate, a chip and fluorescent powder. The heat dissipation substrate has two main functions: firstly, the bracket plays a supporting role; and secondly, the heat conduction and dissipation effects in the working process of the LED are achieved.
The alumina ceramic is the most common ceramic substrate material, and is the most widely used ceramic substrate material at present due to low price, good stability, good insulation and mechanical properties and pure process technology. However, the thermal conductivity of the alumina ceramic is low (20W/m.K), and the thermal expansion coefficient is not matched with that of Si, so that the application of the alumina ceramic in high-power electronic products is limited to a certain extent, and the application range of the alumina ceramic is limited in the packaging field that the voltage which can be borne by a circuit is low and the integration level of the circuit is not high. Beryllium oxide ceramic is a high-thermal-conductivity ceramic substrate material which is commonly used at present, has good comprehensive performance, can meet higher electronic packaging requirements, but has larger thermal conductivity along with temperature fluctuation, and greatly reduces the thermal conductivity when the temperature is increased. In addition, beryllium oxide is extremely toxic and not beneficial to large-scale production, so that the application of beryllium oxide is greatly limited. The silicon carbide ceramic has high thermal conductivity, the thermal expansion coefficient is also closest to that of Si, and the silicon carbide has good physical properties, high wear resistance and high hardness, but the silicon carbide is a compound with strong covalent bonds, the sintering temperature is as high as two thousand or more, and only a small amount of sintering aid needs to be added to enable the silicon carbide ceramic substrate to be sintered to be compact, so that the preparation energy consumption of the silicon carbide ceramic substrate is high, the hot-pressing production cost is high, and the development and the large-batch application of the silicon carbide are limited to a great extent. The aluminum nitride ceramic serving as a novel LED packaging substrate material has the excellent performances of high strength, low thermal expansion coefficient, small dielectric loss, high temperature resistance, chemical corrosion resistance, good insulativity, no toxicity, environmental friendliness and the like, but the current commercial aluminum nitride substrate has poor heat dissipation performance, so that the further development of the aluminum nitride substrate is limited.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problem of low heat dissipation efficiency of the existing LED ceramic substrate, the preparation method of the high-heat-conductivity ceramic material for the LED is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
(1) respectively weighing 20-40 parts of aluminum nitride ceramic, 10-20 parts of silver nitrate, 10-20 parts of ammonia water, 1-2 parts of ethylenediamine, 0.2-0.4 part of sodium thiosulfate, 2-4 parts of potassium hydroxide, 4-8 parts of glucose, 2-4 parts of potassium sodium tartrate, 1-2 parts of polyethylene glycol, 20-40 parts of absolute ethyl alcohol and 80-160 parts of deionized water in parts by weight;
(2) adding silver nitrate into 1/2 parts by weight of deionized water, and stirring at the rotating speed of 120-160 r/min for 10-20 min at normal temperature to obtain a silver nitrate solution;
(3) adding ammonia water, ethylenediamine and sodium thiosulfate into a silver nitrate solution, and stirring at the normal temperature at the rotating speed of 200-250 r/min for 40-60 min to obtain a silver-ammonia suspension;
(4) adding potassium hydroxide into the silver-ammonia suspension, and stirring at the normal temperature at the rotating speed of 250-300 r/min for 20-30 min to obtain a silver-ammonia complex solution;
(5) adding glucose and potassium sodium tartrate into the residual 1/2 parts by weight of deionized water, and stirring for 20-30 min at the rotating speed of 160-200 r/min under the water bath condition of 80-90 ℃ to obtain a glucose mixed solution;
(6) adding polyethylene glycol and absolute ethyl alcohol into the glucose mixed solution, and stirring at the normal temperature at the rotating speed of 200-250 r/min for 30-40 min to obtain a reducing agent solution;
(7) adding aluminum nitride ceramic and a reducing agent solution into a silver-ammonia complex solution, stirring for 2-4 h at 200-300 r/min under the condition of a water bath at 40-60 ℃, filtering, taking a filter cake, washing for 3-5 times by using deionized water, drying for 1-2 h in an oven at 60-80 ℃, and cooling at normal temperature to obtain the high-thermal-conductivity ceramic material for the LED.
The mass fraction of the ammonia water in the step (1) is 10%.
The aluminum nitride ceramic prepared in the step (1) comprises the following specific preparation steps:
(1) respectively weighing 20-30 parts by weight of aluminum nitride powder, 0.8-1.2 parts by weight of calcium carbonate powder, 0.4-0.6 part by weight of magnesium oxide, 0.4-0.6 part by weight of silicon dioxide, 0.2-0.3 part by weight of boric acid, 8-12 parts by weight of polyvinyl butyral and 100-150 parts by weight of absolute ethyl alcohol;
(2) adding aluminum nitride powder, calcium carbonate powder, magnesium oxide, silicon dioxide and boric acid into 1/2 parts by weight of absolute ethyl alcohol, placing the mixture in a ball mill, and ball-milling the mixture for 4-8 hours at the normal temperature at the rotating speed of 160-200 r/min to obtain mixed slurry;
(3) adding polyvinyl butyral into absolute ethyl alcohol, and stirring at the rotating speed of 200-240 r/min for 20-40 min at normal temperature to obtain a polyvinyl butyral ethyl alcohol solution;
(4) adding the polyvinyl butyral ethanol solution into the mixed slurry, stirring at the normal temperature at the rotating speed of 400-600 r/min for 1-2 h to obtain a mixture, and placing the mixture in a hot press for hot pressing for 40-60 min to obtain a blank;
(5) and (3) placing the blank in a tubular atmosphere furnace, heating to 500-600 ℃ at the normal temperature at the speed of 5 ℃/min, preserving heat for 1-2 h, heating to 1600-1800 ℃ at the speed of 1 ℃/min, introducing nitrogen for protection, preserving heat, sintering for 2-4 h, and cooling to the room temperature along with the furnace to obtain the aluminum nitride ceramic.
The average particle size of the calcium carbonate powder in the step (1) is 20-40 μm, the average particle size of the magnesium oxide is 20-40 μm, the average particle size of the silicon dioxide is 30-50 μm, and the average particle size of the boric acid is 60-80 μm.
The hot pressing treatment in the step (4) is carried out at the temperature of 80-90 ℃ and under the pressure of 160-200 MPa.
And (5) introducing the nitrogen at a rate of 150-200 mL/min.
The specific preparation steps of the aluminum nitride powder in the step (1) are as follows:
(1) respectively weighing 20-30 parts of aluminum nitrate, 2-3 parts of calcium nitrate, 2-3 parts of yttrium nitrate, 10-15 parts of glucose and 100-150 parts of deionized water in parts by weight;
(2) adding aluminum nitrate, calcium nitrate, yttrium nitrate and glucose into deionized water, and stirring at the normal temperature at the rotating speed of 200-300 r/min for 20-30 min to obtain a mixed solution;
(3) heating the mixed solution in an oven at 120-140 ℃ for 1-2 h to obtain foam powder;
(4) placing the foamed powder in a muffle furnace, heating to 1000-1200 ℃ at the normal temperature at the speed of 20 ℃/min, and carrying out heat preservation and calcination for 40-60 min to obtain a mixed powder precursor;
(5) and (3) placing the mixed powder precursor in a vacuum carbon tube sintering furnace, introducing nitrogen, heating to 1300-1600 ℃ at the normal temperature at the speed of 50 ℃/min, insulating and nitriding for 2-4 h, cooling to 600-800 ℃, insulating and decarbonizing for 30-40 min, and cooling to room temperature along with the furnace to obtain the aluminum nitride powder.
The nitrogen gas is introduced at a rate of 100-120 mL/min in the step (5), and the average particle size of the aluminum nitride powder is 100-200 μm.
Compared with other methods, the method has the beneficial technical effects that:
the invention takes the aluminum nitride ceramic as the substrate, prepares the high heat conduction ceramic material for the LED through the chemical silver plating process, the aluminum nitride ceramic is a ceramic material with excellent comprehensive performance, the aluminum nitride has the characteristics of low atomic weight, strong interatomic bond, simple crystal structure, high lattice oscillation harmony and the like, thereby having extremely high heat conductivity, the decomposition temperature of the aluminum nitride is as high as 2450 ℃, the stability is excellent in high-temperature non-oxide atmosphere within 2000 ℃, the thermal shock resistance is also very good, in addition, the aluminum nitride has the characteristic of being not eroded by aluminum and other molten metals, has extremely good erosion resistance, good electrical insulation and dielectric properties, the heat dissipation and stability of the material can be effectively improved by taking the aluminum nitride ceramic as the substrate, the chemical plating adopts the principle that the metal salt and the reducing agent in the same solution can carry out oxidation reduction reaction on the surface of the substrate with catalytic activity under the condition of no external current, the surface treatment technology for forming a metal or alloy coating on the surface of a substrate through chemical deposition is characterized in that metal silver is the most effective material for storage and reflection, and has the strongest electric and heat conducting properties among all metals, and silver is chemically plated on the surface of an aluminum nitride ceramic substrate, so that the surface treatment technology has excellent electric conductivity and safe and reliable anti-electromagnetic shielding efficiency; the silver plating layer also has the functions of long-acting antibiosis, good biocompatibility and static resistance, ammonia water and silver ions are used for forming silver-ammonia complex ion solution, the concentration of the ammonia water is improved, the stability of the solution can be improved, amine ethylenediamine and sodium thiosulfate are added to form substances of stable complexes with silver, potassium hydroxide is used as a speed regulator and a pH regulator, the deposition rate can be increased, the silver plating rate can be effectively improved, and therefore the heat dissipation performance of the material can be effectively improved.
Detailed Description
Respectively weighing 20-30 parts of aluminum nitrate, 2-3 parts of calcium nitrate, 2-3 parts of yttrium nitrate, 10-15 parts of glucose and 100-150 parts of deionized water, adding the aluminum nitrate, the calcium nitrate, the yttrium nitrate and the glucose into the deionized water, stirring at the normal temperature at the rotating speed of 200-300 r/min for 20-30 min to obtain a mixed solution, heating the mixed solution in a drying oven at the temperature of 120-140 ℃ for 1-2 h to obtain a foamed powder, placing the foamed powder in a muffle furnace, heating to 1000-1200 ℃ at the normal temperature at the speed of 20 ℃/min, carrying out heat preservation and calcination for 40-60 min to obtain a mixed powder precursor, placing the mixed powder precursor in a carbon tube vacuum sintering furnace, introducing nitrogen at the speed of 100-120 mL/min, heating to 1300-1600 ℃ at the normal temperature at the speed of 50 ℃/min, carrying out heat preservation and nitridation for 2-4 h, cooling to 600-800 ℃, preserving heat and removing carbon for 30-40 min, and cooling to room temperature along with the furnace to obtain aluminum nitride powder with the average particle size of 100-200 mu m;
respectively weighing 20-30 parts by weight of aluminum nitride powder, 0.8-1.2 parts by weight of calcium carbonate powder with the average particle size of 20-40 mu m, 0.4-0.6 part by weight of magnesium oxide with the average particle size of 20-40 mu m, 0.4-0.6 part by weight of silicon dioxide with the average particle size of 30-50 mu m, 0.2-0.3 part by weight of boric acid with the average particle size of 60-80 mu m, 8-12 parts by weight of polyvinyl butyral and 100-150 parts by weight of absolute ethyl alcohol, adding the aluminum nitride powder, the calcium carbonate powder, the magnesium oxide, the silicon dioxide and the boric acid into 1/2 parts by weight of the absolute ethyl alcohol, placing the mixture into a ball mill, ball-milling the mixture at the rotating speed of 160-200 r/min for 4-8 h at normal temperature to obtain mixed slurry, adding the polyvinyl butyral into the absolute ethyl alcohol, stirring the mixture at the rotating speed of 200-240 r/min at normal temperature for 20-40 min to obtain a polyvinyl butyral ethanol solution, adding the polyvinyl butyral solution, stirring at the rotation speed of 400-600 r/min for 1-2 h at normal temperature to obtain a mixture, placing the mixture in a hot press, carrying out hot pressing treatment for 40-60 min under the conditions of the temperature of 80-90 ℃ and the pressure of 160-200 MPa to obtain a blank, placing the blank in a tubular atmosphere furnace, heating to 500-600 ℃ at the normal temperature at the speed of 5 ℃/min, carrying out heat preservation for 1-2 h, heating to 1600-1800 ℃ at the speed of 1 ℃/min, introducing nitrogen at the speed of 150-200 mL/min for protection, carrying out heat preservation sintering for 2-4 h, and cooling to the room temperature along with the furnace to obtain aluminum nitride ceramic;
respectively weighing 20-40 parts of aluminum nitride ceramic, 10-20 parts of silver nitrate, 10-20 parts of 10 mass percent ammonia water, 1-2 parts of ethylenediamine, 0.2-0.4 part of sodium thiosulfate, 2-4 parts of potassium hydroxide, 4-8 parts of glucose, 2-4 parts of potassium sodium tartrate, 1-2 parts of polyethylene glycol, 20-40 parts of absolute ethyl alcohol and 80-160 parts of deionized water, adding silver nitrate into 1/2 parts of deionized water, stirring at the rotating speed of 120-160 r/min at normal temperature for 10-20 min to obtain a silver nitrate solution, adding ammonia water, ethylenediamine and sodium thiosulfate into the silver nitrate solution, stirring at the rotating speed of 200-250 r/min at normal temperature for 40-60 min to obtain a silver ammonia suspension, adding potassium hydroxide into the silver ammonia suspension, stirring at the rotating speed of 250-300 r/min at normal temperature for 20-30 min to obtain a silver ammonia complex solution, adding glucose and potassium sodium tartrate into the residual 1/2 parts by weight of deionized water, stirring at a rotating speed of 160-200 r/min for 20-30 min under a water bath condition of 80-90 ℃ to obtain a glucose mixed solution, adding polyethylene glycol and anhydrous ethanol into the glucose mixed solution, stirring at a rotating speed of 200-250 r/min for 30-40 min at normal temperature to obtain a reducing agent solution, adding aluminum nitride ceramic and the reducing agent solution into the silver-ammonia complex solution, stirring at a rotating speed of 200-300 r/min for 2-4 h under a water bath condition of 40-60 ℃, filtering, taking a filter cake, washing with deionized water for 3-5 times, drying in an oven at 60-80 ℃ for 1-2 h, and cooling at normal temperature to obtain the high-thermal-conductivity ceramic material for the LED.
Example 1
Respectively weighing 20 parts of aluminum nitrate, 2 parts of calcium nitrate, 2 parts of yttrium nitrate, 10 parts of glucose and 100 parts of deionized water according to parts by weight, adding the aluminum nitrate, the calcium nitrate, the yttrium nitrate and the glucose into the deionized water, stirring at normal temperature at a rotation speed of 200r/min for 20min to obtain a mixed solution, heating the mixed solution in an oven at 120 ℃ for 1h to obtain foam powder, placing the foam powder in a muffle furnace, heating to 1000 deg.C at a rate of 20 deg.C/min at room temperature, calcining for 40min to obtain mixed powder precursor, placing the mixed powder precursor in a vacuum carbon tube sintering furnace, introducing nitrogen at the speed of 100mL/min, heating to 1300 ℃ at the speed of 50 ℃/min at normal temperature, preserving heat and nitriding for 2h, cooling to 600 ℃, preserving heat and removing carbon for 30min, and cooling to room temperature along with a furnace to obtain aluminum nitride powder with the average particle size of 100 mu m;
respectively weighing 20 parts by weight of aluminum nitride powder, 0.8 part of calcium carbonate powder with the average particle size of 20 microns, 0.4 part of magnesium oxide with the average particle size of 20 microns, 0.4 part of silicon dioxide with the average particle size of 30 microns, 0.2 part of boric acid with the average particle size of 60 microns, 8 parts of polyvinyl butyral and 100 parts of absolute ethyl alcohol, adding the aluminum nitride powder, the calcium carbonate powder, the magnesium oxide, the silicon dioxide and the boric acid into 1/2 parts by weight of absolute ethyl alcohol, placing the mixture into a ball mill, ball-milling the mixture for 4 hours at the normal temperature at the rotating speed of 160r/min to obtain mixed slurry, adding the polyvinyl butyral into the absolute ethyl alcohol, stirring the polyvinyl butyral ethanol solution for 20 minutes at the normal temperature at the rotating speed of 200r/min to obtain a polyvinyl butyral ethanol solution, adding the polyvinyl butyral ethanol solution into the mixed slurry, stirring the mixed slurry for 1 hour at the normal temperature at the rotating speed of 400r/min to obtain a mixed material, placing the mixed, carrying out hot pressing treatment for 40min at the temperature of 80 ℃ and the pressure of 160MPa to obtain a blank, placing the blank in a tubular atmosphere furnace, heating to 500 ℃ at the normal temperature at the speed of 5 ℃/min, preserving heat for 1h, heating to 1600 ℃ at the speed of 1 ℃/min, introducing nitrogen at the speed of 150mL/min for protection, preserving heat, sintering for 2h, and cooling to room temperature along with the furnace to obtain aluminum nitride ceramic;
respectively weighing 20 parts of aluminum nitride ceramic, 10 parts of silver nitrate, 10 parts of 10 mass percent ammonia water, 1 part of ethylenediamine, 0.2 part of sodium thiosulfate, 2 parts of potassium hydroxide, 4 parts of glucose, 2 parts of potassium sodium tartrate, 1 part of polyethylene glycol, 20 parts of absolute ethyl alcohol and 80 parts of deionized water, adding the silver nitrate into 1/2 parts of deionized water by weight, stirring at the rotating speed of 120r/min for 10min at normal temperature to obtain a silver nitrate solution, adding the ammonia water, the ethylenediamine and the sodium thiosulfate into the silver nitrate solution, stirring at the rotating speed of 200r/min at normal temperature for 40min to obtain a silver-ammonia suspension, adding the potassium hydroxide into the silver-ammonia suspension, stirring at the rotating speed of 250r/min for 20min at normal temperature to obtain a silver-ammonia complex solution, adding the glucose and the potassium sodium tartrate into the rest 1/2 parts of deionized water by weight, stirring at the rotating speed of 160r/min for 20min under the water bath condition of 80 ℃, and (2) obtaining a glucose mixed solution, adding polyethylene glycol and part of absolute ethyl alcohol into the glucose mixed solution, stirring at the normal temperature at the rotating speed of 200r/min for 30min to obtain a reducing agent solution, adding the aluminum nitride ceramic and the reducing agent solution into the silver-ammonia complex solution, stirring at the rotating speed of 200r/min for 2h under the water bath condition of 40 ℃, filtering, taking a filter cake, washing with deionized water for 3 times, drying in a 60 ℃ oven for 1h, and cooling at the normal temperature to obtain the high-thermal-conductivity ceramic material for the LED.
Example 2
Respectively weighing 25 parts of aluminum nitrate, 2.5 parts of calcium nitrate, 2.5 parts of yttrium nitrate, 12.5 parts of glucose and 125 parts of deionized water according to parts by weight, adding the aluminum nitrate, the calcium nitrate, the yttrium nitrate and the glucose into the deionized water, stirring at 250r/min for 25min at normal temperature to obtain mixed solution, heating the mixed solution in a 130 deg.C oven for 1.5 hr to obtain foam powder, placing the foam powder in a muffle furnace, heating to 1100 deg.C at a rate of 20 deg.C/min at room temperature, calcining for 50min to obtain mixed powder precursor, placing the mixed powder precursor in a vacuum carbon tube sintering furnace, introducing nitrogen at a speed of 110mL/min, heating to 1450 ℃ at a speed of 50 ℃/min at normal temperature, carrying out heat preservation and nitridation for 3h, cooling to 700 ℃, carrying out heat preservation and decarbonization for 35min, and cooling to room temperature along with a furnace to obtain aluminum nitride powder with an average particle size of 150 mu m;
respectively weighing 25 parts by weight of aluminum nitride powder, 1 part of calcium carbonate powder with the average particle size of 30 mu m, 0.5 part of magnesium oxide with the average particle size of 30 mu m, 0.5 part of silicon dioxide with the average particle size of 40 mu m, 0.25 part of boric acid with the average particle size of 70 mu m, 10 parts of polyvinyl butyral and 125 parts of absolute ethyl alcohol, adding the aluminum nitride powder, the calcium carbonate powder, the magnesium oxide, the silicon dioxide and the boric acid into 1/2 parts by weight of absolute ethyl alcohol, placing the mixture into a ball mill, ball-milling the mixture at the normal temperature at the rotating speed of 180r/min for 6 hours to obtain mixed slurry, adding the polyvinyl butyral into the absolute ethyl alcohol, stirring the mixture at the normal temperature at the rotating speed of 220r/min for 30 minutes to obtain polyvinyl butyral ethanol solution, adding the polyvinyl butyral ethanol solution into the mixed slurry, stirring the mixture at the normal temperature at the rotating speed of 500r/min for 1.5 hours to obtain a mixed material, placing the mixed material, carrying out hot pressing treatment for 50min at the temperature of 85 ℃ and the pressure of 180MPa to obtain a biscuit, placing the biscuit in a tubular atmosphere furnace, heating to 550 ℃ at the normal temperature at the speed of 5 ℃/min, preserving heat for 1.5h, heating to 1700 ℃ at the speed of 1 ℃/min, introducing nitrogen at the speed of 175mL/min for protection, preserving heat, sintering for 3h, and cooling to room temperature along with the furnace to obtain aluminum nitride ceramic;
then respectively weighing 30 parts of aluminum nitride ceramics, 15 parts of silver nitrate, 15 parts of 10 mass percent ammonia water, 1.5 parts of ethylenediamine, 0.3 part of sodium thiosulfate, 3 parts of potassium hydroxide, 6 parts of glucose, 3 parts of potassium sodium tartrate, 1.5 parts of polyethylene glycol, 30 parts of absolute ethyl alcohol and 120 parts of deionized water, adding the silver nitrate into 1/2 parts of deionized water by weight, stirring at the rotating speed of 140r/min for 15min at normal temperature to obtain a silver nitrate solution, adding the ammonia water, the ethylenediamine and the sodium thiosulfate into the silver nitrate solution, stirring at the rotating speed of 225r/min for 50min at normal temperature to obtain a silver-ammonia suspension, adding the potassium hydroxide into the silver-ammonia suspension, stirring at the rotating speed of 275r/min for 25min at normal temperature to obtain a silver-ammonia complex solution, adding the glucose and the potassium sodium tartrate into the rest 1/2 parts of deionized water by weight, stirring at the rotating speed of 180r/min for 25min under the water bath condition of 85 ℃, and (2) obtaining a glucose mixed solution, adding polyethylene glycol and part of absolute ethyl alcohol into the glucose mixed solution, stirring at the normal temperature for 35min at the rotating speed of 225r/min to obtain a reducing agent solution, adding the aluminum nitride ceramic and the reducing agent solution into the silver-ammonia complex solution, stirring for 3h at the rotating speed of 250r/min under the water bath condition of 50 ℃, filtering, taking a filter cake, washing with deionized water for 4 times, drying in an oven at the temperature of 70 ℃ for 1.5h, and cooling at the normal temperature to obtain the high-thermal-conductivity ceramic material for the LED.
Example 3
Respectively weighing 30 parts of aluminum nitrate, 3 parts of calcium nitrate, 3 parts of yttrium nitrate, 15 parts of glucose and 150 parts of deionized water according to parts by weight, adding the aluminum nitrate, the calcium nitrate, the yttrium nitrate and the glucose into the deionized water, stirring at 300r/min for 30min at normal temperature to obtain mixed solution, heating the mixed solution in a drying oven at 140 deg.C for 2 hr to obtain foam powder, placing the foam powder in a muffle furnace, heating to 1200 ℃ at the normal temperature at the speed of 20 ℃/min, keeping the temperature and calcining for 60min to obtain a mixed powder precursor, placing the mixed powder precursor in a vacuum carbon tube sintering furnace, introducing nitrogen at the speed of 120mL/min, heating to 1600 ℃ at the speed of 50 ℃/min at normal temperature, preserving heat and nitriding for 4h, then cooling to 800 ℃, preserving heat and removing carbon for 40min, and cooling to room temperature along with a furnace to obtain aluminum nitride powder with the average particle size of 200 mu m;
respectively weighing 30 parts by weight of aluminum nitride powder, 1.2 parts by weight of calcium carbonate powder with the average particle size of 40 mu m, 0.6 part by weight of magnesium oxide with the average particle size of 40 mu m, 0.6 part by weight of silicon dioxide with the average particle size of 50 mu m, 0.3 part by weight of boric acid with the average particle size of 80 mu m, 12 parts by weight of polyvinyl butyral and 150 parts by weight of absolute ethyl alcohol, adding the aluminum nitride powder, the calcium carbonate powder, the magnesium oxide, the silicon dioxide and the boric acid into 1/2 parts by weight of absolute ethyl alcohol, placing the mixture into a ball mill, ball-milling the mixture at the normal temperature at the rotating speed of 200r/min for 8 hours to obtain mixed slurry, adding the polyvinyl butyral into the absolute ethyl alcohol, stirring the polyvinyl butyral ethanol solution at the normal temperature at the rotating speed of 240r/min for 40 minutes to obtain a polyvinyl butyral ethanol solution, adding the polyvinyl butyral ethanol solution into the mixed slurry, stirring the mixed slurry at the normal temperature at the rotating speed of, carrying out hot pressing treatment for 60min at the temperature of 90 ℃ and the pressure of 200MPa to obtain a blank, placing the blank in a tubular atmosphere furnace, heating to 600 ℃ at the normal temperature at the speed of 5 ℃/min, preserving heat for 2h, heating to 1800 ℃ at the speed of 1 ℃/min, introducing nitrogen at the speed of 200mL/min for protection, preserving heat, sintering for 4h, and cooling to room temperature along with the furnace to obtain aluminum nitride ceramic;
then respectively weighing 40 parts of aluminum nitride ceramics, 20 parts of silver nitrate, 20 parts of 10 mass percent ammonia water, 2 parts of ethylenediamine, 0.4 part of sodium thiosulfate, 4 parts of potassium hydroxide, 8 parts of glucose, 4 parts of potassium sodium tartrate, 2 parts of polyethylene glycol, 40 parts of absolute ethyl alcohol and 160 parts of deionized water, adding the silver nitrate into 1/2 parts of deionized water by weight, stirring for 20min at the normal temperature at the rotating speed of 160r/min to obtain a silver nitrate solution, adding the ammonia water, the ethylenediamine and the sodium thiosulfate into the silver nitrate solution, stirring for 60min at the normal temperature at the rotating speed of 250r/min to obtain a silver-ammonia suspension, adding the potassium hydroxide into the silver-ammonia suspension, stirring for 30min at the normal temperature at the rotating speed of 300r/min to obtain a silver-ammonia complex solution, adding the glucose and the potassium sodium tartrate into the rest 1/2 parts of deionized water by weight, stirring for 30min at the rotating speed of 200r/min under the water bath condition of 90 ℃, and (2) obtaining a glucose mixed solution, adding polyethylene glycol and part of absolute ethyl alcohol into the glucose mixed solution, stirring at the normal temperature at the rotating speed of 250r/min for 40min to obtain a reducing agent solution, adding the aluminum nitride ceramic and the reducing agent solution into the silver-ammonia complex solution, stirring at the rotating speed of 300r/min for 4h under the water bath condition of 60 ℃, filtering, taking a filter cake, washing with deionized water for 5 times, drying in an oven at the temperature of 80 ℃ for 2h, and cooling at the normal temperature to obtain the high-thermal-conductivity ceramic material for the LED.
Claims (8)
1. A preparation method of a high-thermal-conductivity ceramic material for LEDs is characterized by comprising the following specific preparation steps:
(1) respectively weighing 20-40 parts of aluminum nitride ceramic, 10-20 parts of silver nitrate, 10-20 parts of ammonia water, 1-2 parts of ethylenediamine, 0.2-0.4 part of sodium thiosulfate, 2-4 parts of potassium hydroxide, 4-8 parts of glucose, 2-4 parts of potassium sodium tartrate, 1-2 parts of polyethylene glycol, 20-40 parts of absolute ethyl alcohol and 80-160 parts of deionized water in parts by weight;
(2) adding silver nitrate into 1/2 parts by weight of deionized water, and stirring at the rotating speed of 120-160 r/min for 10-20 min at normal temperature to obtain a silver nitrate solution;
(3) adding ammonia water, ethylenediamine and sodium thiosulfate into a silver nitrate solution, and stirring at the normal temperature at the rotating speed of 200-250 r/min for 40-60 min to obtain a silver-ammonia suspension;
(4) adding potassium hydroxide into the silver-ammonia suspension, and stirring at the normal temperature at the rotating speed of 250-300 r/min for 20-30 min to obtain a silver-ammonia complex solution;
(5) adding glucose and potassium sodium tartrate into the residual 1/2 parts by weight of deionized water, and stirring for 20-30 min at the rotating speed of 160-200 r/min under the water bath condition of 80-90 ℃ to obtain a glucose mixed solution;
(6) adding polyethylene glycol and absolute ethyl alcohol into the glucose mixed solution, and stirring at the normal temperature at the rotating speed of 200-250 r/min for 30-40 min to obtain a reducing agent solution;
(7) adding aluminum nitride ceramic and a reducing agent solution into a silver-ammonia complex solution, stirring for 2-4 h at 200-300 r/min under the condition of a water bath at 40-60 ℃, filtering, taking a filter cake, washing for 3-5 times by using deionized water, drying for 1-2 h in an oven at 60-80 ℃, and cooling at normal temperature to obtain the high-thermal-conductivity ceramic material for the LED.
2. The method for preparing a high thermal conductivity ceramic material for LED according to claim 1, wherein the mass fraction of the ammonia water in step (1) is 10%.
3. The method for preparing the high thermal conductivity ceramic material for the LED according to claim 1, wherein the aluminum nitride ceramic in the step (1) is prepared by the following specific steps:
(1) respectively weighing 20-30 parts by weight of aluminum nitride powder, 0.8-1.2 parts by weight of calcium carbonate powder, 0.4-0.6 part by weight of magnesium oxide, 0.4-0.6 part by weight of silicon dioxide, 0.2-0.3 part by weight of boric acid, 8-12 parts by weight of polyvinyl butyral and 100-150 parts by weight of absolute ethyl alcohol;
(2) adding aluminum nitride powder, calcium carbonate powder, magnesium oxide, silicon dioxide and boric acid into 1/2 parts by weight of absolute ethyl alcohol, placing the mixture in a ball mill, and ball-milling the mixture for 4-8 hours at the normal temperature at the rotating speed of 160-200 r/min to obtain mixed slurry;
(3) adding polyvinyl butyral into absolute ethyl alcohol, and stirring at the rotating speed of 200-240 r/min for 20-40 min at normal temperature to obtain a polyvinyl butyral ethyl alcohol solution;
(4) adding the polyvinyl butyral ethanol solution into the mixed slurry, stirring at the normal temperature at the rotating speed of 400-600 r/min for 1-2 h to obtain a mixture, and placing the mixture in a hot press for hot pressing for 40-60 min to obtain a blank;
(5) and (3) placing the blank in a tubular atmosphere furnace, heating to 500-600 ℃ at the normal temperature at the speed of 5 ℃/min, preserving heat for 1-2 h, heating to 1600-1800 ℃ at the speed of 1 ℃/min, introducing nitrogen for protection, preserving heat, sintering for 2-4 h, and cooling to the room temperature along with the furnace to obtain the aluminum nitride ceramic.
4. The method for preparing a high thermal conductive ceramic material for LED according to claim 3, wherein the average particle size of the calcium carbonate powder in step (1) is 20-40 μm, the average particle size of the magnesium oxide is 20-40 μm, the average particle size of the silicon dioxide is 30-50 μm, and the average particle size of the boric acid is 60-80 μm.
5. The method for preparing the high thermal conductivity ceramic material for the LED according to claim 3, wherein the hot pressing treatment in the step (4) is carried out at a temperature of 80-90 ℃ and a pressure of 160-200 MPa.
6. The method for preparing a high thermal conductivity ceramic material for LED according to claim 3, wherein the nitrogen gas is introduced at a rate of 150-200 mL/min in step (5).
7. The preparation method of the high thermal conductivity ceramic material for the LED according to claim 3, wherein the specific preparation steps of the aluminum nitride powder in the step (1) are as follows:
(1) respectively weighing 20-30 parts of aluminum nitrate, 2-3 parts of calcium nitrate, 2-3 parts of yttrium nitrate, 10-15 parts of glucose and 100-150 parts of deionized water in parts by weight;
(2) adding aluminum nitrate, calcium nitrate, yttrium nitrate and glucose into deionized water, and stirring at the normal temperature at the rotating speed of 200-300 r/min for 20-30 min to obtain a mixed solution;
(3) heating the mixed solution in an oven at 120-140 ℃ for 1-2 h to obtain foam powder;
(4) placing the foam powder in a muffle furnace, heating to 1000-1200 ℃ at the normal temperature at the speed of 20 ℃/min, and carrying out heat preservation and calcination for 40-60 min to obtain a mixed powder precursor;
(5) and (3) placing the mixed powder precursor in a vacuum carbon tube sintering furnace, introducing nitrogen, heating to 1300 ℃ and 1600 ℃ at the speed of 50 ℃/min at normal temperature, carrying out heat preservation and nitridation for 2-4 h, cooling to 600-800 ℃, carrying out heat preservation and decarbonization for 30-40 min, and cooling to room temperature along with the furnace to obtain the aluminum nitride powder.
8. The preparation method of the high thermal conductivity ceramic material for the LED according to claim 7, wherein the nitrogen gas is introduced at a rate of 100-120 mL/min in the step (5), and the average particle size of the aluminum nitride powder is 100-200 μm.
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