CN117720828A - Preparation method of alpha-alumina coated spherical aluminum nitride - Google Patents
Preparation method of alpha-alumina coated spherical aluminum nitride Download PDFInfo
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- CN117720828A CN117720828A CN202311730167.9A CN202311730167A CN117720828A CN 117720828 A CN117720828 A CN 117720828A CN 202311730167 A CN202311730167 A CN 202311730167A CN 117720828 A CN117720828 A CN 117720828A
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 157
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 238000001354 calcination Methods 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
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- GVKJHCRQHGHBQF-UHFFFAOYSA-I [Si+2]=O.[OH-].[Al+3].[OH-].[OH-].[OH-].[OH-] Chemical compound [Si+2]=O.[OH-].[Al+3].[OH-].[OH-].[OH-].[OH-] GVKJHCRQHGHBQF-UHFFFAOYSA-I 0.000 claims description 25
- 239000012153 distilled water Substances 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
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- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 21
- 230000007062 hydrolysis Effects 0.000 abstract description 20
- 230000004048 modification Effects 0.000 abstract description 16
- 238000012986 modification Methods 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 8
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- 238000002844 melting Methods 0.000 abstract description 3
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- 239000010410 layer Substances 0.000 description 50
- 230000000052 comparative effect Effects 0.000 description 32
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 11
- 239000001110 calcium chloride Substances 0.000 description 11
- 229910001628 calcium chloride Inorganic materials 0.000 description 11
- 238000011049 filling Methods 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- -1 phosphoric acid modified aluminum nitride Chemical class 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a preparation method of alpha-alumina coated spherical aluminum nitride, which comprises the following steps: taking irregular aluminum nitride as a raw material, carrying out hydrolysis and coupling agent ball milling modification treatment on the surface of the irregular aluminum nitride to form ball-like aluminum nitride containing an aluminum hydroxide-silica layer; and then the alpha-alumina coated spherical aluminum nitride is obtained by melting and calcining the alpha-alumina coated spherical aluminum nitride with a mineralizer under the protective atmosphere condition. The invention successfully realizes the effective coating of the alpha-alumina on the aluminum nitride, and the obtained alpha-alumina coated spherical aluminum nitride powder has the advantages of excellent spherical morphology, uniform size, excellent dispersion performance, easy obtainment of raw materials, simple process and lower cost, and greatly improves the hydrolysis resistance of the aluminum nitride.
Description
Technical Field
The invention belongs to the field of inorganic nonmetallic powder preparation, and particularly relates to a preparation method of alpha-alumina coated spherical aluminum nitride.
Background
Aluminum nitride (AlN) is an atomic crystal, belongs to diamond-like nitride, has excellent electrical insulation property and high heat conduction property, and is widely used for high-power integrated circuit substrates, electronic devices, optical devices, heat sinks and polymer matrix composite packaging materials. However, the aluminum nitride powder is easy to absorb moisture and oxygen to cause hydrolysis and oxidation of the surface, so that the aluminum nitride powder loses the heat conduction and heat dissipation performance, and meanwhile, the transportation and storage cost of the aluminum nitride powder is increased, which is a great technical problem for restricting the development and application of the aluminum nitride powder at present. On the other hand, the common aluminum nitride powder is difficult to be uniformly mixed with the high polymer material under the condition of not carrying out surface treatment and modification, and a good heat conduction network channel cannot be formed. Therefore, aluminum nitride wants to carry a big flag of the main force of the heat conducting filler, and the problems of hydrolysis, oxidization and difficult dispersion of the aluminum nitride are solved firstly.
In recent years, many studies have been made on the preparation of a modified aluminum nitride material excellent in hydrolysis resistance, good in dispersibility and high in filling amount, for example, by coating aluminum nitride particles or forming a thinner reaction layer, preventing hydrolysis reaction of aluminum nitride powder with water. The invention patent CN1557776A discloses a preparation method of single phosphoric acid modified aluminum nitride powder, which uses single phosphoric acid to coat a layer of aluminum dihydrogen phosphate on the surface of aluminum nitride so as to achieve a certain hydrolysis resistance effect, but the modified aluminum nitride has slightly acidic property, severely corrodes production equipment and instruments, has overlarge production cost, and is difficult to popularize and apply. The patent number CN107298433A is a preparation method of phosphoric acid and castor oil phosphate compound modified aluminum nitride, and a layer of aluminum dihydrogen phosphate is coated on the surface of aluminum nitride by using phosphoric acid and castor oil phosphate compound ball milling modification so as to achieve good hydrolysis resistance effect, but the product is slightly acidic and has extremely low filling amount, so that the application range of the product is limited.
Disclosure of Invention
Based on the problems described in the background art, the invention aims to provide a preparation method of alpha-alumina coated spherical aluminum nitride, which is characterized in that irregular aluminum nitride powder is sphericized by ball milling and heat treatment in a specific solvent, the obtained aluminum nitride has uniform granularity, narrow distribution, no agglomeration and high sphericity, the effective coating of alpha-alumina on the aluminum nitride is realized, and the hydrolysis resistance and the dispersion performance of the aluminum nitride are improved.
The invention provides an alpha-alumina coated spherical aluminum nitride, which is formed by the following steps: firstly, carrying out ball milling modification on irregular aluminum nitride to prepare aluminum hydroxide-silicon oxide layer coated ball-like aluminum nitride, hydrolyzing the surface of aluminum nitride to form an aluminum hydroxide coating layer by adding a mixed solution of ethanol and distilled water, bonding the added silane coupling agent with the aluminum hydroxide on the surface of aluminum nitride to form a hydrophobic silicon oxide layer so as to prevent agglomeration among particles, and changing the original irregular aluminum nitride into the aluminum hydroxide-silicon oxide layer coated ball-like aluminum nitride by combining a ball milling modification process. The method of high-temperature melting and calcining is adopted to realize the coating of alpha-phase alumina on spherical aluminum nitride, the silicon oxide layer on the surface of the spherical aluminum nitride is melted and broken to volatilize in the high-temperature calcining process, and the aluminum hydroxide layer on the surface of the spherical aluminum nitride is dehydrated and decomposed into alumina at high temperature; secondly, the mineralizer added in the calcination process can reduce the melting points of aluminum nitride and an aluminum oxide layer on the surface of the aluminum nitride, which is favorable for the formation of crystal phases of alpha-aluminum oxide, so that the aluminum nitride is deformed into spherical crystal forms from spheroidized crystals, and thus the alpha-aluminum oxide coated spherical aluminum nitride powder material is obtained.
The invention provides a preparation method of alpha-alumina coated spherical aluminum nitride powder, which comprises the following steps:
(1) Preparing aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder: adding the mixed solution of the irregular aluminum nitride powder, ethanol and distilled water into a ball milling tank according to a certain proportion, placing the mixed solution into a planetary ball mill, performing ball milling reaction for 0.5-3 h at the rotating speed of 100-600 r/min at room temperature, adding a silane coupling agent into the ball milling tank according to a certain proportion, continuing the ball milling reaction for 0.5-3 h at the rotating speed of 100-600 r/min at room temperature, cooling to the room temperature, and placing the obtained ball milling material into a constant temperature drying oven at 120 ℃ for 6-12 h to obtain the aluminum hydroxide-silica layer coated spherical aluminum nitride powder;
(2) Preparing alpha-alumina coated spherical aluminum nitride powder: adding the aluminum hydroxide-silica layer coated spherical aluminum nitride powder and a mineralizer into a ball milling tank according to a certain proportion, placing the ball milling tank into a planetary ball mill for ball milling, mixing for 5min at the rotation speed of 300r/min at room temperature, pouring the ball milling mixture into a crucible, placing the crucible into an atmosphere furnace for calcination under nitrogen or ammonia, wherein the calcination temperature is 1200-1800 ℃, the heat preservation time is 1-6 h, placing the sintered body into the planetary ball mill for ball milling for 5-30 min after the sintered body is naturally cooled to the room temperature, and obtaining the alpha-alumina coated spherical aluminum nitride powder.
The median diameter D50 of the irregular aluminum nitride powder in the step (1) is 10-200 mu m.
The mass ratio of the irregular aluminum nitride powder to the ethanol, the distilled water and the silane coupling agent in the step (1) is 300-600:1-6:0.01-0.06:1-6.
The silane coupling agent in the step (1) is one or more of 3- (methacryloxy) propyl trimethoxy silane, gamma-chloropropyl methyl diethoxy silane and 3-aminopropyl trimethoxy silane.
The concentration of the ethanol in the step (1) is 95.0-99.8%.
In the step (2), the mass ratio of the aluminum hydroxide-silica layer coated spherical aluminum nitride powder to the mineralizer is 300-600:3-30.
The calcining temperature in the step (2) is at least above 1200 ℃ to completely form the pure alpha-phase alumina coating.
The mineralizer in the step (2) is one or more of calcium-containing chloride, yttrium-containing chloride and zinc-containing chloride.
Compared with the prior art, the invention has the following advantages:
(1) The invention realizes the effective coating of the alpha-alumina on the spherical aluminum nitride by ball milling and heat treatment, and the alpha-alumina layer with stable surface structure protects the aluminum nitride from hydrolysis, thereby greatly improving the hydrolysis resistance of the aluminum nitride, and the pH of the prepared powder product is neutral, thereby being not easy to cause the damage of equipment and widening the application range. (2) The invention realizes the sphericizing modification of irregular aluminum nitride, and the prepared alpha-aluminum oxide coated spherical aluminum nitride powder has high sphericity, smooth surface, uniform granularity and narrow distribution, and has good dispersibility in organic resin, thereby further improving the filling property and the heat conductivity of the aluminum nitride powder in the composite material.
Drawings
Fig. 1 is an SEM image of an irregular aluminum nitride raw material in example 1.
Fig. 2 is an SEM image of the aluminum hydroxide-silica layer coated spheroidal aluminum nitride powder prepared in example 1.
Fig. 3 is an SEM image of the α -alumina coated spherical aluminum nitride powder prepared in example 1.
Fig. 4 is an SEM image of the product prepared in comparative example 1.
Fig. 5 is an SEM image of the product prepared in comparative example 2.
Fig. 6 is an SEM image of the product prepared in comparative example 3.
Fig. 7 is an SEM image of the product prepared in comparative example 4.
Fig. 8 is an SEM image of the product prepared in comparative example 5.
Fig. 9 is an SEM image of the product prepared in comparative example 6.
Fig. 10 is an XRD pattern of the preparation of the α -alumina-coated spherical aluminum nitride powder of example 1.
FIG. 11 is a graph showing hydrolysis-resistant pH change of powder products prepared in example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5, and comparative example 6.
Detailed Description
The embodiments described below specifically explain the present invention, and in particular, it should be understood that numerous modifications and improvements may be made based on the principles of the present invention, and are also contemplated as falling within the scope of the embodiments of the present invention.
Example 1
(1) Adding 6g of ethanol and 0.06g of distilled water into a 100mL beaker, stirring for 5min at room temperature to obtain ethanol-distilled water mixed solution, adding 300g of 10 mu m irregular aluminum nitride powder into the mixed solution, transferring the mixed solution into a ball milling tank of a planetary ball mill, ball milling and modifying for 3h at the room temperature at the rotating speed of 300r/min, adding 1g of 3- (methacryloyloxy) propyl trimethoxysilane into the ball milling tank of the planetary ball mill, continuing ball milling and modifying for 3h at the rotating speed of 300r/min at the room temperature, cooling to the room temperature, and then placing the modified ball milling material into a constant temperature drying box at 120 ℃ for 6h to obtain aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder (the mass ratio of the irregular aluminum nitride powder to the ethanol to the distilled water to the 3- (methacryloyloxy) propyl trimethoxysilane is 300:6:0.06:1);
(2) And (3) weighing 300g of the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder and 3g of calcium chloride in the step (1) according to the mass ratio of the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder to the calcium chloride of 300:3, pouring the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder and 3g of calcium chloride into a ball milling tank of a planetary ball mill, ball milling and mixing for 5min at the rotating speed of 300r/min at room temperature, pouring the mixture into a crucible, placing the crucible into an atmosphere furnace, calcining the crucible under nitrogen, keeping the calcining temperature at 1200 ℃ for 1h, and transferring the sintered body into the planetary ball mill for ball milling for 5min after the sintered body is naturally cooled to the room temperature, thus obtaining the alpha-alumina coated spherical aluminum nitride powder.
Example 2
(1) 3g of ethanol and 0.03g of distilled water are weighed and added into a 100mL beaker, stirring is carried out for 5min at room temperature, thus obtaining ethanol-distilled water mixed solution, 300g of 100 mu m irregular aluminum nitride powder is added into the mixed solution and then transferred into a ball milling tank of a planetary ball mill, ball milling modification is carried out for 1.5h at room temperature at the rotating speed of 400r/min, 1g of gamma-chloropropyl methyl diethoxy silane is weighed and then poured into the ball milling tank of the planetary ball mill, ball milling modification is carried out for 1.5h at the rotating speed of 400r/min continuously at room temperature, after cooling to room temperature, the modified ball milling material is placed into a constant temperature drying box at 120 ℃ for 12h, thus obtaining aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder (the mass ratio of irregular aluminum nitride powder, ethanol, distilled water and gamma-chloropropyl methyl diethoxy silane is 300:3:0.03:1);
(2) And (3) weighing 300g of the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder and 10g of yttrium chloride in the step (1) according to the mass ratio of the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder to the calcium chloride of 300:10, pouring the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder and 10g of yttrium chloride into a ball milling tank of a planetary ball mill, ball milling and mixing for 5min at the rotating speed of 300r/min at room temperature, pouring the mixture into a crucible, placing the crucible into an atmosphere furnace, calcining the crucible under nitrogen, keeping the calcining temperature at 1500 ℃ for 3h, and transferring the sintered body into the planetary ball mill for ball milling for 10min after the sintered body is naturally cooled to the room temperature, thus obtaining the alpha-alumina coated spherical aluminum nitride powder.
Example 3
(1) 3g of ethanol and 0.03g of ethanol are weighed and added into a 100mL beaker, stirring is carried out for 5min at room temperature to obtain ethanol-distilled water mixed solution, 300g of 150 mu m irregular aluminum nitride powder is added into the mixed solution and then transferred into a ball milling tank of a planetary ball mill, ball milling modification is carried out for 0.5h at room temperature at the rotating speed of 500r/min, then 3g of 3-aminopropyl trimethoxysilane is weighed and poured into the ball milling tank of the planetary ball mill, ball milling modification is carried out for 0.5h at the rotating speed of 500r/min continuously at the room temperature, after cooling to the room temperature, the modified ball milling material is placed into a constant temperature drying box at 120 ℃ for drying for 12h, and thus the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder (the mass ratio of irregular aluminum nitride powder, ethanol, distilled water and 3-aminopropyl trimethoxysilane is 300:3:0.03:3) is obtained;
(2) And (3) weighing 300g of the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder and 20g of zinc chloride according to the mass ratio of the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder to the zinc chloride of 300:20, pouring the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder and 20g of zinc chloride in the step (1) into a ball milling tank of a planetary ball mill, ball milling and mixing for 5min at the rotating speed of 300r/min at room temperature, pouring the mixture into a crucible, placing the crucible into an atmosphere furnace, calcining the crucible under nitrogen, keeping the calcining temperature at 1800 ℃ for 6h, and transferring the sintered body into the planetary ball mill for ball milling for 10min after the sintered body is naturally cooled to the room temperature, thus obtaining the alpha-alumina coated spherical aluminum nitride powder.
Example 4
(1) 1g of ethanol and 0.01g of distilled water are weighed and added into a 100mL beaker, stirring is carried out for 5min at room temperature, thus obtaining ethanol-distilled water mixed solution, 600g of 10 mu m irregular aluminum nitride powder is added into the mixed solution and then transferred into a ball milling tank of a planetary ball mill, ball milling and modification are carried out for 3h at the room temperature at the rotating speed of 300r/min, 1g of 3- (methacryloyloxy) propyl trimethoxysilane is weighed and poured into the ball milling tank of the planetary ball mill, ball milling and modification are carried out for 3h at the rotating speed of 300r/min are continuously carried out at the room temperature, after cooling to the room temperature, the modified ball milling material is placed into a constant temperature drying box at 120 ℃ for 6h, thus obtaining the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder (the mass ratio of irregular aluminum nitride powder, ethanol, distilled water and 3- (methacryloyloxy) propyl trimethoxysilane is 600:1:0.01:1);
(2) 600g of the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder and 3g of calcium chloride in the step (1) are weighed according to the mass ratio of 600:3, are poured into a ball milling tank of a planetary ball mill, are ball-milled and mixed for 5min at the rotating speed of 300r/min at room temperature, are poured into a crucible, are put into an atmosphere furnace and are calcined under nitrogen, the calcining temperature is 1200 ℃, the heat preservation time is 1h, and the sintered body is transferred into the planetary ball mill for ball milling for 5min after being naturally cooled to the room temperature, so that the alpha-aluminum oxide coated spherical aluminum nitride powder is obtained.
Example 5
(1) Adding 6g of ethanol and 0.06g of distilled water into a 100mL beaker, stirring for 5min at room temperature to obtain ethanol-distilled water mixed solution, adding 300g of 200 mu m irregular aluminum nitride powder into the mixed solution, transferring the mixed solution into a ball milling tank of a planetary ball mill, ball milling and modifying for 3h at the room temperature at the rotating speed of 300r/min, adding 6g of 3- (methacryloyloxy) propyl trimethoxysilane into the ball milling tank of the planetary ball mill, continuing ball milling and modifying for 3h at the rotating speed of 300r/min at the room temperature, cooling to the room temperature, and then placing the modified ball milling material into a constant temperature drying box at 120 ℃ for 6h to obtain aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder (the mass ratio of the irregular aluminum nitride powder to the ethanol to the distilled water to the 3- (methacryloyloxy) propyl trimethoxysilane is 300:6:0.06:6);
(2) And (3) weighing 300g of the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder and 30g of calcium chloride according to the mass ratio of the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder to the calcium chloride of 300:30, pouring the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder and 30g of calcium chloride in the step (1) into a ball milling tank of a planetary ball mill, ball milling and mixing for 5min at the rotating speed of 300r/min at room temperature, pouring the mixture into a crucible, placing the crucible into an atmosphere furnace, calcining the crucible under nitrogen, keeping the calcining temperature at 1800 ℃ for 6h, and transferring the sintered body into the planetary ball mill for ball milling for 5min after the sintered body is naturally cooled to the room temperature, thus obtaining the alpha-alumina coated spherical aluminum nitride powder.
Comparative example 1
(1) Weighing 300g of 10 mu m irregular aluminum nitride powder in the embodiment 1, directly pouring the powder into a ball mill tank, ball milling the powder for 3 hours at room temperature by using a planetary ball mill with the rotating speed of 300r/min, and putting the ball milling material into a constant-temperature drying oven at 120 ℃ for drying for 6 hours to obtain modified aluminum nitride powder;
(2) The aluminum hydroxide-silica layer coated spheroidal aluminum nitride powder in step (2) of the example was replaced with the modified aluminum nitride powder prepared in step (1) of comparative example 1, and the other steps were identical to step (2) of example 1.
Comparative example 2
(1) Weighing 6g of ethanol and 0.06g of distilled water according to the mass ratio of 6:0.06, adding the ethanol and the 0.06g into a 100mL beaker, stirring for 5min at room temperature to obtain ethanol-distilled water mixed solution, adding 300g of 10 mu m irregular aluminum nitride powder in the embodiment 1, transferring the mixed solution into a ball milling tank of a planetary ball mill, modifying the mixed solution with ball milling with the rotating speed of 300r/min for 3h at room temperature, cooling the modified ball milling material to room temperature, and placing the modified ball milling material into a constant-temperature drying oven at 120 ℃ for 6h to obtain modified aluminum nitride powder;
(2) The aluminum hydroxide-silica layer coated spheroidal aluminum nitride powder in step (2) of the example was replaced with the modified aluminum nitride powder prepared in step (1) of comparative example 2, and the other steps were identical to step (2) of example 1.
Comparative example 3
(1) Weighing 300g of 10 mu m irregular aluminum nitride powder and 1g of 3- (methacryloyloxy) propyl trimethoxy silane which are the same as those in the embodiment 1 according to the mass ratio of 300:1, pouring the mixture into a ball milling tank of a planetary ball mill, performing ball milling modification for 3 hours at room temperature at the rotating speed of 300r/min, and placing the modified ball milling material in a constant temperature drying oven at 120 ℃ for 6 hours after cooling to room temperature to obtain modified aluminum nitride powder;
(2) The aluminum hydroxide-silica layer coated spheroidal aluminum nitride powder in step (2) of the example was replaced with the modified aluminum nitride powder prepared in step (1) of comparative example 3, and the other steps were identical to step (2) of example 1.
Comparative example 4
(1) 300g of aluminum hydroxide-silica layer coated spherical aluminum nitride powder prepared according to the step (1) of the example 1 is poured into a crucible, the crucible is put into an atmosphere furnace and calcined under nitrogen, the calcining temperature is 1200 ℃, the heat preservation time is 1h, and after the sintered body is naturally cooled to room temperature, the sintered body is transferred into a planetary ball mill for ball milling for 5min, and the alpha-alumina coated spherical aluminum nitride powder is obtained.
Comparative example 5
(1) According to example 1, 6g of ethanol and 0.06g of distilled water are weighed and added into a 100mL beaker, stirring is carried out for 5min at room temperature, thus obtaining ethanol-distilled water mixed solution, 300g of 10 mu m irregular aluminum nitride powder is added into the mixed solution, the mixed solution is transferred into a crusher, crushing and modification are carried out for 3h at the room temperature at the rotating speed of 300r/min, 1g of 3- (methacryloyloxy) propyl trimethoxysilane is weighed and poured into a crushing tank of the crusher, crushing and modification are carried out for 3h at the rotating speed of 300r/min continuously at the room temperature, after cooling to the room temperature, the modified crushed material is placed into a constant temperature drying box at 120 ℃ for 6h, thus obtaining aluminum hydroxide-silica layer coated spheroidal aluminum nitride powder (the mass ratio of irregular aluminum nitride powder, ethanol, distilled water and 3- (methacryloyloxy) propyl trimethoxysilane is 300:6:0.06:1);
(2) And (3) weighing 300g of the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder and 3g of calcium chloride according to the mass ratio of the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder to the calcium chloride of 300:3, pouring the aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder and 3g of calcium chloride into a crushing tank of a crusher, crushing and mixing for 5min at the room temperature of 300r/min, pouring the mixture into a crucible, placing the crucible into an atmosphere furnace, calcining the crucible under nitrogen, keeping the calcining temperature of 1200 ℃ for 1h, and transferring the sintered body into the crusher for crushing for 5min after the sintered body is naturally cooled to the room temperature, thus obtaining the alpha-aluminum oxide coated aluminum nitride powder.
Comparative example 6
(1) 300g of aluminum hydroxide-silica layer coated spheroidal aluminum nitride powder prepared according to the step (1) of the example 1 is poured into a crucible, the crucible is put into an atmosphere furnace and calcined under nitrogen, the calcining temperature is 800 ℃, the heat preservation time is 1h, and the sintered body is naturally cooled to room temperature and then is transferred into a planetary ball mill for ball milling for 5min, so that the alumina coated spheroidal aluminum nitride powder is obtained.
The performance test was performed on each of the examples and comparative examples, and the test results are shown in table 1 and the accompanying drawings.
The hydrolysis resistance test method and standard are as follows:
respectively taking 10g of untreated irregular aluminum nitride powder, 10g of the powder prepared in the final steps of example 1, comparative example 2, comparative example 3, comparative example 4 and comparative example 5, placing the powder in a 500mL beaker filled with 100g of distilled water, soaking the powder for 60min at 85 ℃, and testing the pH value for 1 time every 6min to obtain a change curve of the pH value with time (the sample can be judged to have no hydrolysis resistance when tested by a pH meter instrument to be more than 9).
The filling part test method and standard are as follows:
maximum parts of filling: after 50g of 500cp vinyl silicone oil, 1.5g of hydrogen-containing silicone oil, 0.15g of inhibitor and 0.25g of platinum catalyst are fully and uniformly mixed, a certain amount of aluminum nitride powder is added, the mixture is placed in a vacuum stirring deaerator after preliminary dispersion, the rotation speed is set at 800r/min, stirring is carried out for 2min, then a calender is used for calendering and shaping a gasket with the thickness of 2mm, the gasket is placed in a baking oven at 150 ℃ for drying for 10min, the gasket is taken out and naturally cooled to the room temperature, and the maximum filling part of the gasket is reached without powder dropping.
Table 1: maximum filled fraction of ball-milled modified aluminum nitride prepared in each example and initial pH
As can be seen from the figures and the data in table 1:
(1) The morphology of the aluminum hydroxide-silica-free layer coated aluminum nitride powder of comparative example 1 (fig. 4) is similar to that of spheres but is seriously agglomerated among particles, and the initial value of the pH value is over 9, which means that the aluminum nitride which is still not resistant to hydrolysis is finally obtained by simple ball milling, and the maximum filling part is lower due to agglomeration among particles, through analysis of a scanning electron microscope (fig. 3-9), an XRD (X-ray diffraction) (fig. 10) and a hydrolysis resistance pH change curve (fig. 11); secondly, the morphology of the silica-free layer coated aluminum nitride powder of comparative example 2 (fig. 5) is also similar to that of a sphere but the particles are seriously agglomerated, and the pH value exceeds 9 after 3 hours, and the aluminum hydroxide layer coated aluminum nitride is incomplete due to the agglomeration among the particles, so that the hydrolysis resistance and the filling property of the aluminum hydroxide layer are improved to a limited extent; the aluminum hydroxide-free layer coated aluminum nitride powder in comparative example 3 (figure 6) has a similar spherical morphology, and particles are relatively dispersed, but the pH value of the aluminum hydroxide-free layer coated aluminum nitride powder exceeds 9 after 5min, which indicates that the aluminum hydroxide-free layer coated aluminum nitride powder has no hydrolysis resistance, and the maximum filling part of the aluminum hydroxide-free layer coated aluminum nitride powder is lower because the particles are not spherical; the morphology of the aluminum oxide coated aluminum nitride powder of comparative example 4 (fig. 7) without mineralizer was spheroid; the product of comparative example 5 (fig. 8) in which the planetary ball mill apparatus was changed to the crusher apparatus was irregularly shaped; the product of comparative example 6 (fig. 9) having a calcination temperature of only 800 c was also irregular in morphology, while the morphology of the α -alumina coated spherical aluminum nitride powder (fig. 3) prepared in example 1 according to the method of the present invention was spherical, and the α -alumina diffraction characteristic peak of the XRD pattern (fig. 10) successfully demonstrated the presence of the α -alumina coating, thereby making the product of example 1 excellent in hydrolysis resistance and significantly improved in the maximum packing fraction.
(2) Compared with comparative examples 1-6, the alpha-alumina coated spherical aluminum nitride powder has excellent hydrolysis resistance, and the maximum filling part in 500cP vinyl silicone oil is improved by 300-600 parts, which indicates that the alumina coated spherical aluminum nitride powder greatly improves the dispersion performance of aluminum nitride, can be effectively dispersed in an organic solvent, and further improves the heat conduction capacity of the modified aluminum nitride filled composite material.
From the above embodiments, the present invention successfully realizes that the alumina coats the spherical aluminum nitride powder, solves the defect that the aluminum nitride is not hydrolysis-resistant in the prior art, and successfully reforms the irregular aluminum nitride into the spherical aluminum nitride. And the coating cost is low, the product is neutral, equipment is not easy to damage, and the process popularization is convenient.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The preparation method of the alpha-alumina coated spherical aluminum nitride is characterized by comprising the following steps of:
(1) Preparing aluminum hydroxide-silicon oxide layer coated spherical aluminum nitride powder: adding the mixed solution of the irregular aluminum nitride powder, ethanol and distilled water into a ball milling tank according to a certain proportion, placing the mixed solution into a planetary ball mill, performing ball milling reaction for 0.5-3 h at the rotating speed of 100-600 r/min at room temperature, adding a silane coupling agent into the ball milling tank according to a certain proportion, continuing the ball milling reaction for 0.5-3 h at the rotating speed of 100-600 r/min at room temperature, cooling to the room temperature, and placing the obtained ball milling material into a constant temperature drying oven at 120 ℃ for 6-12 h to obtain the aluminum hydroxide-silica layer coated spherical aluminum nitride powder;
(2) Preparing alpha-alumina coated spherical aluminum nitride powder: adding the aluminum hydroxide-silica layer coated spherical aluminum nitride powder and a mineralizer into a ball milling tank according to a certain proportion, placing the ball milling tank into a planetary ball mill for ball milling, mixing for 5min at the rotation speed of 300r/min at room temperature, pouring the ball milling mixture into a crucible, placing the crucible into an atmosphere furnace for calcination under nitrogen or ammonia, wherein the calcination temperature is 1200-1800 ℃, the heat preservation time is 1-6 h, placing the sintered body into the planetary ball mill for ball milling for 5-30 min after the sintered body is naturally cooled to the room temperature, and obtaining the alpha-alumina coated spherical aluminum nitride powder.
2. The method for producing an α -alumina-coated spherical aluminum nitride according to claim 1, wherein the irregular aluminum nitride powder in step (1) has a median diameter D50 of 10 to 200 μm.
3. The method for preparing the alpha-alumina coated spherical aluminum nitride according to claim 1, wherein the mass ratio of the irregular aluminum nitride powder to the ethanol, the distilled water and the silane coupling agent in the step (1) is 300-600:1-6:0.01-0.06:1-6.
4. The method for preparing alpha-alumina coated spherical aluminum nitride according to claim 1, wherein the silane coupling agent in the step (1) is one or more of 3- (methacryloyloxy) propyl trimethoxysilane, gamma-chloropropyl methyldiethoxysilane, and 3-aminopropyl trimethoxysilane.
5. The method for preparing alpha-alumina coated spherical aluminum nitride according to claim 1, wherein the concentration of ethanol in the step (1) is 95.0% to 99.8%.
6. The method for preparing alpha-alumina coated spherical aluminum nitride according to claim 1, wherein the mass ratio of the aluminum hydroxide-silica layer coated spherical aluminum nitride powder to the mineralizer in the step (2) is 300-600:3-30.
7. The method for preparing alpha-alumina coated spherical aluminum nitride according to claim 1, wherein the mineralizer in the step (2) is one or more of calcium-containing chloride, yttrium-containing chloride and zinc-containing chloride.
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