CN115367717A - Preparation method of low-agglomeration aluminum nitride powder - Google Patents
Preparation method of low-agglomeration aluminum nitride powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 80
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 43
- 238000005054 agglomeration Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 48
- 239000006229 carbon black Substances 0.000 claims abstract description 46
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000919 ceramic Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 238000005121 nitriding Methods 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 2
- 239000002245 particle Substances 0.000 abstract description 48
- 238000009826 distribution Methods 0.000 abstract description 17
- 239000011164 primary particle Substances 0.000 abstract description 16
- 238000002156 mixing Methods 0.000 abstract description 13
- 238000006722 reduction reaction Methods 0.000 abstract description 8
- 241000519995 Stachys sylvatica Species 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000005261 decarburization Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 35
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 30
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 30
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 238000001354 calcination Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011812 mixed powder Substances 0.000 description 10
- 239000011268 mixed slurry Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 238000005303 weighing Methods 0.000 description 4
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 229910017083 AlN Inorganic materials 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011091 composite packaging material Substances 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/072—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with aluminium
- C01B21/0726—Preparation by carboreductive nitridation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The invention discloses a preparation method of low-agglomeration aluminum nitride powder. The invention mixes deionized water, PVP and Al 2 O 3 And adding the carbon black into a ball milling tank according to a certain mass ratio, and carrying out ball milling and mixing to obtain uniform slurry without white spots and with good fluidity. Then the slurry is put into a high-temperature oven for full drying to obtain evenly mixed Al 2 O 3 Carbon black powder. Then AlN/carbon black powder is obtained through carbothermic reduction reaction, and then the AlN/carbon black powder is placed into a high-temperature box type furnace for decarburization to obtain raw material powder for sintering the aluminum nitride ceramic. The PVP has obvious dispersion effect on the mixed raw materials, and finally the aluminum nitride powder with narrow particle size distribution, small median diameter and more primary particles below 2 microns can be obtained.
Description
Technical Field
The invention belongs to the field of ceramic powder preparation, and relates to a preparation method of low-agglomeration aluminum nitride powder.
Background
Aluminum nitride (AlN) has the advantages of higher thermal conductivity, good electrical insulation, high hardness, low dielectric constant and dielectric loss, stable chemical property, thermal expansion coefficient similar to that of silicon and the like, has excellent comprehensive performance compared with other ceramic materials, and can be used for preparing a new generation of ideal substrates, composite materials and packaging materials of high integration level and power devices. Commercial aluminum nitride powders are synthesized by two processes, one being a direct nitridation process and the other being an alumina carbothermic reduction process. Although the direct nitriding method has rich raw materials and simple process, the molten aluminum in the reaction process makes the nitrogen difficult to diffuse, and the reaction product is agglomerated at high temperature, thereby causing the quality reduction of the product. A large part of the aluminum nitride powder available on the market is supplied from carbothermic reduction.
The carbothermic reduction method is a process of mixing alumina and carbon powder in flowing nitrogen at 1550-1800 ℃ to obtain aluminum nitride powder, and Al is reduced by carbon 2 O 3 And reacting the reduced Al with nitrogen in a flowing state to generate AlN:
Al 2 O 3 (s)+3C(s)+N 2 (g)→2AlN(s)+3CO(g)
the aluminum nitride powder produced by the method has the characteristics of high purity, easy sintering, strong stability and the like. However, the method is difficult to realize homogeneous mixing of alumina and carbon powder, the activity of the alumina is low, long-time reaction in high-temperature nitrogen is required, and the production cost is high. At present, the main homogeneous mixing methods for synthesizing the aluminum nitride powder by the carbothermic method comprise dry mixing and wet ball milling. The dry mixing process is simple, but the mixing uniformity is poor, the time consumption is long, and dust is easy to generate; when homogeneous mixing is carried out by adopting a ball mill wet mixing method, although no dust flies, the viscosity of slurry obtained after ball milling is higher, the particle size distribution of the aluminum nitride product obtained after high-temperature synthesis is wide, the median diameter is larger, the proportion of primary particles is very low, more agglomerated particles are needed, and ball milling is carried out again to break the agglomerated particles.
The inventors have previously found that the use of some polymers as dispersants helps to prepare a well-dispersed aluminium nitride product and in application CN113292053A it was proposed to pre-dissolve the dispersants (polyvinyl alcohol PVA, polyacrylic acid PAA, polyethylene glycol PEG) and then to disperse the carbon black particles evenly between the aluminium oxide particles by wet ball milling to improve the agglomeration of the final aluminium nitride product. However, the pre-dissolution of these polymeric dispersants requires a certain time and temperature, for example, PVA needs to be pre-swollen in a solvent for 1-2 hours, then heated to 90-95 ℃, and continuously stirred for 2-3 hours to obtain a transparent solution. If the dispersion is directly mixed with alumina and carbon powder, flocculation is likely to occur, and the final dispersion effect is difficult to exert.
Aiming at the problem of high mixing difficulty in the patent CN113292053A, the invention provides that polyvinylpyrrolidone (PVP) is directly mixed with raw materials, so that the production process can be obviously shortened, and an aluminum nitride product with narrower particle size distribution, smaller median diameter and higher primary particle ratio can be obtained.
Disclosure of Invention
The invention aims to provide a preparation method of low-agglomeration aluminum nitride powder aiming at the defects of the prior art, which comprises the steps of introducing PVP dispersing agent into a solvent, uniformly dispersing carbon black particles among alumina particles through wet ball milling to obtain slurry with better fluidity, and then obtaining the aluminum nitride powder with narrower particle size distribution, small median diameter and higher primary particle ratio through a carbothermic reduction method.
The invention adopts the following technical scheme:
the invention uses deionized water, polyvinylpyrrolidone (PVP) and Al 2 O 3 And sequentially adding carbon black into the ball-milling tank according to certain mass, stirring, and performing wet ball milling by using a planetary ball mill to obtain uniform slurry without white spots and with good fluidity. Then the slurry is put into a high-temperature oven for full drying to obtain evenly mixed Al 2 O 3 Carbon black powder. Then AlN/carbon black powder is obtained through carbothermic reduction reaction, and then the AlN/carbon black powder is placed into a high-temperature box type furnace for decarburization to obtain raw material powder for sintering the aluminum nitride ceramic.
The method comprises the following specific steps:
step (1), deionized water, PVP and Al 2 O 3 Carbon black according toAdding the mixture into a ball milling tank according to certain mass, stirring, and performing wet ball milling by a planetary ball mill to obtain uniform slurry A1 without white spots and with good fluidity.
Step (2), putting the slurry A1 into a high-temperature oven for fully drying to obtain uniformly mixed Al 2 O 3 Carbon black powder A2.
And (3) putting a certain amount of powder A2 into a graphite crucible, putting the graphite crucible into a graphite sintering furnace, and performing carbothermic reduction for 2-4 h at 1550-1625 ℃ in a flowing nitrogen atmosphere to obtain nitrided product powder A3.
And (4) putting a certain amount of powder A3 into a high-temperature box-type furnace, preserving the heat for 4-6 hours at the temperature of 600-700 ℃, and removing redundant carbon in the powder A3 of the nitriding product to obtain raw material powder for sintering the aluminum nitride ceramic.
Preferably, the alumina is superfine nano powder, and the median diameter is 300-800 nm.
Preferably, the carbon black is ultrafine nano powder, and the median diameter is 20-100 nm.
Preferably, the mass ratio of the alumina to the carbon black is 100.
Preferably, the molecular weight of the PVP is 40000, and the mass content of the PVP is 1 to 10%, preferably 4 to 6%, of the total amount of the alumina and the carbon black.
Preferably, the Al is 2 O 3 The mass ratio of the total amount of the carbon black to the deionized water is 100:300 to 100 parts of.
Preferably, the ball milling medium is mixed with deionized water, PVP and Al 2 O 3 The mass ratio of the total amount of the carbon black is 100: 10-100 parts of.
Preferably, the rotation speed of the ball milling is 100-150 r/min, and the time is 0.5-2 h.
Preferably, the drying temperature is 110-120 ℃.
Compared with the prior art, the invention has the following advantages:
(1) The PVP adopted by the invention does not need to be dissolved for a long time in advance, and can be directly subjected to wet ball milling mixing with alumina and carbon powder, and in the ball milling process, the PVP is dissolved and synchronously coated on the surfaces of alumina particles and carbon black particles, so that slurry with low viscosity and good fluidity is finally obtained (Table 1). The slurry obtained by one-time ball milling and mixing has good dispersibility, so the mixing time can be greatly shortened at room temperature. In addition, since the melting point of PVP is near 130 ℃, the production efficiency can be improved by adopting higher drying temperature (110-120 ℃).
(2) Compared with non-carbon inorganic dispersant, the PVP thin layer coated on the surface of the raw material particles can inhibit the agglomeration of alumina particles and can be decomposed at 400-500 ℃, so that new impurities can not be introduced into an aluminum nitride product, and the generation of the aluminum nitride can not be hindered.
(3) The aluminum nitride powder synthesized by carbothermic reduction by adding a proper amount of PVP and deionized water has narrow particle size distribution, smaller median diameter, greatly improved proportion of primary particles and lower oxygen content, and can meet the requirement of raw material powder for aluminum nitride ceramics with excellent sintering performance.
Drawings
FIG. 1 is a diagram showing the morphology of the synthesized powder in example 2.
FIG. 2 is a diagram showing the morphology of the synthesized powder in example 4.
FIG. 3 is a schematic diagram of the synthesized powder in comparative example 1.
FIG. 4 is a diagram showing the morphology of the synthesized powder in comparative example 2.
FIG. 5 is a schematic diagram of the synthesized powder in comparative example 3.
FIG. 6 is a graph showing the particle size distribution of the synthetic powders of examples 1, 2, 3 and 4 and comparative examples 1 and 2.
FIG. 7 is a TG plot of PVP at 25-800 ℃.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
The mass ratio of the ball milling medium to the material in the ball milling tank in the following examples is 100:10 to 100 parts of; the alumina is superfine nano powder, and the median diameter is 300-800 nm; the carbon black is superfine nanometer powder with a median diameter of 20-100 nm.
Example 1
160g of deionized water, 1.6g of PVP and 25g of Al are weighed 2 O 3 And 15g of carbon black are sequentially added into a ball milling tank, and are stirred and then are subjected to wet ball milling for 2 hours by a planetary ball mill to obtain uniform slurry without white dots and with good fluidity. Placing the obtained mixed slurry in a high-temperature oven at 110 ℃ for drying for 3h to obtain Al 2 O 3 Carbon black powder mixture. And (3) putting 5g of the mixed powder into a vacuum sintering furnace, and calcining for 4 hours at 1600 ℃ under flowing nitrogen atmosphere and under the nitrogen flow rate controlled at 2L/min. And (3) preserving the heat of 1.5g of the nitriding product at 650 ℃ in a high-temperature box type furnace for 5 hours to remove carbon, thereby obtaining the high-purity aluminum nitride powder. Measuring the viscosity of the slurry subjected to ball milling by using a rotary viscometer to be 109.2 Pa.s (1.0 r/min); the particle size distribution of the obtained product is measured by a laser particle size analyzer, the median diameter particle size is 2.87 micrometers, the proportion of primary particles below 2 micrometers is 37.08%, and the proportion of powder below 5 micrometers is 69.88%.
Example 2
160g of deionized water, 2.4g of PVP and 25g of Al are weighed 2 O 3 And 15g of carbon black are sequentially added into a ball milling tank, and are stirred and then are subjected to wet ball milling for 2 hours by a planetary ball mill to obtain uniform slurry without white dots and with good fluidity. Placing the obtained mixed slurry in a high-temperature oven at 110 ℃ for drying for 3h to obtain Al 2 O 3 Carbon black powder mixture. And (3) putting 5g of mixed powder into a vacuum sintering furnace, and calcining for 4 hours at 1600 ℃ under flowing nitrogen atmosphere and under the nitrogen flow rate of 2L/min to obtain a nitrided product. And (3) preserving the heat of 1.5g of the nitriding product at 650 ℃ in a high-temperature box type furnace for 5 hours to remove carbon, thereby obtaining the high-purity aluminum nitride powder. Measuring the viscosity of the slurry after ball milling by using a rotary viscometer to be 73.7 Pa.s (1.0 r/min); the particle size distribution of the obtained product is measured by a laser particle size analyzer, the median diameter particle size is 2.61 microns, the proportion of primary particles below 2 microns is 39.03%, the proportion of powder below 5 microns is 75.45%, and the morphology is shown in figure 1.
Example 3
160g of deionized water, 4g of PVP and 25g of Al are weighed 2 O 3 15g of carbon black are added into a ball milling tank in sequence, and are stirred and then are ball milled for 0.5h by a planetary ball mill wet method to obtain uniform and white-point-free carbon blackAnd a slurry having good fluidity. Placing the obtained mixed slurry in a high-temperature oven at 120 ℃ for drying for 2.5h to obtain Al 2 O 3 Carbon black powder mixture. And (3) putting 5g of the mixed powder into a vacuum sintering furnace, and calcining for 4 hours at 1600 ℃ under flowing nitrogen atmosphere and under the nitrogen flow rate controlled at 2L/min. And (3) preserving the heat of 1.5g of the nitriding product for 5 hours at the temperature of 650 ℃ in a high-temperature box type furnace to remove carbon, thus obtaining the high-purity aluminum nitride powder. Measuring the viscosity of the slurry subjected to ball milling by using a rotary viscometer to be 59 Pa.s (1.0 r/min); the particle size distribution of the obtained product is measured by a laser particle size analyzer, the median diameter particle size is 2.76 mu m, the proportion of primary particles below 2 mu m is 38.48%, and the proportion of powder below 5 mu m is 71.81%.
Example 4
Weighing 180g of deionized water, 2.4g of PVP and 25g of Al 2 O 3 And 15g of carbon black are sequentially added into a ball milling tank, and are stirred and then are subjected to wet ball milling for 2 hours by a planetary ball mill to obtain uniform slurry without white dots and with good fluidity. Placing the obtained mixed slurry in a high-temperature oven at 120 ℃ for drying for 2.5h to obtain Al 2 O 3 Carbon black powder mixture. And (3) putting 5g of the mixed powder into a vacuum sintering furnace, and calcining for 4 hours at 1600 ℃ under flowing nitrogen atmosphere and under the nitrogen flow rate controlled at 2L/min. And (3) preserving the heat of 1.5g of the nitriding product for 5 hours at the temperature of 650 ℃ in a high-temperature box type furnace to remove carbon, thus obtaining the high-purity aluminum nitride powder. Measuring the viscosity of the slurry after ball milling by using a rotary viscometer to be 13.7 Pa.s (1.0 r/min); the particle size distribution of the obtained product is measured by a laser particle size analyzer, the median diameter particle size is 2.40 microns, the proportion of primary particles below 2 microns is 43.07 percent, the proportion of powder below 5 microns is 76.57 percent, and the morphology is shown in figure 2.
Example 5
Weighing 140g of deionized water, 2.4g of PVP and 25g of Al 2 O 3 And 10g of carbon black are sequentially added into a ball milling tank, and are stirred and then are subjected to wet ball milling for 2 hours by a planetary ball mill to obtain uniform slurry without white dots and with good fluidity. Placing the obtained mixed slurry in a high-temperature oven at 110 ℃ for drying for 3h to obtain Al 2 O 3 Carbon black powder mixture. 5g of mixed powder is put into a vacuum sintering furnaceIn the flowing nitrogen atmosphere, the nitrogen flow rate is controlled at 2L/min, and the temperature is controlled at 1550 ℃ for calcining for 6h to obtain the nitriding product. And (3) preserving the heat of 1.5g of the nitriding product for 6 hours at the temperature of 600 ℃ in a high-temperature box type furnace to remove carbon, thus obtaining the high-purity aluminum nitride powder. The particle size distribution of the obtained product is measured by a laser particle size analyzer, the median diameter particle size is 2.38 mu m, the proportion of primary particles below 2 mu m is 45.25%, and the proportion of powder below 5 mu m is 78.32%.
Example 6
Weighing 180g of deionized water, 2.4g of PVP and 25g of Al 2 O 3 And 15g of carbon black are sequentially added into a ball milling tank, and are stirred and then are subjected to wet ball milling for 1 hour by a planetary ball mill to obtain uniform slurry without white dots and with good fluidity. Placing the obtained mixed slurry in a high-temperature oven at 110 ℃ for drying for 3h to obtain Al 2 O 3 Carbon black powder mixture. And (3) putting 5g of mixed powder into a vacuum sintering furnace, and calcining for 3h at 1625 ℃ under flowing nitrogen atmosphere and with the nitrogen flow rate controlled at 2L/min to obtain a nitrided product. And (3) preserving the heat of 1.5g of the nitriding product at the high-temperature box type furnace at 700 ℃ for 4h for decarbonization to obtain the high-purity aluminum nitride powder. The particle size distribution of the obtained product is measured by a laser particle size analyzer, the median diameter particle size is 2.92 mu m, the proportion of primary particles below 2 mu m is 39.46%, and the proportion of powder below 5 mu m is 68.23%.
Example 7
Weighing 105g of deionized water, 2.4g of PVP and 25g of Al 2 O 3 And 10g of carbon black are sequentially added into a ball milling tank, and are stirred and then are subjected to wet ball milling for 2 hours by a planetary ball mill to obtain uniform slurry without white dots and with good fluidity. Placing the obtained mixed slurry in a high-temperature oven at 110 ℃ for drying for 2.5h to obtain Al 2 O 3 Carbon black powder mixture. And (3) putting 5g of the mixed powder into a vacuum sintering furnace, and calcining for 4 hours at 1600 ℃ under flowing nitrogen atmosphere and under the nitrogen flow rate controlled at 2L/min. And (3) preserving the heat of 1.5g of the nitriding product for 5 hours at the temperature of 650 ℃ in a high-temperature box type furnace to remove carbon, thus obtaining the high-purity aluminum nitride powder. Measuring the viscosity of the slurry after ball milling by using a rotary viscometer, wherein the viscosity is higher and exceeds the measuring range; measuring the resultant product by means of a laser particle size analyzerThe particle size distribution is that the median diameter particle size is 3.51 mu m, the proportion of primary particles below 2 mu m is 30.37%, and the proportion of powder below 5 mu m is 61.67%.
Comparative example 1
160g of deionized water and 25g of Al are weighed 2 O 3 And 15g of carbon black are sequentially added into a ball milling tank, and are stirred and then are subjected to wet ball milling for 2 hours by a planetary ball mill to obtain uniform slurry without white spots. Placing the slurry in a high-temperature oven at 110 ℃ for drying for 3h to obtain Al 2 O 3 Carbon black powder mixture. And (3) putting 5g of the mixed powder into a vacuum sintering furnace, and calcining for 4 hours at 1600 ℃ under flowing nitrogen atmosphere and under the nitrogen flow rate controlled at 2L/min. And (3) preserving the heat of 1.5g of the nitriding product for 5 hours at the temperature of 650 ℃ in a high-temperature box type furnace to remove carbon, thus obtaining the high-purity aluminum nitride powder. Measuring the viscosity of the slurry after ball milling by using a rotary viscometer, wherein the viscosity is higher and exceeds the measuring range; the particle size distribution of the obtained product is measured by a laser particle size analyzer, the median diameter particle size is 5.06 mu m, the proportion of primary particles below 2 mu m is 17.76%, the proportion of powder below 5 mu m is 49.7%, and the morphology is shown in figure 3.
Comparative example 2
1.6g of polyvinyl alcohol is weighed and added into 160g of deionized water to be ultrasonically heated and dispersed into a transparent impurity-free solution. Adding 25g of alumina and 15g of carbon black into a ball milling tank in batches, stirring, and carrying out wet ball milling for 2 hours by a planetary ball mill to obtain uniform slurry without white spots. Placing the slurry in a high-temperature oven at 65 ℃ for drying for 12h to obtain Al 2 O 3 Carbon black powder mixture. And (3) putting 5g of mixed powder into a vacuum sintering furnace, and calcining for 4 hours at 1600 ℃ under flowing nitrogen atmosphere and under the nitrogen flow rate of 2L/min to obtain a nitrided product. And (3) preserving the heat of 1.5g of the nitriding product for 5 hours at the temperature of 650 ℃ in a high-temperature box furnace to remove carbon, thus obtaining the aluminum nitride powder. Measuring the viscosity of the slurry after ball milling by using a rotary viscometer to be 130.65 Pa.s (1.0 r/min); the particle size distribution of the obtained product is measured by a laser particle size analyzer, the median diameter particle size is 2.77 mu m, the proportion of primary particles below 2 mu m is 37.81%, the proportion of powder below 5 mu m is 69.96%, and the morphology is shown in figure 4.
Comparative example 3:
2.4g of PVP is weighed and added into 180g of deionized water for ultrasonic treatment for 3h, and the mixture is dispersed into a transparent impurity-free solution. Adding 25g of alumina and 15g of carbon black into a ball milling tank in batches, stirring, and carrying out wet ball milling for 2 hours by a planetary ball mill to obtain uniform slurry without white spots. Placing the slurry in a high-temperature oven at 120 ℃ for drying for 2.5h to obtain Al 2 O 3 Carbon black powder mixture. And (3) putting 5g of mixed powder into a vacuum sintering furnace, and calcining for 4 hours at 1600 ℃ under flowing nitrogen atmosphere and under the nitrogen flow rate of 2L/min to obtain a nitrided product. And (3) preserving the heat of 1.5g of the nitriding product for 5 hours at the temperature of 650 ℃ in a high-temperature box furnace to remove carbon, thus obtaining the aluminum nitride powder. Measuring the viscosity of the slurry after ball milling by using a rotary viscometer to be 13.5 Pa.s (1.0 r/min); the particle size distribution of the obtained product is measured by a laser particle size analyzer, the median diameter particle size is 2.38 mu m, the proportion of primary particles below 2 mu m is 43.48%, the proportion of powder below 5 mu m is 76.51%, and the morphology is shown in figure 5.
TABLE 1 comparison of viscosities of ball-milled slurries at 1r/min in examples 1, 2, 3 and 4 and comparative examples 1 and 2
It can be seen from table 1 that the viscosity of the slurry is reduced and the fluidity is improved after adding PVP, which is beneficial to more uniform mixing under the same ball milling condition. When PVP is not added, the viscosity of the slurry is very high, cannot be measured, almost has no fluidity, and the mixing effect is poor. The PVP is pre-dissolved for a long time and then ball-milled, and the viscosity of the slurry is not obviously different from that of a direct ball-milled sample. Therefore, the PVP is adopted, so that a long-time pre-dissolving process link can be omitted.
From FIG. 6, it can be seen that the median particle size in examples 1 to 4 is smaller than that in comparative example, and the dispersibility of the product is better. From FIG. 7, it is clear that PVP decomposes between 400-500 degrees.
It can be seen from the data of the above examples and comparative examples that the dispersion effect of PVP on the mixed raw material is obvious and superior to that of the sample without PVP or with PVA, the obtained aluminum nitride has a narrow particle size distribution, a small median diameter, a higher proportion of primary particles less than 2 microns and powder less than 5 microns, and no adverse effect on the synthetic product, and the obtained aluminum nitride powder has a higher purity.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as they meet the requirements of the present invention.
Claims (9)
1. A preparation method of low-agglomeration aluminum nitride powder is characterized by comprising the following steps:
step (1), deionized water, PVP and Al 2 O 3 Adding carbon black into a ball milling tank in sequence according to a certain mass ratio, stirring, and performing wet ball milling by a planetary ball mill to obtain uniform slurry A1 without white dots and with good fluidity;
step (2), the slurry A1 is placed into a high-temperature oven to be fully dried, and uniformly mixed Al is obtained 2 O 3 Carbon black powder A2;
step (3), putting a certain amount of powder A2 into a graphite crucible, putting the graphite crucible into a graphite sintering furnace, and performing carbothermic reduction for 2-4 h at 1550-1625 ℃ in a flowing nitrogen atmosphere to obtain nitrided product powder A3;
and (4) putting a certain amount of powder A3 into a high-temperature box-type furnace, preserving the heat for 4-6 hours at the temperature of 600-700 ℃, and removing redundant carbon in the powder A3 of the nitriding product to obtain raw material powder for sintering the aluminum nitride ceramic.
2. The method for preparing low-agglomeration aluminum nitride powder according to claim 1, wherein the median diameter of the aluminum oxide is 300-800 nm.
3. The method for preparing low-agglomeration aluminum nitride powder according to claim 1, wherein the carbon black has a median diameter of 20-100 nm.
4. The method for preparing the low-agglomeration aluminum nitride powder according to claim 1, wherein the mass ratio of the aluminum oxide to the carbon black is 100.
5. The method of claim 1, wherein the molecular weight of PVP is 40000, and the mass content of PVP is 1-10% of the total mass of alumina and carbon black.
6. The method of claim 5, wherein the molecular weight of PVP is 40000, and the mass content of PVP is 4-6% of the total mass of alumina and carbon black.
7. The method of claim 1, wherein the Al is selected from the group consisting of Al, cu, and Al 2 O 3 The mass ratio of the total amount of the carbon black to the deionized water is 100:300 to 100 parts of.
8. The method for preparing low-agglomeration aluminum nitride powder according to claim 1, wherein the rotation speed of the ball mill is 100-150 r/min, and the time is 0.5-2 h.
9. The method for preparing low-agglomeration aluminum nitride powder according to claim 1, wherein the drying temperature is 110-120 ℃.
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