CN115367717B - Preparation method of low-agglomeration aluminum nitride powder - Google Patents
Preparation method of low-agglomeration aluminum nitride powder Download PDFInfo
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- CN115367717B CN115367717B CN202210867967.4A CN202210867967A CN115367717B CN 115367717 B CN115367717 B CN 115367717B CN 202210867967 A CN202210867967 A CN 202210867967A CN 115367717 B CN115367717 B CN 115367717B
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- 239000000843 powder Substances 0.000 title claims abstract description 83
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 48
- 238000005054 agglomeration Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 49
- 239000006229 carbon black Substances 0.000 claims abstract description 46
- 239000002002 slurry Substances 0.000 claims abstract description 38
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 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 17
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000919 ceramic Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 238000005121 nitriding Methods 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000004220 aggregation Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- 241000519995 Stachys sylvatica Species 0.000 claims description 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 14
- 238000006722 reduction reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000005262 decarbonization Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 28
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 28
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011812 mixed powder Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 239000011268 mixed slurry Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000011858 nanopowder Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 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
- 239000002131 composite material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 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
- 230000002411 adverse Effects 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000011091 composite packaging material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 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
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
-
- 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
-
- 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
Abstract
The invention discloses a preparation method of low-agglomeration aluminum nitride powder. The invention uses deionized water, PVP and Al 2 O 3 Adding carbon black into a ball milling tank according to a certain mass ratio, and ball milling and mixing to obtain uniform slurry with no white point and good fluidity. Then the slurry is put into a high-temperature oven for full drying, and the Al which is uniformly mixed is obtained 2 O 3 Carbon black powder. And 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 decarbonization to obtain raw material powder for sintering aluminum nitride ceramics. PVP has obvious dispersion effect on the mixed raw materials, and finally can obtain aluminum nitride powder with narrow particle size distribution, small median diameter and more primary particles below 2 microns.
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 heat conductivity, good electrical insulation, high hardness, low dielectric constant, dielectric loss, stable chemical property, thermal expansion coefficient similar to that of silicon and the like, and compared with other ceramic materials, the aluminum nitride (AlN) has excellent comprehensive performance, and can be used for preparing new-generation ideal substrates, composite materials and packaging materials with high integration level and power devices. Commercial aluminum nitride powders are synthesized by two methods, one is the direct nitridation method and the other is the carbothermic reduction of aluminum oxide. Although the direct nitriding method has rich raw materials and simple process, molten aluminum in the reaction process makes nitrogen difficult to diffuse, and reaction products agglomerate at high temperature, so that the quality of the products is reduced. A significant portion of the aluminum nitride powder supply in the market is derived from this process of carbothermic reduction.
The carbothermic reduction method is a process of mixing alumina and carbon powder in nitrogen flowing at 1550-1800 ℃ to obtain aluminum nitride powder, and uses carbon to reduce Al 2 O 3 The reduced Al reacts 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 is required to be carried out in high-temperature nitrogen, and the production cost is high. At present, the main homogeneous mixing method for synthesizing aluminum nitride powder by a carbothermic method comprises 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 exist; when the homogeneous mixing is carried out by adopting a ball mill wet mixing method, although no dust flies, the slurry obtained after ball milling has larger viscosity, the aluminum nitride product obtained after high-temperature synthesis has wide particle size distribution and larger median diameter, the primary particles have low proportion, and the agglomerated particles are more, so that the agglomerated particles need to be broken by ball milling again.
The inventors have previously found that the use of some polymers as dispersants helps to prepare an aluminum nitride product with good dispersibility, and in CN113292053a application it is proposed to pre-dissolve the dispersants (polyvinyl alcohol PVA, polyacrylic acid PAA, polyethylene glycol PEG) and then uniformly disperse the carbon black particles between the alumina particles by wet ball milling to improve the agglomeration of the final aluminum nitride product. However, these polymeric dispersants require a certain time and temperature for pre-dissolution, for example, PVA is pre-swelled in a solvent for 1-2 hours, then heated to 90-95℃and stirred for 2-3 hours to give a clear solution. If it is directly mixed with alumina and carbon powder, flocculation is liable to occur, and the final dispersion effect is hardly exhibited.
Aiming at the problem of high mixing difficulty in the CN113292053A patent, the invention provides the method for directly mixing polyvinylpyrrolidone (PVP) with the raw materials, which not only can remarkably shorten the yield, but also can obtain an aluminum nitride product with narrower particle size distribution, smaller median diameter and higher primary particle occupation ratio.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of low-agglomeration aluminum nitride powder, 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 good fluidity, and obtaining aluminum nitride powder with narrow particle size distribution, small median diameter and high primary particle occupation 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 adding carbon black into a ball milling tank according to a certain mass, stirring, and performing wet ball milling through a planetary ball mill to obtain uniform slurry with no white point and good fluidity. Then the slurry is put into a high-temperature oven for full drying, and the Al which is uniformly mixed is obtained 2 O 3 Carbon black powder. And 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 decarbonization to obtain raw material powder for sintering aluminum nitride ceramics.
The method comprises the following specific steps:
step (1), deionized water, PVP and Al 2 O 3 Adding carbon black into a ball milling tank according to certain mass, stirring, and performing wet ball milling through 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 full drying to obtain uniformly mixed Al 2 O 3 Carbon black powder A2.
And (3) placing a certain amount of powder A2 into a graphite crucible, then placing the graphite crucible into a graphite sintering furnace, and performing carbothermal reduction for 2-4 h at 1550-1625 ℃ in a flowing nitrogen atmosphere to obtain a nitriding product powder A3.
And (4) placing a certain amount of powder A3 into a high-temperature box type furnace, preserving heat for 4-6 hours at 600-700 ℃, and removing redundant carbon in the nitriding product powder A3 to obtain raw material powder for firing the aluminum nitride ceramics.
Preferably, the alumina is ultrafine nanometer 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 100:40-100:60.
Preferably, the PVP has a molecular weight of 40000 and a mass content of 1 to 10% of the total amount of alumina and carbon black, preferably 4 to 6%.
Preferably, the Al 2 O 3 The mass ratio of the total carbon black to deionized water is 100: 300-100:450.
Preferably, the ball milling medium and deionized water, PVP and Al 2 O 3 The mass ratio of the total carbon black is 100: 10-100:30.
Preferably, the rotation speed of the ball mill is 100-150 r/min, and the time is 0.5-2 h.
Preferably, the drying temperature is 110 to 120 ℃.
Compared with the prior art, the invention has the following advantages:
(1) PVP adopted by the invention does not need to be dissolved for a long time in advance, and can be directly mixed with alumina and carbon powder by wet ball milling, and PVP is dissolved and synchronously coated on the surfaces of alumina particles and carbon black particles in the ball milling process, so that the slurry with low viscosity and good fluidity is finally obtained (table 1). The slurry obtained by ball milling and mixing at one time has good dispersibility, so that the mixing time can be greatly shortened at room temperature. In addition, the PVP melting point is near 130 ℃, and the production efficiency can be improved by adopting a higher drying temperature (110-120 ℃).
(2) Compared with a non-carbon inorganic dispersing agent, the PVP thin layer coated on the surface of the raw material particles can inhibit the aggregation of the alumina particles and can be decomposed at 400-500 ℃, so that new impurities are not introduced into the aluminum nitride product, and the generation of aluminum nitride is not hindered.
(3) Proper PVP and deionized water are added, the aluminum nitride powder synthesized by carbothermic reduction has narrower particle size distribution, smaller median diameter, greatly improved primary particle occupation ratio and lower oxygen content, and can meet the requirement of raw material powder for aluminum nitride ceramics with excellent firing performance.
Drawings
FIG. 1 is a morphology diagram of the synthetic powder of example 2.
FIG. 2 is a morphology of the synthetic powder of example 4.
FIG. 3 is a morphology diagram of the synthetic powder of comparative example 1.
FIG. 4 is a morphology diagram of the synthetic powder in comparative example 2.
FIG. 5 is a morphology of the composite powder of comparative example 3.
FIG. 6 shows particle diameter distribution diagrams of the synthesized powders in examples 1, 2, 3, and 4 and comparative examples 1 and 2.
FIG. 7 is a graph of PVP TG 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 materials in the ball milling tank in the following examples is 100: 10-100:30; the alumina is superfine nano powder, and the median diameter is 300-800 nm; the carbon black is superfine nano powder, and the median diameter is 20-100 nm.
Example 1
160g deionized water, 1.6g PVP, 25g Al were weighed 2 O 3 15g of carbon black is sequentially added into a ball milling tank, and after stirring, wet ball milling is carried out for 2 hours through a planetary ball mill, so that uniform slurry with no white point and good fluidity is obtained. The obtained mixed slurry is placed in a high-temperature oven at 110 ℃ for drying for 3 hours to obtain Al 2 O 3 Carbon black powder blend. 5g of the mixed powder is put into a vacuum sintering furnace, and calcined for 4 hours at 1600 ℃ under the flowing nitrogen atmosphere with the nitrogen flow rate controlled at 2L/minNitriding the product. 1.5g of the nitriding product is subjected to heat preservation for 5 hours at 650 ℃ in a high-temperature box-type furnace to remove carbon, so that high-purity aluminum nitride powder is obtained. The viscosity of the slurry after ball milling is measured to be 109.2 Pa.s (1.0 r/min) by a rotational viscometer; the particle size distribution of the obtained product is measured by a laser particle size analyzer, the median diameter particle size is 2.87 mu m, the proportion of primary particles below 2 mu m is 37.08%, and the proportion of powder below 5 mu m is 69.88%.
Example 2
Weigh 160g deionized water, 2.4g PVP, 25g Al 2 O 3 15g of carbon black is sequentially added into a ball milling tank, and after stirring, wet ball milling is carried out for 2 hours through a planetary ball mill, so that uniform slurry with no white point and good fluidity is obtained. The obtained mixed slurry is placed in a high-temperature oven at 110 ℃ for drying for 3 hours to obtain Al 2 O 3 Carbon black powder blend. 5g of the mixed powder is placed into a vacuum sintering furnace, the flow rate of nitrogen is controlled to be 2L/min under the flowing nitrogen atmosphere, and the temperature is controlled to 1600 ℃ for calcination for 4 hours to obtain a nitriding product. 1.5g of the nitriding product is subjected to heat preservation for 5 hours at 650 ℃ in a high-temperature box-type furnace to remove carbon, so that high-purity aluminum nitride powder is obtained. The viscosity of the slurry after ball milling is 73.7 Pa.s (1.0 r/min) by using a rotational viscometer; the particle size distribution of the obtained product is measured by a laser particle size analyzer, the median diameter particle size is 2.61 mu m, the proportion of primary particles below 2 mu m is 39.03%, the proportion of powder below 5 mu m is 75.45%, and the morphology is shown in figure 1.
Example 3
160g deionized water, 4g PVP and 25g Al are weighed 2 O 3 15g of carbon black is sequentially added into a ball milling tank, and after stirring, wet ball milling is carried out for 0.5h through a planetary ball mill, so that uniform slurry with no white point and good fluidity is obtained. The obtained mixed slurry is placed in a high-temperature oven at 120 ℃ for drying for 2.5 hours to obtain Al 2 O 3 Carbon black powder blend. 5g of the mixed powder is placed into a vacuum sintering furnace, the flow rate of nitrogen is controlled at 2L/min under the flowing nitrogen atmosphere, and the temperature is controlled at 1600 ℃ for calcination for 4 hours to obtain a nitriding product. 1.5g of the nitriding product is subjected to heat preservation for 5 hours at 650 ℃ in a high-temperature box-type furnace to remove carbon, so that high-purity aluminum nitride powder is obtained. The viscosity of the slurry after ball milling was measured to be 59 Pa.s (1.0 r/mi) by using a rotational viscometern); 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
Weigh 180g deionized water, 2.4g PVP, 25g Al 2 O 3 15g of carbon black is sequentially added into a ball milling tank, and after stirring, wet ball milling is carried out for 2 hours through a planetary ball mill, so that uniform slurry with no white point and good fluidity is obtained. The obtained mixed slurry is placed in a high-temperature oven at 120 ℃ for drying for 2.5 hours to obtain Al 2 O 3 Carbon black powder blend. 5g of the mixed powder is placed into a vacuum sintering furnace, the flow rate of nitrogen is controlled to be 2L/min under the flowing nitrogen atmosphere, and the temperature is controlled to 1600 ℃ for calcination for 4 hours to obtain a nitriding product. 1.5g of the nitriding product is subjected to heat preservation for 5 hours at 650 ℃ in a high-temperature box-type furnace to remove carbon, so that high-purity aluminum nitride powder is obtained. Measuring the viscosity of the slurry after ball milling to be 13.7 Pa.s (1.0 r/min) by using a rotational viscometer; the particle size distribution of the obtained product is measured by a laser particle size analyzer, the median diameter particle size is 2.40 mu m, the proportion of primary particles below 2 mu m is 43.07%, the proportion of powder below 5 mu m is 76.57%, and the morphology is shown in figure 2.
Example 5
140g deionized water, 2.4g PVP, 25g Al were weighed 2 O 3 And adding 10g of carbon black into a ball milling tank in sequence, stirring, and performing wet ball milling for 2 hours through a planetary ball mill to obtain uniform slurry with no white point and good fluidity. The obtained mixed slurry is placed in a high-temperature oven at 110 ℃ for drying for 3 hours to obtain Al 2 O 3 Carbon black powder blend. 5g of the mixed powder is placed into a vacuum sintering furnace, the flow rate of nitrogen is controlled to be 2L/min under the flowing nitrogen atmosphere, and the temperature is controlled to be 1550 ℃ and calcined for 6 hours to obtain a nitriding product. 1.5g of the nitriding product is subjected to heat preservation for 6 hours at 600 ℃ in a high-temperature box furnace to remove carbon, so that high-purity aluminum nitride powder is obtained. 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
Weigh 180g deionized water, 2.4g PVP, 25g Al 2 O 3 15g of carbon black is sequentially added into a ball milling tank, and after stirring, wet ball milling is carried out for 1h through a planetary ball mill, so that uniform slurry with no white point and good fluidity is obtained. The obtained mixed slurry is placed in a high-temperature oven at 110 ℃ for drying for 3 hours to obtain Al 2 O 3 Carbon black powder blend. 5g of the mixed powder is placed into a vacuum sintering furnace, and the nitrogen is calcined for 3 hours at the temperature of 1625 ℃ under the flowing nitrogen atmosphere with the flow rate of 2L/min. 1.5g of the nitriding product is subjected to heat preservation for 4 hours at 700 ℃ in a high-temperature box-type furnace to remove carbon, so that high-purity aluminum nitride powder is obtained. 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
Weigh 105g deionized water, 2.4g PVP, 25g Al 2 O 3 And adding 10g of carbon black into a ball milling tank in sequence, stirring, and performing wet ball milling for 2 hours through a planetary ball mill to obtain uniform slurry with no white point and good fluidity. The obtained mixed slurry is placed in a high-temperature oven at 110 ℃ for drying for 2.5 hours to obtain Al 2 O 3 Carbon black powder blend. 5g of the mixed powder is placed into a vacuum sintering furnace, the flow rate of nitrogen is controlled to be 2L/min under the flowing nitrogen atmosphere, and the temperature is controlled to 1600 ℃ for calcination for 4 hours to obtain a nitriding product. 1.5g of the nitriding product is subjected to heat preservation for 5 hours at 650 ℃ in a high-temperature box-type furnace to remove carbon, so that high-purity aluminum nitride powder is obtained. The viscosity of the slurry after ball milling is measured by adopting a rotational viscometer, the viscosity is larger, and the measurement range is exceeded; the particle size distribution of the obtained product is measured by a laser particle size analyzer, 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 deionized water and 25g Al were weighed 2 O 3 15g of carbon black is sequentially added into a ball milling tank, stirred and then ball-milled for 2 hours by a wet method of a planetary ball mill, so that uniform white-spot-free slurry is obtained. Placing the slurry in a high-temperature oven at 110 ℃ for drying for 3 hours to obtain Al 2 O 3 Carbon blackAnd (5) mixing powder materials. 5g of the mixed powder is placed into a vacuum sintering furnace, the flow rate of nitrogen is controlled at 2L/min under the flowing nitrogen atmosphere, and the temperature is controlled at 1600 ℃ to calcine 4h to obtain a nitriding product. 1.5g of the nitriding product is subjected to heat preservation for 5 hours at 650 ℃ in a high-temperature box-type furnace to remove carbon, so that high-purity aluminum nitride powder is obtained. The viscosity of the slurry after ball milling is measured by adopting a rotational viscometer, the viscosity is larger, and the measurement range is exceeded; 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 transparent impurity-free solution. Adding 25g of aluminum oxide and 15g of carbon black into a ball milling tank in batches, stirring, and performing wet ball milling for 2 hours through a planetary ball mill to obtain uniform white-spot-free slurry. Placing the slurry in a high-temperature oven at 65 ℃ for drying for 12 hours to obtain Al 2 O 3 Carbon black powder blend. 5g of the mixed powder is placed into a vacuum sintering furnace, the flow rate of nitrogen is controlled at 2L/min under the flowing nitrogen atmosphere, and the temperature is controlled at 1600 ℃ for calcination for 4 hours to obtain a nitriding product. 1.5g of the nitriding product is subjected to heat preservation for 5 hours at 650 ℃ in a high-temperature box-type furnace to remove carbon, and aluminum nitride powder is obtained. Measuring the viscosity of the slurry after ball milling to be 130.65 Pa.s (1.0 r/min) by adopting a rotational viscometer; 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 3 hours, and the mixture is dispersed into transparent impurity-free solution. Adding 25g of aluminum oxide and 15g of carbon black into a ball milling tank in batches, stirring, and performing wet ball milling for 2 hours through a planetary ball mill to obtain uniform white-spot-free slurry. Placing the slurry in a high-temperature oven at 120 ℃ for drying for 2.5h to obtain Al 2 O 3 Carbon black powder blend. 5g of the mixed powder is put into a vacuum sintering furnace, the flow rate of nitrogen is controlled to be 2L/min under the flowing nitrogen atmosphere, and the temperature is controlledCalcining at 1600 ℃ for 4 hours to obtain a nitriding product. 1.5g of the nitriding product is subjected to heat preservation for 5 hours at 650 ℃ in a high-temperature box-type furnace to remove carbon, and aluminum nitride powder is obtained. Measuring the viscosity of the slurry after ball milling to be 13.5 Pa.s (1.0 r/min) by using a rotational viscometer; 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 viscosity comparison of the slurries after ball milling in examples 1, 2, 3, 4 and comparative examples 1, 2 at a rotational speed of 1r/min
From table 1, it can be seen that the viscosity of the slurry is reduced after PVP is added, and the fluidity is improved, which is favorable for more uniform mixing under the same ball milling condition. When PVP is not added, the viscosity of the slurry is very high, the slurry can not be measured, the fluidity is almost absent, and the mixing effect is poor. 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-milling sample. Therefore, the adoption of PVP can omit a long-time pre-dissolution process link.
As is clear from FIG. 6, examples 1 to 4 have smaller median diameter particle sizes than comparative examples, and have better product dispersibility. From fig. 7 it can be seen that PVP breaks down between 400 and 500 degrees.
From the data of the above examples and comparative examples, it can be seen that the PVP has an obvious dispersion effect on the mixed raw materials, and is superior to the sample without PVP or PVA, the obtained aluminum nitride has a narrow particle size distribution, a small median diameter, primary particles below 2 microns and powder below 5 microns with a higher ratio, and the synthesized product is not adversely affected, and the purity of the obtained aluminum nitride powder is higher.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and falls within the scope of the present invention as long as the present invention meets the requirements.
Claims (9)
1. The preparation method of the low-agglomeration aluminum nitride powder is characterized by comprising the following steps of:
step (1), deionized water, PVP and Al 2 O 3 Adding carbon black into a ball milling tank in turn according to a certain mass ratio, stirring, and performing wet ball milling through 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 full drying to obtain uniformly mixed Al 2 O 3 Carbon black powder A2;
step (3), placing a certain amount of powder A2 into a graphite crucible, then placing the graphite crucible into a graphite sintering furnace, and performing carbothermal reduction at 1550-1625 ℃ under flowing nitrogen atmosphere for 2-4 h to obtain nitriding product powder A3;
and (4) placing a certain amount of powder A3 into a high-temperature box type furnace, preserving heat at 600-700 ℃ for 4-6 h, and removing redundant carbon in the nitriding product powder A3 to obtain raw material powder for firing the aluminum nitride ceramics.
2. The method for preparing low-agglomeration aluminum nitride powder according to claim 1, wherein the Al is 2 O 3 The median diameter of (2) is 300-800 nm.
3. The method for producing a low-aggregation aluminum nitride powder according to claim 1, wherein the carbon black has a median diameter of 20 to 100nm.
4. The method for preparing low-agglomeration aluminum nitride powder according to claim 1, wherein the Al is 2 O 3 The mass ratio of the carbon black to the carbon black is 100:40-100:60.
5. The method for preparing low-aggregation aluminum nitride powder according to claim 1, wherein the PVP has a molecular weight of 40000 and a mass content of Al 2 O 3 1 to 10 percent of the total amount of carbon black.
6. The method for preparing low-aggregation aluminum nitride powder according to claim 5, wherein the PVP isMolecular weight of 40000 and mass content of Al 2 O 3 4 to 6 percent of the total amount of the carbon black.
7. The method for preparing low-agglomeration aluminum nitride powder according to claim 1, wherein the Al is 2 O 3 The mass ratio of the total carbon black to deionized water is 100: 300-100:450.
8. The method for preparing the 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 producing a low-agglomeration aluminum nitride powder according to claim 1, wherein the drying temperature is 110 to 120 ℃.
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