CN112919914A - Preparation method of AlN ceramic powder - Google Patents
Preparation method of AlN ceramic powder Download PDFInfo
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- CN112919914A CN112919914A CN202110347568.0A CN202110347568A CN112919914A CN 112919914 A CN112919914 A CN 112919914A CN 202110347568 A CN202110347568 A CN 202110347568A CN 112919914 A CN112919914 A CN 112919914A
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/581—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on aluminium nitride
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Abstract
The invention provides a preparation method of Al N ceramic powder, which comprises the following steps: adding an aluminum source and a carbon source into a solvent for mixing to form a solution, and heating the solution for reaction to obtain hydrosol; the aluminum source comprises aluminum iso-butoxide, and the carbon source comprises an organic precursor. The organic matter precursor comprises at least one of sucrose, PVA, fructose, glucose or maltose. The molar ratio of the aluminum element in the aluminum source to the carbon element in the carbon source is 1: 3 to 4. And drying the hydrosol to form dry gel. Calcining the xerogel to form Al2O3-C composite powder. Using a carbothermic method to reduce the Al2O3Carrying out nitridation reaction on-C composite powder under a flowing atmosphere, wherein the flowing atmosphere comprises NH3Or N2At leastOne, preparing Al N ceramic powder. The preparation method of the Al N ceramic powder provided by the invention is simple and practical, has high production efficiency, saves energy, and has high quality stability and excellent comprehensive performance.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a preparation method of AlN ceramic powder.
Background
The aluminum nitride (AlN) ceramic has the advantages of high thermal conductivity, high thermal expansion coefficient, no toxicity, high hardness and the like. The thermal conductivity is more than 170W/m.K, which is 8-10 times of that of alumina. A coefficient of thermal expansion of 4.0 to 4.5 x 10-6The temperature per DEG C is close to the thermal expansion coefficient of a semiconductor, and is an ideal heat dissipation material of a semiconductor package. The aluminum nitride is mainly used for phonon heat dissipation, the influence of the lattice oxygen content on the thermal conductivity is large, and 3AlN + Al2O3＝2Al* Al+2N* N+30·N+V″′Al. When the oxygen content of the crystal lattice exceeds 2 wt%, but the oxygen content is still low, the nitrogen atoms in the Al-O tetrahedron are substituted by oxygen atoms and an aluminum vacancy is formed, and the generation of the aluminum vacancy causes a decrease in the thermal conductivity of aluminum nitride. When the oxygen content is higher, defects such as faults, reverse domain boundaries and the like can be formed, so that the phonon scattering cross section is greatly increased, and the thermal conductivity is reduced. The N and O atoms have small difference but have large influence on the thermal conductivity, and Al atomic nucleus vacancy is the main reason of reducing the thermal conductivity. Therefore, the inventors found that for aluminum nitride ceramics requiring high thermal conductivity, the control of the oxygen content below 2 wt% is the key point in the preparation process for preparing high quality aluminum nitride powder.
At present, the commonly used preparation methods of the aluminum nitride powder include the following methods: 1. carbothermic reduction of alumina; 2. aluminum powder direct nitriding method; 3. a self-propagating combustion method; 4. chemical vapor phase processes; 5. direct cracking of organic aluminum source, etc. Among them, the carbothermic method and the direct nitriding method of aluminum powder have been commercialized, but the carbothermic method is generally used in which alumina and carbon black are first mechanically mixed and then nitrided. In the premixing process, alumina and carbon black are difficult to be uniformly mixed, so that the activity of the alumina is low, a higher nitriding temperature is required, the nitriding efficiency is low, the energy consumption is high, and the economical efficiency is poor in the nitriding process. The aluminum nitride powder prepared by the direct aluminum powder nitriding method has the following problems: and at the beginning of nitriding, the formed aluminum nitride is wrapped around the aluminum powder, nitrogen needs to diffuse and penetrate through the aluminum nitride layer during further nitriding reaction, the reaction is mainly controlled by gas phase diffusion, the time is long, meanwhile, the nitriding reaction is a strong exothermic reaction, and the heat released during the reaction is enough to enable the aluminum nitride powder body to be self-sintered, so that the prepared aluminum nitride powder is poor in quality and stability.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides the preparation method of the AlN ceramic powder, which is simple and practical, high in production efficiency, energy-saving, high in quality stability of the prepared AlN ceramic powder and excellent in comprehensive performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of AlN ceramic powder comprises the following steps:
selecting aluminum iso-butoxide as an aluminum source and an organic precursor as a carbon source;
adding an aluminum source and a carbon source into a solvent for mixing to form a solution, and heating the solution for reaction to obtain hydrosol; wherein the aluminum source comprises aluminum iso-butoxide, and the carbon source comprises an organic precursor;
drying the hydrosol to form dry gel;
calcining the xerogel to form Al2O3-C composite powder;
using a carbothermic method to reduce the Al2O3And carrying out nitridation reaction on the-C composite powder in a flowing atmosphere to prepare AlN ceramic powder.
The further improvement of the technical scheme is as follows:
the organic matter precursor comprises at least one of sucrose, PVA, fructose, glucose or maltose.
The molar ratio of the aluminum element in the aluminum source to the carbon element in the carbon source is 1: 3 to 4.
The heating temperature of the calcination is 900-1100 ℃, and the heat preservation time is 1-2 h.
The flowing atmosphere comprises NH3Or N2At least one of (1).
The Al is subjected to a carbothermic reduction method2O3The step of carrying out nitridation reaction on the-C composite powder in a flowing atmosphere to prepare AlN ceramic powder further comprises the following steps: and performing decarbonization treatment on the AlN ceramic powder.
The temperature of the decarbonization treatment is 650-850 ℃.
The flow rate of the flowing atmosphere is 0.8-1.8L/min.
And drying the hydrosol to form a dried gel at the temperature of 80-120 ℃ for 2-5 h.
And heating the solution for reaction to obtain hydrosol, wherein the reaction comprises the following steps: and heating the solution in a water bath at the temperature of 60-85 ℃ for reaction for 10-24 h.
According to the technical scheme, the preparation method of the AlN ceramic powder adopts the aluminum iso-butoxide as the aluminum source, adopts the organic precursor as the carbon source, and leads the C and Al to be cracked at high temperature by the organic matter2O3Reaching microscopic uniformity, then introducing flowing atmosphere, and preparing the AlN ceramic powder by a carbothermic method. The technical scheme of the invention overcomes the defects of the prior artThe alumina and carbon black are difficult to be mixed evenly by carbothermic method in the technology. And preparing Al by a sol-gel method2O3the-C composite powder and the sol-gel have the advantages that the raw materials can be mixed more uniformly, so that the activity of the alumina is improved, the nitridation can be carried out at a lower chlorination temperature, the efficiency of the nitridation reaction is improved, and the energy consumption is effectively reduced.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing AlN ceramic powder according to an embodiment of the invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As shown in fig. 1, the method for preparing AlN ceramic powder according to this embodiment includes the following steps:
s1, uniformly mixing the aluminum source and the carbon source, dissolving the aluminum source and the carbon source into a solvent together to form a solution, and heating the solution in a water bath at the temperature of 60-85 ℃ for reaction for 10-24 hours to obtain hydrosol with uniformly mixed aluminum source and carbon source. During the heating reaction, in order to make the mixing more uniform, the solution can be stirred while being heated in a water bath. The stirring may be magnetic stirring or ultrasonic stirring.
Wherein the aluminum source consists of aluminum iso-butoxide. The carbon source includes an organic precursor, and may be at least one of sucrose, PVA, fructose, glucose, or maltose, for example. The solvent is deionized water. The molar ratio of the aluminum element in the aluminum source to the carbon element in the carbon source is 1: 3 to 4.
And S2, placing the hydrosol in an oven, and drying to form a dry gel.
The temperature during drying is 80-120 ℃, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃ and the like, and the heat preservation time is 2-5 h.
S3, placing the xerogel into a vacuum furnace for calcining to form Al2O3-C composite powder.
The heating temperature of the calcination is 900-1100 ℃, for example, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, or 1100 ℃, and the like, and the heat preservation time is 1-2 hours.
S4, carrying out carbothermic reduction on the Al2O3And carrying out nitridation reaction on the-C composite powder in a flowing atmosphere to prepare AlN ceramic powder.
The flowing atmosphere comprises NH3Or N2At least one of the above, wherein the flow rate of the flowing atmosphere is 0.8 to 1.8L/min. The temperature of the nitridation reaction is 1250-1400 ℃, for example, 1250 ℃, 1300 ℃, 1350 ℃, or 1400 ℃, and the like, and the heat preservation time is 3-8 h.
Since the sol-gel method has a problem of excessive carbon source, it is necessary to subject the AlN ceramic powder to a decarbonization treatment after the nitridation reaction.
And S5, performing decarbonization treatment on the AlN ceramic powder prepared in the step S4, wherein the decarbonization treatment temperature is 650-850 ℃, for example, 650 ℃, 700 ℃, 750 ℃, 800 ℃ or 850 ℃, and the like, and the heat preservation time is 1-4 h, so that the AlN ceramic powder with low oxygen content, high purity and uniform particle size is finally obtained.
Example 1, the preparation method of AlN ceramic powder according to this example was consistent with the above method, and the specific implementation data was as follows:
s1, wherein the molar ratio of the aluminum element in the aluminum source to the carbon element in the carbon source is 1: 4. the organic matter precursor is sucrose.
S4, wherein the heating temperature of the calcination is 1100 ℃.
S5, the temperature of the nitridation reaction is 1350 ℃, and the heat preservation time is 5 h.
Example 2, the preparation method of AlN ceramic powder in this example was substantially the same as example 1, except that:
s1, wherein the molar ratio of the aluminum element in the aluminum source to the carbon element in the carbon source is 1: 3.
s4, the heating temperature of the calcination is 1050 ℃.
And S5, the temperature of the nitridation reaction is 1300 ℃, and the heat preservation time is 3 h.
Example 3, the preparation method of AlN ceramic powder of this example was substantially the same as example 1, except that:
s1, wherein the molar ratio of the aluminum element in the aluminum source to the carbon element in the carbon source is 1: 3.5. the organic matter precursor is fructose.
S4, wherein the heating temperature of the calcination is 950 ℃.
S5, the temperature of the nitridation reaction is 1350 ℃, and the heat preservation time is 4 h.
Example 4, the preparation method of AlN ceramic powder in this example was substantially the same as example 1, except that:
s1, wherein the molar ratio of the aluminum element in the aluminum source to the carbon element in the carbon source is 1: 3.5. the organic matter precursor is fructose.
S4, the heating temperature of the calcination is 1050 ℃.
S5, the temperature of the nitridation reaction is 1400 ℃, and the heat preservation time is 8 h.
Example 5, the preparation method of AlN ceramic powder in this example was substantially the same as example 1, except that:
s1, wherein the molar ratio of the aluminum element in the aluminum source to the carbon element in the carbon source is 1: 4. the organic matter precursor is PVA.
S4, wherein the heating temperature of the calcination is 900 ℃.
S5, the temperature of the nitridation reaction is 1250 ℃, and the heat preservation time is 3 h.
In order to prove the effectiveness of the preparation method of the present invention, the properties of the AlN ceramic powder prepared in the above five examples were examined, and the examination results are shown in table 1.
TABLE 1
As shown in the test results in Table 1, the AlN ceramic powder prepared by the method of the present invention has a particle size of no more than 1.3 μm, an oxygen content of no more than 1.5 wt/%, and an N content of no less than 32 wt/%, and thus the AlN ceramic powder prepared by the method of the present invention has the advantages of uniform particle size, high purity, low oxygen content, high quality stability and excellent comprehensive performance.
The preparation method combines the advantages of the sol-gel preparation method, and the sol-gel method is firstly used for preparing the Al uniformly wrapped by the C2O3Powder, and C source is provided by vacuum high-temperature cracking of organic matter, C and Al2O3Can achieve microcosmic uniformity, and C is uniformly wrapped on Al2O3And introducing nitrogen gas to carry out nitridation reaction to prepare high-purity aluminum nitride powder. Which prepare Al by a sol-gel method2O3-C composite powder, forming the composite powder into a core-shell structure, Al2O3The surface of the particle is uniformly coated with a layer of structure C. Compared with the prior art, Al2O3As C powder is directly added into the powder, the powder is more uniformly mixed with C mechanically, so that Al is ensured2O3The reaction activity is higher, the nitriding efficiency is higher, the nitriding temperature is lower, the particle size of AlN ceramic powder formed after nitriding is more uniform, and the purity is higher.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only express preferred embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of AlN ceramic powder is characterized by comprising the following steps: the method comprises the following steps:
adding an aluminum source and a carbon source into a solvent for mixing to form a solution, and heating and reacting the solution to obtain hydrosol, wherein the aluminum source comprises aluminum iso-butoxide, and the carbon source comprises an organic precursor;
drying the hydrosol to form dry gel;
calcining the xerogel to form Al2O3-C composite powder;
using a carbothermic method to reduce the Al2O3And carrying out nitridation reaction on the-C composite powder in a flowing atmosphere to prepare AlN ceramic powder.
2. The method for producing an AlN ceramic powder according to claim 1, wherein: the organic matter precursor comprises at least one of sucrose, PVA, fructose, glucose or maltose.
3. The method for producing an AlN ceramic powder according to claim 1, wherein: the molar ratio of the aluminum element in the aluminum source to the carbon element in the carbon source is 1: 3 to 4.
4. The method for producing an AlN ceramic powder according to claim 1, wherein: the heating temperature of the calcination is 900-1100 ℃, and the heat preservation time is 1-2 h.
5. The method for producing an AlN ceramic powder according to claim 1, wherein: the flowing atmosphere comprises NH3Or N2At least one of (1).
6. The method for producing an AlN ceramic powder according to claim 1, wherein: the Al is subjected to a carbothermic reduction method2O3The step of carrying out nitridation reaction on the-C composite powder in a flowing atmosphere to prepare AlN ceramic powder further comprises the following steps:
and performing decarbonization treatment on the AlN ceramic powder.
7. The method according to claim 6, wherein: the temperature of the decarbonization treatment is 650-850 ℃.
8. The method for producing an AlN ceramic powder according to claim 1, wherein: the flow rate of the flowing atmosphere is 0.8-1.8L/min.
9. The method for producing an AlN ceramic powder according to claim 1, wherein: and drying the hydrosol to form a dried gel at the temperature of 80-120 ℃ for 2-5 h.
10. The method for producing an AlN ceramic powder according to claim 1, wherein: the heating reaction is carried out on the solution to obtain hydrosol, and the method comprises the following steps: and heating the solution in a water bath at the temperature of 60-85 ℃ for reaction for 10-24 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116396082A (en) * | 2023-05-24 | 2023-07-07 | 郑州大学 | Preparation method of aluminum nitride powder |
Citations (2)
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| CN102502539A (en) * | 2011-11-08 | 2012-06-20 | 中国计量学院 | Method for preparing yttrium-doped nano aluminum nitride powder |
| CN107903069A (en) * | 2017-12-29 | 2018-04-13 | 苏州图纳新材料科技有限公司 | Aluminium nitride powder and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502539A (en) * | 2011-11-08 | 2012-06-20 | 中国计量学院 | Method for preparing yttrium-doped nano aluminum nitride powder |
| CN107903069A (en) * | 2017-12-29 | 2018-04-13 | 苏州图纳新材料科技有限公司 | Aluminium nitride powder and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 王宇等: "超细AlN粉体合成与陶瓷制备研究", 《功能材料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116396082A (en) * | 2023-05-24 | 2023-07-07 | 郑州大学 | Preparation method of aluminum nitride powder |
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