CN1228242C - Preparation method of hexagonal phase nano-aluminium nitride powder - Google Patents
Preparation method of hexagonal phase nano-aluminium nitride powder Download PDFInfo
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- CN1228242C CN1228242C CN 03129582 CN03129582A CN1228242C CN 1228242 C CN1228242 C CN 1228242C CN 03129582 CN03129582 CN 03129582 CN 03129582 A CN03129582 A CN 03129582A CN 1228242 C CN1228242 C CN 1228242C
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Abstract
The present invention provides a method for preparing hexagonal phase nanometer aluminum nitride powder by using common metal aluminum powder (100 to 200 meshes) as raw material. The present invention mainly uses ammonium chloride and potassium chloride as additive agents, nitriding operation is carried out for more than 5 h in flowing ammonia gas and at the temperature of 1000 to 1200 DEGC, and nanometer crystal aluminum nitride powder whose average grain size is 13.5 nm and average grain size of one time agglomerated particles is 33 nm is obtained. The additive agents can reduce the nitriding temperature and inhibit the particle size enlargement, and no residue exists. Ammonia gas is used as raw material gas and ensures the higher purity of the aluminum nitride powder. The method has the characteristics of simple technology, low production cost, large scale production, etc.
Description
Technical field
The present invention relates to a kind of preparation method of six side's phase nano aluminum nitride powders, prepare the method for nano aluminum nitride powder or rather from the plain metal aluminium powder, belong to field of nanometer material technology.
Technical background
Aluminium nitride has very high thermal conductivity coefficient, and (six sides are 170-260W m mutually
-1K
-1), and hardness is big, have good insulating property, low-expansion coefficient, molten metal and salt there is the excellent anti erosion, therefore being considered to a kind of inorganic materials with wide application prospect, can be again high-power and optional material high-temperature device as electronic isolation substrate material and microelectronic packaging material both.
The purity of aluminium nitride powder, the character of the aluminium nitride ceramics goods of size and distribution and specific surface area and coking property and gained all has extremely confidential relation, therefore, preparation method's tool of studying and seeking the aluminium nitride powder that particle size is little, purity is high has very important significance.The main method of present industrial production aluminium nitride is aluminum oxide powder carbothermic method and metallic aluminium powder direct nitridation method.The powder size that carbothermic method obtains is more even, but the temperature of reaction requirement is high, generally at 1600～1800 ℃, and needs secondary oxidation remove unnecessary carbon, the production cost height.By contrast, the direct nitridation method cheap and simple makes the aluminium powder fusing but its shortcoming is high temperature (often reaching 1500 ℃) and nitrogenizing reaction liberated heat, is difficult to obtain ultra-fine aluminum nitride powder.The aluminium nitride protective layer of aluminium powder surface formation can hinder the carrying out of reaction in addition, therefore needs intermediate steps such as grinding, so that the aluminium powder nitrogenize is complete, this causes the concentration of impurity to improve greatly.
In recent years, Chinese scholars is developed some novel methods direct nitridation method is improved, the nitriding that for example suspends (A.J.Chang et al., J.Am.Ceram.Soc., 1995,78[1], 33-40), the gas-phase reaction method of aluminum vapor and ammonia, (S.E.Pratsinis et al., J.Mater.Res., 1995,10[3] 512-20), with adding metallic lithium additive (K.Komeya et al., J.Ceram.Soc.Jap., 1993,101[12] 1319-23) etc.But some method is not suitable for industrial production, and also there is obstacle technically in some.
Summary of the invention
The objective of the invention is to overcome the shortcoming that existing direct nitridation method prepares aluminium nitride, and a kind of method for preparing nanocrystalline aluminium nitride powder from the plain metal aluminium powder is provided.
The objective of the invention is to implement like this: is starting raw material with purity greater than 99% plain metal aluminium powder (100～200 order), add purity greater than 99.5% ammonium chloride and Repone K as additive, mass ratio is: aluminium powder: ammonium chloride: Repone K=1: 0.5: 0.5～1: 1.5: 1.5, with acetone is medium, sphere of powder mass ratio is 1: 8～1: 10, ball milling mixed 32～48 hours, then 80～100 ℃ of oven dry, obtained the mixed uniformly powder of aluminium powder and additive.This powder is put into aluminium oxide boat, and the tubular type of packing into atmosphere furnace feeds ammonia and drives away inner air tube.Logical ammonia was warming up to 1000～1200 ℃ after one hour, and keeping ammonia flow is 0.5～5 liter/minute, and temperature rise rate is as follows: room temperature～600 ℃: 10 ℃/minute, and 600 ℃～800 ℃: 7 ℃/minute, after 800 ℃: 5 ℃/minute.Under this temperature, insulation is more than 5 hours.Then, under mobile ammonia or nitrogen protection, naturally cool to room temperature, obtain the nano aluminum nitride powder.Can control the particle diameter and the nitriding velocity of nano aluminum nitride by temperature of reaction; Purity by control temperature retention time of nitrogenization control nano aluminum nitride; Shorten the reaction times by control ammonia flow velocity.Temperature of reaction is high more, and the particle diameter of powder is big more, and the time of nitrogenize is short more fully; Soaking time is long more, and the purity of gained powder is high more; The flow velocity of ammonia is big more, and reaction is carried out soon more.So the selection of these three parameters all has fundamental influence to reacted particle diameter, output, these three parameters of choose reasonable, it is very important making it organic coupling.
Reaction process is as follows:
Total reaction is:
The preparation method's of nano aluminum nitride provided by the invention characteristics are:
(1) adopting 100～200 order plain metal aluminium powders is the aluminium source, adds suitable additive, and direct nitrogenize prepares the nano aluminum nitride powder under the high temperature in the ammonia that flows;
(2) adopt ammonium chloride and Repone K as additive, reduce nitriding temperature, and suppress powder granule and grow up and reunite, and additive noresidue in product;
(3) adopting ammonia is reactant gases, and the aluminium nitride powder purity that obtains is higher than 95%;
(4) low to ingredient requirement, production technique is simple, can utilize existing direct nitridation method to produce the equipment of aluminium nitride, and production cost is low.
Description of drawings
The process flow sheet of Fig. 1 nano aluminum nitride powder preparing
The X-ray diffractogram of 5 hours gained aluminium nitride powders of 1000 ℃ of nitrogenize of Fig. 2
The transmission electron microscope and the selected diffraction photo of 5 hours gained aluminium nitride of 1000 ℃ of nitrogenize of Fig. 3
Embodiment
Further specify embodiment and effect with following indefiniteness embodiment:
Embodiment 1
Get aluminium powder (100～200 order) 3g, ammonium chloride and Repone K are neat as adding, its mass ratio is: aluminium powder: ammonium chloride: Repone K=1: 0.8: 0.8, the 5mm stainless steel bead that powder quality is 10 times, acetone 100ml is loaded in the ball grinder, ball milling 48 hours, obtain bulk mixed powder, with it 80 ℃ of oven dry.The mixed powder that obtains is put into aluminium oxide boat, and the tubular type of packing into atmosphere furnace feeds ammonia, and ammonia flow is 3～5 liters/minute, to drive away air in tube.After one hour, ammonia flow is reduced and remain on 0.6 liter/minute, be warming up to 1000 ℃.Temperature rise rate is as follows: room temperature～600 ℃: 10 ℃/minute, and 600～800 ℃: 7 ℃/minute, 800～1000 ℃: 5 ℃/minute.1000 ℃ of insulations 5 hours, then, under the ammonia that flows, naturally cool to room temperature.Obtain nano aluminum nitride.Fig. 2 is the X-ray diffractogram of the nano aluminum nitride of present embodiment preparation, and what generation was described is six side's phase aluminium nitride, and does not find Al
2O
3With the diffraction peak of AlON, the purity of aluminium nitride powder is more than 95%.Fig. 3 is its transmission electron microscope photo, shows that its particle mean size is 13.5nm.The aluminium nitride powder that the explanation of selected diffraction photo generates is a polycrystalline.
Embodiment 2
Method by embodiment 1 prepares nano aluminum nitride, aluminium powder: ammonium chloride: potassium nitride=1: 1.2: 1.2 (mass ratio) temperature of reaction is 1200 ℃, obtains the nano aluminum nitride powder.Present embodiment shows the purity of the nano aluminum nitride powder that prepared under the condition in 5 hours 1200 ℃ of ammonia nitrogenize more than 95%, and particle size is 20～45nm, illustrates with nitriding temperature to raise, and aluminum nitride particle is grown up.
Embodiment 3
Method by embodiment 1 prepares nano aluminum nitride, and temperature of reaction is 1100 ℃, and the reaction times was respectively 3 hours and 5 hours.When nitrogenize only contained the Al of trace after 3 hours in the nano aluminum nitride that obtains
2O
3And AlON.In nitrogenize after 5 hours, Al
2O
3Disappear with the AlON impurity peaks.Show that nitridation time should could guarantee the purity of gained aluminium nitride more than or equal to 5 hours.The size of an agglomerating particles of 1100 ℃ of 5 hours gained aluminium nitride powders of reaction is less than 100nm.
Claims (4)
1. the preparation method of side's phase nano aluminum nitride powder is characterized in that:
(1) adopting the plain metal aluminium powder is the aluminium source, adds ammonium chloride and Repone K additive, and ball milling is made uniform mixed powder; The mass ratio of described aluminium powder and additive is: aluminium powder: ammonium chloride: Repone K=1: 0.5: 0.5～1: 1.5: 1.5;
(2) under the ammonia atmosphere that flows, with the direct nitrogenize of mixed powder; Nitriding temperature is 1000～1200 ℃; Nitridation time is more than or equal to 5 hours; Ammonia flow is 0.5～5 liter/minute.
2. according to the method for the described preparation six side's phase nano aluminum nitride powders of claim 1, it is characterized in that:
The granularity of plain metal aluminium powder is 100～200 orders, and purity is greater than 99%; The purity of additive ammonium chloride and Repone K additive is greater than 99.5%.
3. according to the method for the described preparation six side's phase nano aluminum nitride powders of claim 1, it is characterized in that the medium during the mixed powder ball milling is an acetone, sphere of powder mass ratio is 1: 8～1: 10, and the ball milling time is 32～48 hours.
4. according to the method for the described preparation six side's phase nano aluminum nitride powders of claim 1, it is characterized in that:
(1) the nitrogenize temperature rise rate is room temperature～600 ℃: 10 ℃/minute, and 600 ℃～800 ℃: 7 ℃/minute, after 800 ℃: 5 ℃/minute;
(2) under mobile ammonia or nitrogen protection, naturally cool to room temperature.
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| CN1228242C true CN1228242C (en) | 2005-11-23 |
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| CN101973532B (en) * | 2010-09-30 | 2012-02-22 | 中国计量学院 | Method for preparing nano aluminum nitride powder |
| CN102502538B (en) * | 2011-11-08 | 2013-04-10 | 中国计量学院 | Method for synthesizing ultrafine aluminum nitride powder at low temperature under assistance of calcium |
| CN102502539B (en) * | 2011-11-08 | 2013-04-10 | 中国计量学院 | Method for preparing yttrium-doped nano aluminum nitride powder |
| CN102584244A (en) * | 2012-03-09 | 2012-07-18 | 东华大学 | Method for preparing hexagonal phase aluminum nitride nanofiber by using electrostatic spinning and ammonia nitridation |
| CN103539088B (en) * | 2013-11-05 | 2015-10-07 | 河北工业大学 | A kind of synthetic method of aluminum nitride nanometer particle |
| CN113120908B (en) * | 2021-04-13 | 2023-12-29 | 中民驰远实业有限公司 | alpha-Si 3 N 4 Preparation method of SiC refractory composite powder |
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