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CN103304223B - Preparation method of high-purity aluminum oxide ceramic - Google Patents

Preparation method of high-purity aluminum oxide ceramic Download PDF

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CN103304223B
CN103304223B CN201310232294.6A CN201310232294A CN103304223B CN 103304223 B CN103304223 B CN 103304223B CN 201310232294 A CN201310232294 A CN 201310232294A CN 103304223 B CN103304223 B CN 103304223B
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preparation
aluminum oxide
purity
alumina
sintering
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CN103304223A (en
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汪永清
周健儿
常启兵
张小珍
梁健
胡学兵
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Foshan China made glaze Co.,Ltd.
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Jingdezhen Ceramic Institute
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Abstract

The invention discloses a preparation method of a high-purity aluminum oxide ceramic. According to the preparation method, a nano Al2O3 coating formed on the surfaces of aluminum oxide particles is used as a sintering aid to ensure that a small amount of the sintering aid can be uniformly dispersed in a main phase, so that uniform adding of a small dose of the sintering aid is realized. The preparation method not only ensures the purity and performance of the high-purity aluminum oxide ceramic and meets process requirements for preparation of the aluminum oxide ceramic, but also effectively solves the problem that when the particle size difference of main phase powder and the sintering aid is large, particles of a nano auxiliary agent are gathered in a main phase powder particle gap; and moreover, partial over-firing is avoided, so that the uniformity of sintering of the main phase powder particles and the sintering assisting effect of the sintering aid are effectively improved.

Description

A kind of preparation method of high-purity alumina ceramic
Technical field
The present invention relates to technical field of ceramic material, particularly relate to a kind of preparation method of high-purity alumina ceramic.
Background technology
Alumina-ceramic is a kind of with aluminum oxide (AL 2o 3) be the material of main body, there is good conductivity, physical strength and high thermal resistance, be the base mateiral manufacturing high strength, wear-resistant, high temperature resistant contour performance ceramic component, be widely used in the fields such as machinery, communication, semi-conductor, medicine, food, oil, chemical industry, space flight and aviation.
The fusing point of aluminum oxide is higher, and its sintering temperature is also corresponding higher, and especially the sintering of Large stone alumina particle is all the more so, thus can cause higher energy consumption, produce very high preparation cost.For reducing the sintering temperature of aluminum oxide, preparing in sintering process at it and usually needing to add sintering aid, obviously to reduce the sintering temperature of high-melting-point alumina-ceramic, realize the object reducing preparation cost.The mechanism of action of ceramic post sintering auxiliary agent generally includes following three kinds:
(1) sintering aid itself can form liquid phase at a lower temperature, is promoted the mass transfer speed of high-melting-point pottery, such as kaolin, B by liquid phase 2o 3, albite, potassium felspar sand etc. is as the sintering of sintering aid for alumina-ceramic.
(2) sintering aid forms eutectic by solid state reaction and sinter, thus reduction sintering temperature, diffusion and sintering velocity are increased, and such as magnesium oxide can fuse with the silicon-dioxide of silicon nitride surface and form Magnesium Silicate q-agent liquid phase under the high temperature of 1500 DEG C, forms Mg with silicon nitride simultaneously 2siO 4and MgSi 3n 2, Mg 2siO 4and MgSi 3n 2more than 1600 DEG C, form eutectic with silicon nitride, can sintering temperature be reduced, and promote the sintering of silicon nitride.
(3) using nano-powder as sintering aid, the character utilizing nano-powder fusing point to reduce, makes nano-powder have higher sintering activity at a lower temperature, promotes the sintering of principal phase with this.
Below no matter which kind of mechanism of action, sintering aid generally can stay the combining site of principal phase particle, i.e. grain boundaries, and these materials can cause obvious impact to the character of aluminum oxide.Such as, kaolinic interpolation can make the sintering temperature of alumina-ceramic film support (particle diameter of aluminum oxide used is 20 ~ 40 μm) reduce by 50 ~ 100 DEG C, but kaolin is acid-alkali-corrosive-resisting not, use 1wt%NaOH solution corrosion after 24 hours, although mass loss only has 0.9%, the intensity of supporter reduces 35%.In addition, the sintering aid containing potassium, sodium adds in aluminum oxide, obviously can reduce the dielectric coefficient of aluminum oxide, make it more easily breakdown.And for the principal phase powder of Large stone, nano-powder sintering aid is easy to reunite in the space of Large stone principal phase powder granule, cannot play the effect helping sintering.And in some particular application, need high-purity alumina ceramic goods (foreign matter content is lower than 1% or even 0.5%), the use of above-mentioned sintering aid can bring adverse influence to the purity of goods and performance undoubtedly.
For preparing high-purity alumina ceramic, prior art also has and uses nano-aluminum hydroxide colloidal sol as sintering aid, is not introducing other materials with while ensureing purity, the effectively sintering temperature of reduction alumina-ceramic.But it is alumina powder jointed that this method is only suitable for for small particle size, because the alumina powder jointed of small particle size is just easy to and nano-aluminum hydroxide colloidal sol Homogeneous phase mixing, promoted the alumina powder jointed sintering of small particle size by the sintering of nano-aluminum hydroxide colloidal sol.For the α-Al of Large stone 2o 3powder, nano-aluminum hydroxide colloidal sol can at Large stone α-Al 2o 3assemble in the gap of particle packing, the colloidal sol that these are assembled in sintering process preferentially sinters large-size particles into, and cannot play and help nodulizing.In addition, this method is not suitable for the preparation of the alumina-ceramic needing dry process or need clean compact dimensions yet.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of high-purity alumina ceramic is provided, by the nanometer Al formed at Membranes On Alumina Particles Surface 2o 3coating, as sintering aid, to improve the Even Sintering of alumina particle, and ensures purity and the performance of high-purity alumina ceramic, meets process requirements prepared by alumina-ceramic.
Object of the present invention is achieved by the following technical programs:
The preparation method of a kind of high-purity alumina ceramic provided by the invention, comprises the following steps:
(1) aluminum isopropylate is dissolved in solvent forms aluminum isopropylate solution, the volume that wherein volume>=principal phase of solvent is alumina powder jointed, the nanometer Al that the consumption of aluminum isopropylate generates according to it 2o 30.5 ~ the 25wt% accounting for principal phase aluminum oxide determines;
(2) described aluminum isopropylate solution and alumina powder jointed being uniformly mixed of principal phase are obtained mixing suspension;
(3) described mixing suspension is placed in hydrothermal reaction kettle, at 120 ~ 180 DEG C of temperature, processes 6 ~ 12 hours; Then remove suspension mixed upper solution, obtain the aluminum oxide powder slurry of bottom;
(4) by after the drying of described aluminum oxide powder slurry, calcine at 750 ~ 900 DEG C of temperature in retort furnace, obtain pre-treatment alumina powder jointed;
(5) carry out shaping, calcining to described pre-treatment is alumina powder jointed, obtain high-purity alumina ceramic product.
Further, in step of the present invention (1), solvent is dimethylbenzene, also can be the solvent of other solubilized aluminum isopropylates.The median size that in described step (1), principal phase is alumina powder jointed is 0.05 ~ 500 μm, preferably 0.5 ~ 50 μm.
The present invention is applicable to the forming methods such as dry-pressing formed, extrusion moulding, gel pouring, injection molding, and in described step (5), calcining temperature is 1100 ~ 1800 DEG C.
The present invention has following beneficial effect:
1, the present invention is by forming the nano oxidized aluminum coating of one deck at Membranes On Alumina Particles Surface, makes a small amount of sintering aid can be dispersed in principal phase, utilizes the nano particle formed as sintering aid, achieves the even interpolation of low dose of sintering aid.Be distributed in the surface of main body alumina particle prepared nano aluminium oxide coating uniform, and can not be filled in oarse-grained gap, solve the problem that when particle diameter differs greatly, nano assistant powder granule is assembled in Large stone principal phase powder granule space, effectively prevent the agglomeration of ceramic post sintering auxiliary agent, achieve dispersed, evenly and sinter, avoid the problem of local burning simultaneously.
2, the present invention is using the nano aluminium oxide formed at Membranes On Alumina Particles Surface as sintering aid, is just effectively improve help nodulizing by the interpolation of low dose; And do not introduce other material, sintering aluminum oxide that is rear and principal phase becomes overall, thus ensure that the purity of high-purity alumina ceramic, does not affect the character of the alumina-ceramic after sintering simultaneously.
3, suitability is wide.No matter the present invention is the alumina powder jointed of the alumina powder jointed of Large stone or relatively small particle size, and nano aluminium oxide can both be evenly distributed in particle surface, soilless sticking phenomenon; And the present invention is applicable to various forming method, be particularly useful for the preparation of the alumina-ceramic needing dry process or need clean compact dimensions.
Accompanying drawing explanation
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail:
Fig. 1 is the stereoscan photograph of its section of the embodiment of the present invention one high-purity alumina ceramic goods;
Fig. 2 is the transmission electron microscope photo of its section of the embodiment of the present invention one high-purity alumina ceramic goods;
Fig. 3 is the stereoscan photograph of its section of the embodiment of the present invention two high-purity alumina ceramic goods.
Embodiment
Embodiment one:
The preparation method of a kind of high-purity alumina ceramic of the present embodiment, its step is as follows:
(1) get 20g aluminum isopropylate to be dissolved in 100ml dimethylbenzene and to form aluminum isopropylate solution;
(2) get 100g alumina powder jointed (W40, median size is 40 μm) and be obtained by mixing mixing suspension with above-mentioned aluminum isopropylate solution stirring;
(3) above-mentioned mixing suspension is placed in hydrothermal reaction kettle, at 150 DEG C of temperature, processes 10 hours; Then remove suspension mixed upper solution, obtain the aluminum oxide powder slurry of bottom;
(4) above-mentioned aluminum oxide powder is starched after drying at 100 DEG C of temperature in baking oven, in retort furnace, rise to 800 DEG C with the temperature rise rate of 3 DEG C/min calcine, be incubated 2 hours, obtain pre-treatment alumina powder jointed;
(5) in above-mentioned pre-treatment is alumina powder jointed, 2wt%PVA is added, dry-pressing formed under 6Mpa pressure, be pressed into 10 × 10 × 400mm rectangle examination bar; Rise to 600 DEG C with the temperature rise rate of 1 DEG C/min, then rise to 1650 DEG C with the temperature rise rate of 2 DEG C/min, be incubated 2 hours, obtain high-purity porous alumina ceramic product, can be used as ceramic film support.
As can be seen from Figure 1, nano aluminium oxide covers the surface of Large stone alumina particle.As can be seen from Figure 2, the thickness of nano oxidized aluminum coating is about 10nm.
Embodiment two:
The preparation method of a kind of high-purity alumina ceramic of the present embodiment, its step is as follows:
(1) get 20g aluminum isopropylate to be dissolved in 100ml dimethylbenzene and to form aluminum isopropylate solution;
(2) alumina powder jointed (W40 of 90g is got, median size is 40 μm), the alumina powder jointed (W1 of 10g, median size is 1 μm) ball milling mixes and obtains mixed aluminium oxides powder, is then obtained by mixing mixing suspension with above-mentioned aluminum isopropylate solution stirring;
(3) above-mentioned mixing suspension is placed in hydrothermal reaction kettle, at 180 DEG C of temperature, processes 8 hours; Then remove suspension mixed upper solution, obtain the aluminum oxide powder slurry of bottom;
(4) above-mentioned aluminum oxide powder is starched after drying at 100 DEG C of temperature in baking oven, in retort furnace, rise to 750 DEG C with the temperature rise rate of 3 DEG C/min calcine, be incubated 2 hours, obtain pre-treatment alumina powder jointed;
(5) in above-mentioned pre-treatment is alumina powder jointed, 2wt%PVA is added, dry-pressing formed under 6Mpa pressure, be pressed into 10 × 10 × 400mm rectangle examination bar; Rise to 600 DEG C with the temperature rise rate of 1 DEG C/min, then rise to 1500 DEG C with the temperature rise rate of 2 DEG C/min, be incubated 2 hours, obtain high-purity porous alumina ceramic product, can be used as ceramic film support.
As can be seen from Figure 3, nano aluminium oxide is evenly distributed in the surface of alumina particle.
Embodiment three:
Preparation method and embodiment one difference of a kind of high-purity alumina ceramic of the present embodiment are:
Alumina powder jointed in step (2) is 120g; Step adds methylcellulose gum, tung oil, glycerol, water in (5) in pre-treatment is alumina powder jointed, through batch mixing, mud refining, old etc. obtains suitable pug, obtains circular tube shaped (or cylindric, hyperchannel tubulose) through extrusion moulding; Then at 1650 DEG C of temperature lower calcinations, be incubated 2 hours, obtain high purity aluminium oxide rod (pipe).
Embodiment four:
Preparation method and embodiment one difference of a kind of high-purity alumina ceramic of the present embodiment are:
Step adds polyacrylic acid and water in (5) in pre-treatment is alumina powder jointed, ammoniacal liquor adjustment suspension pH value is used to be 9.5, at powder: zirconium white mill is situated between: water=1: mix 12 hours with rotating speed 350r/min ball milling under 1.5: 1 conditions, obtain stable suspension, after flow casting molding, obtain curtain coating raw cook; Then at 1550 DEG C of temperature lower calcinations, be incubated 2 hours, obtain high purity aluminium oxide sheet.

Claims (5)

1. a preparation method for high-purity alumina ceramic, is characterized in that comprising the following steps:
(1) aluminum isopropylate is dissolved in solvent forms aluminum isopropylate solution, the volume that wherein volume>=principal phase of solvent is alumina powder jointed, the nanometer Al that the consumption of aluminum isopropylate generates according to it 2o 30.5 ~ the 25wt% accounting for principal phase aluminum oxide determines;
(2) described aluminum isopropylate solution and alumina powder jointed being uniformly mixed of principal phase are obtained mixing suspension;
(3) described mixing suspension is placed in hydrothermal reaction kettle, at 120 ~ 180 DEG C of temperature, processes 6 ~ 12 hours; Then remove suspension mixed upper solution, obtain the aluminum oxide powder slurry of bottom;
(4) by after the drying of described aluminum oxide powder slurry, calcine at 750 ~ 900 DEG C of temperature in retort furnace, obtain pre-treatment alumina powder jointed;
(5) carry out shaping, calcining to described pre-treatment is alumina powder jointed, obtain high-purity alumina ceramic product.
2. the preparation method of high-purity alumina ceramic according to claim 1, is characterized in that: in described step (1), solvent is dimethylbenzene.
3. the preparation method of high-purity alumina ceramic according to claim 1, is characterized in that: the median size that in described step (1), principal phase is alumina powder jointed is 0.05 ~ 500 μm.
4. the preparation method of high-purity alumina ceramic according to claim 1, is characterized in that: the median size that in described step (1), principal phase is alumina powder jointed is 0.5 ~ 50 μm.
5. the preparation method of high-purity alumina ceramic according to claim 1, is characterized in that: in described step (5), calcining temperature is 1100 ~ 1800 DEG C.
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CN104193310A (en) * 2014-08-29 2014-12-10 潮州三环(集团)股份有限公司 Ceramic material and preparation method thereof
CN104987113A (en) * 2015-07-24 2015-10-21 合肥凯士新材料贸易有限公司 Zirconium silicate whisker modified tabular alumina porous ceramic used in LED lamp heat dissipation, and preparation method thereof
CN105036717A (en) * 2015-07-24 2015-11-11 合肥凯士新材料贸易有限公司 Flake alumina porous ceramic used for packaging high-power LED and preparation method thereof
CN105461293A (en) * 2016-01-08 2016-04-06 梁小利 Low thermal-conductivity aluminum oxide ceramic and preparation method thereof
CN106747557A (en) * 2016-11-25 2017-05-31 山东硅元新型材料有限责任公司 The preparation method of plate diamond spar ceramic film support
CN107245323A (en) * 2017-01-10 2017-10-13 白鸽磨料磨具有限公司 Production method of alumina abrasive and products thereof
CN107963883A (en) * 2017-12-14 2018-04-27 上海卡贝尼精密陶瓷有限公司 A kind of preparation method of high-purity alumina ceramic powder
CN108298947B (en) * 2018-01-10 2020-10-30 淮阴师范学院 Attapulgite ceramic membrane support, preparation method and application of boron-containing sintering aid
CN110240492B (en) * 2018-03-07 2020-07-28 海加尔(厦门)科技有限公司 Preparation method of acid-alkali-resistant ceramic separation membrane support
CN113121209B (en) * 2021-03-26 2022-07-29 福建华清电子材料科技有限公司 Preparation method of 996 aluminum oxide ceramic substrate

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