CN101456561B - Method for preparing nano mullite powder - Google Patents
Method for preparing nano mullite powder Download PDFInfo
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- CN101456561B CN101456561B CN2008101641197A CN200810164119A CN101456561B CN 101456561 B CN101456561 B CN 101456561B CN 2008101641197 A CN2008101641197 A CN 2008101641197A CN 200810164119 A CN200810164119 A CN 200810164119A CN 101456561 B CN101456561 B CN 101456561B
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- citric acid
- mullite powder
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Abstract
The invention discloses a method for preparing nano mullite powder, which comprises: firstly, mixing an aluminum inorganic salt aqueous solution and silicasol, wherein the mol ratio of silicon element to aluminum element is 1:3; secondly, dissolving citric acid into ethylene glycol, wherein the mol ratio of the citric acid to the ethylene glycol is between 1:4 and 1:8; and thirdly, mixing the two solutions, wherein the mol ratio of the citric acid to an aluminum inorganic salt is between 1:1 and 1:4, raising the temperature to be between 125 and 135 DEG C and maintaining at the temperature for 2 to 4 hours, continuously raising the temperature to be between 180 and 220 DEG C and maintaining at the temperature for 2 to 4 hours, and roasting the mixture at a temperature of between 1,100 and 1,300 DEG C to obtain the nano mullite powder. Raw materials adopted by the method have wide sources and low cost, and are easily obtained; the preparation technology is simple and controllable, and has low equipment requirements; and the prepared nano mullite powder has fine particle diameter, uniform distribution, and good industrial application value.
Description
Technical field
The present invention relates to a kind of preparation method of nano mullite powder, belong to materials science field.
Background technology
With aluminum oxide and silicon oxide is the synthetic mullite that obtains of raw material, is Al
2O
3-SiO
2Unique stable compound in the system, creep resistance and heat-shock resistance, excellent electric insulation, chemical stability and hot strength etc. with low heat-conduction coefficient and thermal expansivity, excellence, be the preferred material of high-temperature structural material, infrared permeation window, microelectronic substrate material and support of the catalyst, also improve its mechanical behavior under high temperature in the alumina-ceramic through being usually used in adding to.Size and distribution that an important factor that influences the above-mentioned materials performance is a mullite crystal grain, when the granular size of mullite is reduced to nano level, not only have little volume effect, play good particulate reinforcement effect, also have huge surface energy, its reactive behavior is greatly improved.For example, Chinese invention patent 200310108594.X has announced a kind of method of manufacturing technology that strengthens household china, it is main raw material that this patent adopts natural china clay, make the top grade that contains nano mullite crystal grain and refinement corundum crystal grain and strengthen household china, utilize the particle of nano mullite crystal grain to strengthen intensity and the thermostability that improves household china.The applied research of nano mullite powder on shortening (Industrial Catalysis, 2003,2,33-35) reported that nano mullite as the hydrogenation reaction carrier time, has more excellent performances such as ratio silicon oxide, magnesium oxide.Therefore, nano mullite powder is subject to people's attention day by day, but seldom there is natural mullite raw material in occurring in nature, says nothing of to have natural nano mullite powder.
At present, the synthetic method of mullite mainly adopts pyroreaction method (1700-1750 ℃ of calcining) and electric smelting method, but the production cost of these two kinds of methods is too high, severe reaction conditions, preparation process complexity, and the mullite powder particle diameter that obtains is in the micron order scope.In order to obtain nano level mullite powder, adopt the wet-chemical synthesis method to obtain broad research.
(silicate journal, 2003,31 such as Zhao Huizhong, 12, be main raw material 1216-1220) with aluminum isopropylate and tetraethoxy, adopt sol-gel and supercritical fluid drying technology to prepare the bielement nano aerogel, by middle temperature calcining, obtained the nano level mullite powder again; Chen Hao etc. (the Jiangxi science, 2006,24,6, be that main raw material prepares the nano mullite precursor sol 428-431) with tetraethoxy and crystal aluminum chloride, adopt the supercritical fluid drying treatment technology to prepare Al then
2O
3-SiO
2System nano ultrafine powders body; He Wen (the material Leader, 2000,14, be raw material 337-338) with positive silicic acid second vinegar and aluminum nitrate, adopt sol-gel and supercritical fluid drying to synthesize the nanoparticle of mullite; The processing condition of above-mentioned preparation process are had relatively high expectations, and particularly the material cost costliness of aluminum isopropylate and tetraethoxy is not suitable for suitability for industrialized production.Yu Jian etc. (silicate journal, 1998,26,5,578-585) with tetraethoxy (TEOS, analytical pure) and crystal aluminum chloride (AlCl
36H
2O, analytical pure) be raw material, adopt quick hydrolysis method to prepare the aluminium silicon gel of different chemical proportioning, calcining back compression moulding and sintering, the thing to nano mullite does not launch to inquire into particle diameter, and the material cost height of tetraethoxy, and it is unsatisfactory to be used for industrial production.
Wang Yinye etc. adopt cheap natural kaolin synthesis of nano mullite composite oxides (University Of Tianjin's journal, 2001,34,2,225-228), pass through hydrothermal crystallization method, to prepare with the mullite be the composite nanocrystalline of principal crystalline phase to constant temperature 373K under normal pressure, but contain Al
2O
3, SiO
2Deng dephasign.The horse pine is adopted the synthetic Al of sol-gel method
2O
3-SiO
2Nano-powder (National University of Defense technology's journal, 2002,24,4,25-28), be raw material with aluminum chloride, silicon sol and hexamethylenetetramine, synthesized the higher mullite powder of degree of crystallinity at 1300 ℃, but powder granule has not been characterized.Application number is 200710134951.8 patent with sodium hydroxide or yellow soda ash, urea, water, Glacial acetic acid is raw material, through filter again, wash after the reaction, drying, calcination promptly gets nano mullite, and this method need be passed through operations such as filtration, washing, and condition is loaded down with trivial details and introduce impurity easily.
Summary of the invention
The purpose of this invention is to provide that a kind of material cost is cheap, facility investment is few, the preparation method of the nano mullite powder of preparation technology's simple controllable.
The preparation method of a kind of nano mullite powder that the present invention proposes may further comprise the steps:
(1) inorganic salt with aluminium are dissolved in the deionized water, form the inorganic salt solution of 0.5～1.5mol/l aluminium; Be 1: 3 mol ratio adding silicon sol again by element silicon and aluminium element, stirred 1～5 hour;
(2) citric acid is dissolved in the ethylene glycol, the mol ratio of citric acid and ethylene glycol is 1: 4～1: 8;
(3) mol ratio by citric acid and al inorganic salt is 1: 1～1: 4, and above-mentioned (1) is mixed with (2) solution, stirs; Be warmed up to 125 ℃～135 ℃ insulations 2～4 hours then, continue to be warmed up to 180 ℃～220 ℃ insulations 2～4 hours, obtain crisp atrament;
(4) above-mentioned crisp atrament is ground, put into the high alumina crucible,, obtain the nano-ceramic powder of white, be nano mullite powder of the present invention 1100 ℃～1300 ℃ calcinings.
In the technique scheme, the inorganic salt of the described aluminium of step (1) can be Al (NO
3)
39H
2O, Al (OH) (CH
3COO)
22H
2O, C
6H
9AlO
6, C
9H
21AlO
3, AlCl
36H
2O, Al (OH)
3Perhaps one or more in the aluminium colloidal sol.
The present invention compared with prior art has following advantage:
1, inorganic salt and the silicon sol with aluminium is raw material, and low price and raw material are easy to get, and have low material cost;
2, only need heated and stirred in the preparation process, carry out high-temperature calcination then, required equipment is simple, preparation technology's simple controllable;
3, utilize citric acid to bonding and the sterically hindered effect of the complexing action of metal ion, ethylene glycol, metal ion is evenly distributed in the polymkeric substance, thereby finally can obtains the uniform nano mullite powder of particle distribution metal ion.
Embodiment
Below in conjunction with example the present invention is further described.
Embodiment 1:
Take by weighing the Al (NO of 1mol
3)
39H
2O is dissolved in a certain amount of deionized water, forms the aluminum nitrate aqueous solution of 1mol/l; In this aluminum nitrate aqueous solution, be that the amount of 1/3mol adds silicon sol, stir it to be mixed in 3 hours by silicon.The citric acid (CA) of 1mol is joined in the ethylene glycol (EG) of 4mol, be heated to 90 ℃ citric acid is dissolved in ethylene glycol.
Above-mentioned two solution are mixed, stir, and slowly heating makes the moisture evaporation in the mixing solutions, obtains transparent colloidal sol shape liquid.The colloidal sol shape liquid that this is transparent is warmed up to 130 ℃ of insulations 3 hours, can produce bubble when beginning to be incubated and with volumetric expansion, insulation its volume of later stage no longer changes, and continues to be warmed up to 210 ℃ of insulations 2 hours, furnace cooling obtains crisp atrament then.
Above-mentioned crisp atrament is ground, put into the high alumina crucible,, obtain white powder, be nano mullite powder of the present invention 1200 ℃ of calcinings 2 hours.This nano-powder is through the transmission electron microscope tem analysis, and particle diameter is between 60～100nm, and dispersion of particles is better; XRD analysis shows that this nano-powder is single mullite crystalline phase.
Embodiment 2:
Take by weighing Al (the OH) (CH of 1mol
3COO)
22H
2O is dissolved in a certain amount of deionized water, forms the Burow Solution aqueous solution of 0.8mol/l; In this Burow Solution aqueous solution, be that the amount of 1/3mol adds silicon sol, stir it to be mixed in 4 hours by silicon.The citric acid (CA) of 2mol is joined in the ethylene glycol (EG) of 9mol, be heated to 90 ℃ citric acid is dissolved in ethylene glycol.
Above-mentioned two solution are mixed, stir, and slowly heating makes the moisture evaporation in the mixing solutions, obtains transparent colloidal sol shape liquid.The colloidal sol shape liquid that this is transparent is warmed up to 130 ℃ of insulations 2 hours, can produce bubble when beginning to be incubated and with volumetric expansion, insulation its volume of later stage no longer changes, and continues to be warmed up to 220 ℃ of insulations 2 hours, furnace cooling obtains crisp atrament then.
Above-mentioned crisp atrament is ground, put into the high alumina crucible,, obtain white powder, be nano mullite powder of the present invention 1250 ℃ of calcinings 2 hours.This nano-powder is through the transmission electron microscope tem analysis, and particle diameter is between 80～120nm, and dispersion of particles is better; XRD analysis shows that this nano-powder is single mullite crystalline phase.
Embodiment 3:
The acidic aluminum sol that takes by weighing aluminium element content and be 1mol is dissolved in a certain amount of deionized water, forms the aluminium colloidal sol aqueous solution of 1.5mol/l; In this aqueous solution, be that the amount of 1/3mol adds acidic silicasol, stir it to be mixed in 4 hours by silicon.The citric acid (CA) of 1.5mol is joined in the ethylene glycol (EG) of 9mol, be heated to 90 ℃ citric acid is dissolved in ethylene glycol.
Above-mentioned two solution are mixed, stir, and slowly heating makes the moisture evaporation in the mixing solutions, obtains transparent colloidal sol shape liquid.The colloidal sol shape liquid that this is transparent is warmed up to 125 ℃ of insulations 4 hours, can produce bubble when beginning to be incubated and with volumetric expansion, insulation its volume of later stage no longer changes, and continues to be warmed up to 200 ℃ of insulations 3 hours, furnace cooling obtains crisp atrament then.
Above-mentioned crisp atrament is ground, put into the high alumina crucible,, obtain white powder, be nano mullite powder of the present invention 1200 ℃ of calcinings 2 hours.This nano-powder is through the transmission electron microscope tem analysis, and particle diameter is between 80～100nm, and dispersion of particles is better; XRD analysis shows that this nano-powder is single mullite crystalline phase.
Claims (1)
1. the preparation method of a nano mullite powder may further comprise the steps:
(1) inorganic salt with aluminium are dissolved in the deionized water, form the inorganic salt solution of 0.5～1.5mol/l aluminium; Be 1: 3 mol ratio adding silicon sol again by element silicon and aluminium element, stirred 1～5 hour;
(2) citric acid is dissolved in the ethylene glycol, the mol ratio of citric acid and ethylene glycol is 1: 4～1: 8;
(3) mol ratio by citric acid and al inorganic salt is 1: 1～1: 4, and above-mentioned (1) is mixed with (2) solution, stirs; Be warmed up to 125 ℃～135 ℃ insulations 2～4 hours, continue to be warmed up to 180 ℃～220 ℃ insulations 2～4 hours, obtain crisp atrament;
(4) above-mentioned crisp atrament is ground, put into the high alumina crucible,, obtain nano mullite powder 1100 ℃～1300 ℃ calcinings;
The inorganic salt of described aluminium are Al (NO
3)
39H
2O, Al (OH) (CH
3COO)
22H
2In O and the aluminium colloidal sol one or more.
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|---|---|---|---|
| CN2008101641197A CN101456561B (en) | 2008-12-25 | 2008-12-25 | Method for preparing nano mullite powder |
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|---|---|---|---|
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| CN101456561B true CN101456561B (en) | 2010-12-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102503387B (en) * | 2011-09-27 | 2013-05-22 | 中国地质大学（武汉） | Method for preparing high-purity super-fine mullite powder |
| CN102963896B (en) * | 2012-11-28 | 2014-05-28 | 华北水利水电大学 | Preparation method of mullite precursor and nano mullite |
| CN107935553A (en) * | 2017-12-17 | 2018-04-20 | 李巧珍 | A kind of preparation method of fire resistant environment-friendly pipe insulation material |
| CN110921674A (en) * | 2019-12-23 | 2020-03-27 | 苏州纳迪微电子有限公司 | Hollow spherical mullite and preparation method and application thereof |
| CN114272916B (en) * | 2022-01-06 | 2022-07-12 | 中国科学院宁波材料技术与工程研究所 | High-catalytic-activity mullite material, and preparation method and application thereof |
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