CN1587450A - Method for preparing mullite single crystal nano belt - Google Patents
Method for preparing mullite single crystal nano belt Download PDFInfo
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- CN1587450A CN1587450A CN 200410062552 CN200410062552A CN1587450A CN 1587450 A CN1587450 A CN 1587450A CN 200410062552 CN200410062552 CN 200410062552 CN 200410062552 A CN200410062552 A CN 200410062552A CN 1587450 A CN1587450 A CN 1587450A
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- mullite
- belt
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- single crystal
- nanometer
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Abstract
The present invention relates to composite material and electronic material, and is the simple process for preparing nanometer monocrystal mullite belt. The material including silicate ester, aluminum salt and citric acid and mixed tungstate or molybdenate catalyst are hydrolyzed to prepare sol containing mullite WO3 or MoO3 component; and the sol is stoved and heated to synthesize nanometer mullite belt. Increasing the content of catalyst properly can increase the thickness of the nanometer mullite belt. The prepared nanometer mullite belt is in monocrytal structure, straight and smooth, and may be used in preparing ceramic base, metal base and polymer base composite reinforced material used widely in optics and electronics. The present invention has the advantages of simple preparation process, easy control, high yield, etc.
Description
Technical field
The present invention is a kind of method for preparing mullite single crystal nano belt, relates to matrix material, electronic material.
Technical background
Mullite is Al
2O
3-SiO
2Unique stable compound in the binary system, has very high fusing point (1890 ℃), the good high-temperature creep-resistant property, higher high-temperature machinery intensity (intensity does not reduce in the time of 1300 ℃), advantages such as very low thermal expansivity and chemical property are stable are a kind of high temperature resistant structure ceramicses of excellent property.In addition because the mullite material synthesis technique is simple, have lower specific inductivity, dielectric loss coefficient and low thermal expansivity, also have wide practical use at aspects such as electronic package material, hard disk substrate material and radome materials, even be considered to the new type integrated circuit baseplate material that get a good chance of future, also can become traditional Al
2O
3The substitute of ceramic substrate material.
Because the unidimensional mullite material---whisker can improve the machinery and the thermal characteristics of metal, polymer and ceramic matric composite, and the synthetic of mullite crystal whisker receives much concern, people have carried out big quantity research to the synthetic method of unidimensional mullite crystal whisker.People such as Okada utilize and form xerogel and the AlF identical with mullite
4Mix, synthesized mullite crystal whisker by gas-phase reaction at 1100 ℃-1400 ℃.Human boehmite such as Ismail makes mullite forerunner gel powder with the HF reaction again with after silicon sol mixes, 1400 ℃ down calcining 1h prepared mullite crystal whisker.People such as Moyer utilize Al
2O
3, SiO
2With SiF
41100 ℃ of prepared in reaction mullite crystal whisker.People such as Messing are by mixing B
2O
3Or TiO
2Synthesized anisotropic mullite crystal grain with sol-gel method.People such as Souza utilize to mix under 1550 ℃ of the rare earth element sol-gel methodes and have synthesized mullite crystal whisker.People such as Kong utilize oxide compound to be raw material, make active raising of raw material synthesize mullite crystal whisker by mechanical grinding activation.Above method synthetic diameter of whiskers is about 0.5～3 μ m, do not reach nano-scale, the shape of whisker is also irregular, and because synthetic method adopts vapor deposition reaction or forms through high temperature sintering after high pressure is pressed into sheet again, its productive rate is lower, mostly be non-free dispersive whisker greatly, be difficult to disperse to utilize.
Recently the research of monodimension nanometer material causes people's extensive concern, studies show that: unidimensional nanometer rod, nanotube have higher Young's modulus and intensity than its large-sized whisker or coacervate, therefore, the unidimensional nano material is considered to more effective strongthener.And mullite material has advantages such as very high fusing point, good high-temperature creep-resistant property, higher high-temperature machinery intensity, very low thermal expansivity and chemical property are stable, therefore, the mullite nano band can be widely used in preparation ceramic base, metal matrix and polymer-based composite reinforcing material
Making to nano electron device is the focus of studying recently always, and nano-device has shown excellent characteristic.The making of nano-device need have the deposition substrate material of good physical chemical property, and people have utilized Al
2O
3, nano belt such as AlN as on the substrate deposition multiple semiconductor material, and obtained good effect.Mullite material have very low-k and dielectric loss coefficient and with aluminum oxide (7.2 * 10
-6) compare mullite (4.4 * 10
-6) and silicon (4.0 * 10
-6) characteristic such as thermal expansivity is more approaching, be more suitable for packaged material and baseplate material as microelectronics, nano-electron.And complete, the flawless single crystal structure mullite nano band in preparation surface pair is with to make Nanoelectronic Technology packaged material and baseplate material also very important.
The objective of the invention is to prepare a kind of nano level mullite one-dimensional material, can the potential application prospect be arranged as the wild phase of matrix material and at microelectronics, optical field, substrate material as other nano level functional materials of deposition, and can regulate the nano belt that processing parameter prepares different thickness according to the purposes difference.
Summary of the invention:
The present invention is achieved in that tungstate or the molybdate with the solubility of aluminium salt, estersil or silicon sol, a small amount of citric acid and different content is dissolved in deionized water, heating makes it to form colloidal sol, colloidal sol is dried into xerogel, again xerogel is burnt till through high temperature, can obtain the mullite material of nano belt structure.In mullite heating forming process, tungstate or molybdate are decomposed to form WO
3Or MoO
3, again with Al
2O
3Reaction forms Al
2O
33WO
3Or Al
2O
33MoO
3Intermediate phase, the two can play certain template action in the forming process of mullite, make mullite growth in a certain direction in crystallisation process, and then develop into the nano belt structure.WO
3Or MoO
3Content play crucial effects for the pattern of mullite, its content is crossed and is not had template action when low, increases gradually with the thickness of the raising mullite nano band of its add-on, can form section is foursquare nanometer rod.But when too high levels, but be difficult to form the nano belt structure.Temperature is also very important for forming nanostructure, and temperature is crossed when hanging down can not form the mullite phase, and mullite phase particle agglomeration can not form the nano belt structure when temperature was too high.
Step of the present invention is: with aluminium salt, estersil or silicon sol are raw material, as catalyzer, 0～4 between form colloidal sol by regulating pH value with tungstate or molybdate, and after drying formed xerogel, reheat reacted and both obtained the mullite nano band.Catalyst levels is with Al
2O
3With WO
3Or MoO
3Molar ratio computing, Al
2O
3/ WO
3Between 1: 0.05～1: 0.4).Colloidal sol at reacting by heating 2～10h more than 800 ℃, can obtain the mullite nano band behind dry formation xerogel more than 50 ℃, the mullite nano bandwidth is 50～500nm, thick about 40～200nm, and length is 4～8 μ m.
Specific implementation of the present invention is: adopting soluble aluminium salt, estersil or silicon sol is basic raw material, with the potential of hydrogen of citric acid regulating solution, is catalyzer with tungstate or molybdate.Aluminium salt, estersil or silicon sol, citric acid, tungstate or molybdate are dissolved in deionized water, and (catalyst tungstate or molybdate content are with Al
2O
3/ WO
3Molar ratio computing is 1: 0.05～0.4), solution PH remains on 0～4, and solution is formed transparent colloidal sol at 60 ℃ of heating in water bath 4～5h, pours colloidal sol into alumina crucible and forms xerogel at oven dry 10h more than 50 ℃.Xerogel is put into tube furnace calcining 2～10h more than 800 ℃, take out after being cooled to room temperature with body of heater, can obtain the mullite nano band.
The present invention adopts tungstate or molybdate as catalyzer sol-gel method mullite synthesizing nano belt first, and can regulate the thickness of nano belt by changing catalyst content, and the influence of synthesis temperature to the nano belt pattern proposed, this synthetic method craft is simple, it is in enormous quantities synthetic to be easy to.Key problem in technology is:
1. rational catalyst consumption, the i.e. Al of mullite
2O
3With WO
3Or MoO
3Mol ratio, should be controlled between 1: 0.05～1: 0.4, could obtain the mullite nano band.In above-mentioned range of catalysts, improve catalyst content and can improve nano belt thickness.
2. rational synthesis temperature has only synthesis temperature in ability mullite synthesizing nano belt more than 800 ℃.
With X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), electronics selected diffraction (SEAD) is studied the mullite of preparation, and show: the synthetic nano belt is the mullite phase under these conditions, the nano belt shape is straight, complete, smooth, zero defect is grown on the surface, is single crystal structure, the about 50～500nm of nanometer bandwidth, thick about 40～200nm is about 4～8 μ m.
Advantage of the present invention is: present method mullite synthesizing nano belt have technological process simple, be easy to control, synthesis device is simple, productive rate is high, be easy to advantages such as synthetic in batches, and synthetic nano belt shape is straight, complete, smooth, zero defect is grown on the surface, is single crystal structure.
Embodiment
Embodiment 1: adopting aluminum nitrate, tetraethyl silicate is basic raw material (Al
2O
3With SiO
2Mol ratio 3: 2), with the potential of hydrogen of citric acid regulating solution, use ammonium tungstate as catalyzer.Aluminum nitrate salt, tetraethyl silicate, citric acid, ammonium tungstate are dissolved in deionized water, and (content of catalyzer ammonium tungstate is with Al
2O
3/ WO
3Molar ratio computing is 1: 0.05), solution PH remains on about 3, and solution is formed transparent colloidal sol at 60 ℃ of heating in water bath 5h, pours colloidal sol into alumina crucible and forms xerogel at 150 ℃ of oven dry 8h.Xerogel is put into tube furnace at 1100 ℃ of calcining 6h, only take out after the room temperature with the body of heater cooling, can obtain width is 300nm, and thickness is that 40～200nm length is 6 μ m mullite nano bands.
Embodiment 2: adopting aluminum nitrate, tetraethyl silicate is basic raw material (Al
2O
3With SiO
2Mol ratio 3: 2), with the potential of hydrogen of citric acid regulating solution, use ammonium tungstate as catalyzer.Aluminum nitrate salt, tetraethyl silicate, citric acid, ammonium tungstate are dissolved in deionized water, and (catalyzer ammonium tungstate content is with AlXO
3/ WO
3Molar ratio computing is 1: 0.1), solution PH remains on about 3, and solution is formed transparent colloidal sol at 60 ℃ of heating in water bath 5h, pours colloidal sol into alumina crucible and forms xerogel at 150 ℃ of oven dry 8h.Xerogel is put into tube furnace at 1100 ℃ of calcining 6h, only take out after the room temperature with the body of heater cooling, can obtain width is 250nm, and thickness is 6 μ m mullite nano bands for 80nm length.
Embodiment 3: adopting aluminum nitrate, tetraethyl silicate is basic raw material (Al
2O
3With SiO
2Mol ratio 3: 2), with the potential of hydrogen of citric acid regulating solution, use ammonium tungstate as catalyzer.Aluminum nitrate salt, tetraethyl silicate, citric acid, ammonium tungstate are dissolved in deionized water, and (catalyzer ammonium tungstate content is with Al
2O
3/ WO
3Molar ratio computing is 1: 0.3), solution PH remains on about 3, and solution is formed transparent colloidal sol at 60 ℃ of heating in water bath 5h, pours colloidal sol into alumina crucible and forms xerogel at 150 ℃ of oven dry 8h.Xerogel is put into tube furnace at 1100 ℃ of calcining 6h, only take out after the room temperature with the body of heater cooling, can obtain width is 180nm, and thickness is 6 μ m mullite nano bands for 100nm length.
Embodiment 4: adopting aluminum nitrate, tetraethyl silicate is basic raw material (Al
2O
3With SiO
2Mol ratio 3: 2), with the potential of hydrogen of citric acid regulating solution, use ammonium tungstate as catalyzer.Aluminum nitrate salt, tetraethyl silicate, citric acid, ammonium tungstate are dissolved in deionized water, and (catalyzer ammonium tungstate content is with Al
2O
3/ WO
3Molar ratio computing is 1: 0.4), solution PH remains on about 3, and solution is formed transparent colloidal sol at 60 ℃ of heating in water bath 4～5h, pours colloidal sol into alumina crucible and forms xerogel at 150 ℃ of oven dry 8h.Xerogel is put into tube furnace at 1100 ℃ of calcining 6h, only take out after the room temperature with the body of heater cooling, can obtain width is 150nm, and thickness is 6 μ m mullite nano bands for 150nm length.
Embodiment 5: adopting aluminum nitrate, silicon sol is basic raw material (Al
2O
3With SiO
2Mol ratio 3: 2), with the potential of hydrogen of citric acid regulating solution, use ammonium tungstate as catalyzer.Aluminum nitrate, tetraethyl silicate, citric acid, ammonium tungstate are dissolved in deionized water, and (catalyzer ammonium tungstate content is with Al
2O
3/ WO
3Molar ratio computing is 1: 0.08), solution PH remains on about 3, and solution is formed transparent colloidal sol at 60 ℃ of heating in water bath 5h, pours colloidal sol into alumina crucible and forms xerogel at 150 ℃ of oven dry 8h.Xerogel is put into tube furnace at 1100 ℃ of calcining 6h, only take out after the room temperature, can obtain the mullite nano band with the body of heater cooling.
Embodiment 6: adopting aluminum chloride, tetraethyl silicate is basic raw material (Al
2O
3With SiO
2Mol ratio 3: 2), with the potential of hydrogen of citric acid regulating solution, use ammonium tungstate as catalyzer.Aluminum nitrate, tetraethyl silicate, citric acid, ammonium tungstate are dissolved in deionized water, and (catalyzer ammonium tungstate content is with Al
2O
3/ WO
3Molar ratio computing is 1: 0.08), solution PH remains on about 3, and solution is formed transparent colloidal sol at 60 ℃ of heating in water bath 5h, pours colloidal sol into alumina crucible and forms xerogel at 150 ℃ of oven dry 8h.Xerogel is put into tube furnace at 1200 ℃ of calcining 6h, only take out after the room temperature, can obtain the mullite nano band with the body of heater cooling.
Embodiment 7: adopting aluminum chloride, silicon sol is basic raw material (Al
2O
3With SiO
2Mol ratio 3: 2), with the potential of hydrogen of citric acid regulating solution, use ammonium tungstate as catalyzer.Aluminum nitrate salt, tetraethyl silicate, citric acid, ammonium tungstate are dissolved in deionized water, and (catalyzer ammonium tungstate content is with Al
2O
3/ WO
3Molar ratio computing is 1: 0.1), solution PH remains on 3 between left and right, and solution is formed transparent colloidal sol at 60 ℃ of heating in water bath 5h, pours colloidal sol into alumina crucible and forms xerogel at 150 ℃ of oven dry 8h.Xerogel is put into tube furnace at 1100 ℃ of calcining 6h, only take out after the room temperature, can obtain the mullite nano band with the body of heater cooling.
Embodiment 8: adopting aluminum chloride, tetraethyl silicate is basic raw material (Al
2O
3With SiO
2Mol ratio 3: 2), with the potential of hydrogen of citric acid regulating solution, use ammonium molybdate as catalyzer.Aluminum chloride, tetraethyl silicate, citric acid, ammonium molybdate are dissolved in deionized water, and (catalyzer ammonium molybdate content is with Al
2O
3/ MoO
3Molar ratio computing is 1: 0.08), solution PH remains on 3 between left and right, and solution is formed transparent colloidal sol at 60 ℃ of heating in water bath 5h, pours colloidal sol into alumina crucible and forms xerogel at 150 ℃ of oven dry 8h.Xerogel is put into tube furnace at 1100 ℃ of calcining 6h, only take out after the room temperature, can obtain the mullite nano band with the body of heater cooling.
Claims (4)
1. method for preparing mullite single crystal nano belt, it is characterized in that: with aluminium salt, estersil or silicon sol are raw material, with tungstate or molybdate as catalyzer, form colloidal sol by regulating the pH value between 0～4, after drying formed xerogel, the reheat reaction had both obtained the mullite nano band.
2. as claim 1 described a kind of method for preparing mullite single crystal nano belt, it is characterized in that: catalyst levels is with Al
2O
3With WO
3Or MoO
3Molar ratio computing, Al
2O
3/ WO
3Between 1: 0.05～1: 0.4).
3. as claim 1 described a kind of method for preparing mullite single crystal nano belt, it is characterized in that: colloidal sol at reacting by heating 2～10h more than 800 ℃, can obtain the mullite nano band behind dry formation xerogel more than 50 ℃.
4. as claim 1 described a kind of method for preparing mullite single crystal nano belt, it is characterized in that: the mullite nano bandwidth is 50～500nm, thick about 40～200nm, and length is 4～8 μ m.
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|---|---|---|---|
| CNB2004100625521A CN1301348C (en) | 2004-07-02 | 2004-07-02 | Method for preparing mullite single crystal nano belt |
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|---|---|---|---|
| CNB2004100625521A CN1301348C (en) | 2004-07-02 | 2004-07-02 | Method for preparing mullite single crystal nano belt |
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| Publication Number | Publication Date |
|---|---|
| CN1587450A true CN1587450A (en) | 2005-03-02 |
| CN1301348C CN1301348C (en) | 2007-02-21 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767793B (en) * | 2010-01-19 | 2011-09-21 | 天津大学 | Method for preparing mullite nanowire |
| CN101700979B (en) * | 2009-10-30 | 2012-01-25 | 陕西科技大学 | Method for preparing nano-mullite powder by sol-gel-ultrasonic chemistry method |
| CN103943290A (en) * | 2014-04-01 | 2014-07-23 | 中国人民解放军国防科学技术大学 | Mullite composite material insulation base sheet used for preparing thick-film resistor, thick-film resistor and preparation method thereof |
| CN104801705A (en) * | 2015-04-24 | 2015-07-29 | 第一拖拉机股份有限公司 | Ultra-fine aluminum oxide and tungsten mixed powder and preparation method thereof |
| CN106630987A (en) * | 2016-09-19 | 2017-05-10 | 齐鲁工业大学 | Oxide catalyst for preparation of mullite ceramic whiskers |
| CN108059449A (en) * | 2017-12-23 | 2018-05-22 | 景德镇陶瓷大学 | A kind of preparation method of high length-diameter ratio mullite crystal whisker ceramic material |
| CN111253150A (en) * | 2020-03-03 | 2020-06-09 | 武汉理工大学 | Preparation method of mullite-corundum composite ceramic substrate for electronic packaging |
| CN113105223A (en) * | 2021-04-08 | 2021-07-13 | 大连理工大学 | Preparation and application of whisker-shaped ceramic membrane with low cost and high permeability |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4910172A (en) * | 1989-02-08 | 1990-03-20 | The United States Of America As Represented By The Secretary Of The Navy | Preparation of mullite whiskers from AlF3, SiO2, and Al2 O3 powders |
| CN1028776C (en) * | 1992-04-30 | 1995-06-07 | 清华大学 | Process for preparation of highly pure mullite crystal whisker |
-
2004
- 2004-07-02 CN CNB2004100625521A patent/CN1301348C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700979B (en) * | 2009-10-30 | 2012-01-25 | 陕西科技大学 | Method for preparing nano-mullite powder by sol-gel-ultrasonic chemistry method |
| CN101767793B (en) * | 2010-01-19 | 2011-09-21 | 天津大学 | Method for preparing mullite nanowire |
| CN103943290A (en) * | 2014-04-01 | 2014-07-23 | 中国人民解放军国防科学技术大学 | Mullite composite material insulation base sheet used for preparing thick-film resistor, thick-film resistor and preparation method thereof |
| CN103943290B (en) * | 2014-04-01 | 2017-02-22 | 中国人民解放军国防科学技术大学 | Mullite composite material insulation base sheet used for preparing thick-film resistor, thick-film resistor and preparation method thereof |
| CN104801705A (en) * | 2015-04-24 | 2015-07-29 | 第一拖拉机股份有限公司 | Ultra-fine aluminum oxide and tungsten mixed powder and preparation method thereof |
| CN106630987A (en) * | 2016-09-19 | 2017-05-10 | 齐鲁工业大学 | Oxide catalyst for preparation of mullite ceramic whiskers |
| CN108059449A (en) * | 2017-12-23 | 2018-05-22 | 景德镇陶瓷大学 | A kind of preparation method of high length-diameter ratio mullite crystal whisker ceramic material |
| CN108059449B (en) * | 2017-12-23 | 2020-04-28 | 景德镇陶瓷大学 | Preparation method of mullite whisker ceramic material with high length-diameter ratio |
| CN111253150A (en) * | 2020-03-03 | 2020-06-09 | 武汉理工大学 | Preparation method of mullite-corundum composite ceramic substrate for electronic packaging |
| CN113105223A (en) * | 2021-04-08 | 2021-07-13 | 大连理工大学 | Preparation and application of whisker-shaped ceramic membrane with low cost and high permeability |
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| Publication number | Publication date |
|---|---|
| CN1301348C (en) | 2007-02-21 |
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