CN1031396C - Method for preparing alpha-alumina particles with nanometers size - Google Patents
Method for preparing alpha-alumina particles with nanometers size Download PDFInfo
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- CN1031396C CN1031396C CN 93108450 CN93108450A CN1031396C CN 1031396 C CN1031396 C CN 1031396C CN 93108450 CN93108450 CN 93108450 CN 93108450 A CN93108450 A CN 93108450A CN 1031396 C CN1031396 C CN 1031396C
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- high polymer
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- gel
- weight ratio
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Abstract
The present invention relates to a preparation method of nanometer-scale alpha-Al2O3 superfine particles which is necessary chemical material for electronic industry and hi-tech ceramics. The preparation method of the present invention adopts common aluminum salt as raw material. Certain additive is added to the raw material for forming colloidal sol. High polymers or high polymer monomers and cross-linking agents or initiating agents are respectively added into the colloidal sol. Under certain temperature, high polymer gel is formed in an organic high-polymer type sol-gel process. Moreover, 10 to 50-nanometer alpha-Al2O3 granules can be obtained from the gel through the heat treatment of 1200 DEG C. The method has the advantages that because the method adopts aluminum salt, the cost is low; operation and control are convenient; nanometer-scale generation effects are good; the present invention is suitable for industrialization.
Description
The invention belongs to the preparation skill wood of the oxide of metallic aluminium, relate to nanometer alpha-Al
2O
3The preparation method of particle.
Ultra-fine α-Al
2O
3Particle is integrated circuit substrate on the production electronics industry, crystalline ceramics fluorescent tube, fluorescent material, recording (phase) tape, the important industrial chemicals of laser material and high performance structure ceramic.α-Al
2O
3Granular size directly affects the said goods quality.By universal law, particle scale is more little, more is conducive to prepare the product of various high performance index, and therefore, people pay much attention to ultra-fine α-Al
2O
3The research of particle preparation.Only has at present preparation submicron-grade superfine α-Al
2O
3The patent of particle or report, and nano level superfine α-Al
2O
3Particle preparation report is very few.
In general, people are particle diameter that particle calls the submicron-grade superfine particle between 0.05～1.00 μ m, and diameter is called nano level superfine (abbreviation nano level) particle less than the 50nm particle.
Commodity production submicron order α-Al
2O
3The particle major technique has the alum pyrolysismethod, aluminum alcoholate hydrolysis roasting method, improvement Bayer process, inorganic polymer type sol-gal process etc.Wherein former three is comparatively commonly used.French Patent (FRP) 2436058 has been reported present up-to-date alum pyrolysismethod technology, its preparation process places cone-rotary steel enamel tire dehydration furnace for the aluminum sulfate crystal grain that diameter is about 1mm, product behind the thermal dehydration is put into the round kiln calcination, makes it to form α-Al under 1250 ℃ of left and right sides temperature
2O
3Particle, its yardstick is about 0.1～0.5 μ.But alum is transformed into Al
2O
3The heat of solution phenomenon can occur in the process, the dehydration volumetric expansion can not obtain the SO that produces contaminated environment in high yield and the thermal decomposition
2The problems such as gas.In order to solve the said method existing problems, people propose to replace SO
4 2Root and form another kind of aluminium salt, i.e. aluminium carbonate ammonium method.This method is that a certain amount of ammonium bicarbonate soln is joined in the alum aqueous solution, produces immediately reaction between the two, forms NH
4AlO (OH) HCO
3With a small amount of Al (OH)
3Sediment by after washing for several times, removes remaining SO with sediment
4 2Behind the root, carry out drying and become α-Al with 1200 ℃ of roastings
2O
3Particle, its yardstick are about between 0.2～1.0 μ m.But the final α-Al of the method
2O
3Performance indications and synthesis technologic parameter (temperature, concentration, pH value etc.) and between the drying precipitate mode (spray-drying adds surfactant convection drying, freeze drying) exist substantial connection, therefore the method control is difficult for, and relates to a large amount of deionized waters and numerous equipment.Aluminum alcoholate hydrolysis roasting method is to add water rear generation hydrolysis in the alcoholic solution with aluminium isopropoxide or aluminium secondary butylate, by controlling the polycondensation process of its hydrolysate, reaches control polymerizate Al
2O
33H
2O grain husk grain size is with Al
2O
33H
2The O particle forms α-Al after by 1200～1350 ℃ of roastings
2O
3Grain husk grain yardstick is between 20nm～10000nm.Although the method can be prepared nano level superfine α-Al
2O
3Particle, but the requirement of the method Control of chemical reaction is very tight, and in addition, the method needs the aluminum alcoholate of expensive and difficult preservation.
Above-mentioned introduction prepares α-Al
2O
3Particl method mainly is to prepare submicron order.But at present the nano ceramics that is gone out by preparation of nanoparticles be studies show that, general nano ceramics and micron order pottery have the difference of obvious essence aspect, show that mainly nano ceramics has high strength, high tenacity, sintering temperature and low, the exclusive superplasticity of high-compactness and nano ceramics.Its last performance can make general pottery processing by the metal material forge like that, push, the processing mode such as bending, need not the ceramic component that conventional the sort of loaded down with trivial details grinding just can be prepared precise measure.Therefore nano ceramics is very attractive studies.For with Al
2O
3For the pottery of base will have above-mentioned advantageous characteristic, nanometer alpha-Al must be arranged
2O
3Particle is front topic.
The object of the invention be intended to develop a kind of prepare easy, process is easy to control, productive rate is high, adopting conventional aluminium salt is raw material, and easily at the preparation nanometer alpha-Al of industrial popularization
2O
3The method of grain husk grain.
Technical thought of the present invention:
The aluminium salt formation aqueous solution with cheap adds a certain amount of another kind of chemical substance then.Make in the solution and to form water-fast and contain the atomic small-particle (being colloidal sol) of Al.In colloidal sol, add organic superpolymer and linking agent or add superpolymer monomer and linking agent and initiator and make organic polymer or polymer monomer produce polyreaction to form more macromolecule polymkeric substance, make sol system be transformed into gelling system simultaneously.This reaction process is called superpolymer type sol-gel process on materialogy.Solid phase particle is evenly distributed in the organism reaction system all the time in this process.Be spaced from each other by the organic polymer gel network between particulate and the particulate, will be so the solid-state organic polymer gel of class and can place easily under the different temperatures and process, after 1200 ℃ of left and right sides temperature roastings, organic substance decomposing, α-Al
2O
3Particle forms.Although forming α-Al
2O
3Al in the phase process
2O
3Particle can be grown up, but because primary particles includes Al
2O
3Amount is few, and yardstick is again little, therefore the final α-Al that forms
2O
3Particle scale is generally less than 50nm, i.e. the nano level superfine particle.
According to above-mentioned thinking, flesh and blood of the present invention:
Technical process as shown in drawings, the meaning of symbol among the figure:
A---aluminum salt solution, 1---certain adds chemical substance, B---colloidal sol, 2---high polymer or polymer monomer, C---colloidal sol, 3---crosslinking agent or crosslinking agent and initator, D---high polymer gel, 4---heat 1150 ℃～1200 ℃, E---nanometer alpha-Al
2O
3Particle.
2. the chemical feedstocks that adopts in the technical process:
Form the aluminium salt of solution: alum or aluminum nitrate or aluminium chloride or eston or aluminum sulfate etc.;
The chemical substance of adding: ammonium water or carbonic hydroammonium or hexamethylenetetramine etc.;
Superpolymer: polyvinyl alcohol or chitosan or polymethylmethacrylate;
Polymer monomer: the acid of Alpha-hydroxy acrylic or methacrylic or acrylamide etc.;
Crosslinking agent: glutaraldehyde or NVP or ethylenediamine or diethylenetriamine or methylene bis acrylamide;
Initator: peroxide toluene or azo fourth two fine or hydrogen peroxide or ammonium persulfate or potassium peroxydisulfates etc.
3. Fa Ming preparation method:
In 0.01～0.1M concentration aluminum saline solution, (its concentration is for containing NH to add a certain amount of ammoniacal liquor
325～1% (weight contents), NH
3/ Al
2O
3Weight ratio 0.01～1) or ammonium bicarbonate soln (its concentration is 1～0.01M, NH
4HCO
3/ Al
2O
3Weight ratio 25～4) or hexamethylenetetramine solution (its concentration is 1～0.5M, (CH
2)
8N
4/ Al
2O
3Weight ratio is 10～1), be 10～70 ℃ of lower reactions in temperature, after formation contains the sol system of aluminium particulate, add high polymer and crosslinking agent or add the high polymer monomer and crosslinking agent and initator (high polymer or polymer monomer amount and Al
2O
3Weight ratio be 10～40), the weight ratio of cross-linked dosage and high polymer or polymer monomer is 0.01～0.30, the mol ratio of amount of initiator and polymer monomer is 0.1～0.05, after carrying out the molten gel process reaction of high polymer type under 25～100 ℃ of temperature conditions, in several seconds to tens hours, can produce the high polymer gel, with gel behind 100 ℃ of lower dry a few minutes～tens hour, place crucible heat-treating a few minutes under 1100～1300 ℃ after several hours, can obtain the α-Al that forms by containing the aluminium particulate breakup with the stove cooling
2O
3Particle, its yardstick is in 10nm～50nm scope.
4. embodiments of the invention:
Dropwise add 200 gram 1M ammonium bicarbonate solns in 1000 gram 0.1M aluminum ammonium sulfate solutions, can produce NH this moment immediately
4AlO (OH)
2HCO
3Molecule, temperature of reaction are 15 ℃, add 300 gram polyvinyl alcohol (PVA) then, after PVA has dissolved, add 100 gram glutaraldehyde again, the sol system that at this moment will contain superpolymer and linking agent places 90 ℃ water-bath to react, after 15 minutes, form the superpolymer gel.Gel after 1 day, is put into Al 70 ℃ of lower dryings
2O
3In the crucible, in silicon carbide rod furnace, rise to 1200 ℃ of insulations with 5 ℃/min heating rate and cool off with stove after 2 hours.α-the Al that obtains like this
2O
3Grain husk grain average-size can reach 30nm, and it is quite even to distribute.
Compared with the prior art have remarkable result than the present invention:
The prices of raw and semifnished materials that adopt are cheap, easy to operate, and control is easy, and the output capacity height need not Large-scale special equipment is easily promoted the use of industrial.
Claims (5)
1. the preparation method of nano level superfine α-alundum (Al2O3) particle is characterized in that: in 0.01～0.1M concentration aluminum saline solution, add its concentration of ammoniacal liquor for containing NH
325～1% (weight contents), NH
3/ Al
2O
3Weight ratio is 0.01～1 or to add its concentration of ammonium bicarbonate soln be 1～0.01M, NH
4HCO
3/ Al
2O
3Weight ratio is 25～4 or to add its concentration of hexamethylenetetramine solution be 1～0.5M, (CH
2)
6N
4/ Al
2O
3Weight ratio is 10～1, in 10～70 ℃ of lower reactions of temperature, after formation contains the sol system of aluminium particulate, adds high polymer and crosslinking agent or adds the high polymer monomer and crosslinking agent and initator, high polymer or polymer monomer amount and Al
2O
3Weight ratio be 10～40, the weight ratio of cross-linked dosage and high polymer or polymer monomer is 0.01～0.30, the mol ratio of amount of initiator and polymer monomer is 0.1～0.025, after carrying out the molten gel process reaction of high polymer type under 25～100 ℃ of temperature, in several seconds to tens hours, can produce the high polymer gel, gel hour was placed in the crucible under 1100～1300 ℃ of conditions 100 ℃ of lower dry a few minutes to tens, insulation a few minutes to after several hours with the stove cooling, namely obtain α-Al
2O
3Particle, its yardstick is in 10～50nm scope.
2. nano level superfine α according to claim 1-aluminium sesquioxide particulate preparation method is characterized in that aluminium salt comprises exsiccated ammonium alum or aluminum nitrate or aluminum chloride or eston or Tai-Ace S 150.
3. nano level superfine α according to claim 1-aluminium sesquioxide particulate preparation method is characterized in that superpolymer is polyvinyl alcohol or chitosan or polymethyl acrylic acid, and polymer monomer is an acrylamide etc.
4. nano level superfine α according to claim 1-aluminium sesquioxide particulate preparation method is characterized in that linking agent is glutaraldehyde or N-vinyl pyrrolidone or diethylenetriamine or methylene bis acrylamide.
5. nano level superfine α according to claim 1-aluminium sesquioxide particulate preparation method is characterized in that initiator is peroxide toluene or azo succinonitrile or hydrogen peroxide or ammonium persulphate or Potassium Persulphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93108450 CN1031396C (en) | 1993-07-20 | 1993-07-20 | Method for preparing alpha-alumina particles with nanometers size |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93108450 CN1031396C (en) | 1993-07-20 | 1993-07-20 | Method for preparing alpha-alumina particles with nanometers size |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1085187A CN1085187A (en) | 1994-04-13 |
| CN1031396C true CN1031396C (en) | 1996-03-27 |
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ID=4987152
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93108450 Expired - Fee Related CN1031396C (en) | 1993-07-20 | 1993-07-20 | Method for preparing alpha-alumina particles with nanometers size |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1031396C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006523178A (en) * | 2003-04-02 | 2006-10-12 | サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド | Nanoporous ultrafine alpha-alumina powder and sol-gel method for preparing the powder |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085679C (en) * | 1998-05-09 | 2002-05-29 | 中国科学院长春应用化学研究所 | Synthesis of vinyl organic/inorganic nano-size hybridized material |
| CN1125794C (en) * | 1999-02-05 | 2003-10-29 | 北京航空材料研究院 | Process for synthesizing composite ceramic powder body |
| DE10035679A1 (en) | 2000-07-21 | 2002-01-31 | Inst Neue Mat Gemein Gmbh | Nanoscale corundum powder, sintered bodies made therefrom and process for their production |
| TWI348457B (en) * | 2003-03-04 | 2011-09-11 | Sumitomo Chemical Co | Method for producing 帢-alumina particulate |
| CN1295152C (en) * | 2005-03-25 | 2007-01-17 | 天津大学 | Electric arc spraying reaction synthesis system and process of preparing nano alumina powder |
| CN100443409C (en) * | 2005-08-26 | 2008-12-17 | 大连路明纳米材料有限公司 | Method of preparing good dispersion and high-purity ultra-fine alpha-Al2O3 |
| CN101746786B (en) * | 2008-12-08 | 2013-08-14 | 中国科学院福建物质结构研究所 | Method for preparing high-purity alpha-Al2O3 nano-crystalline material |
| CN101885500B (en) * | 2010-07-09 | 2012-07-04 | 西安交通大学 | Process for preparing catalysis nano Al2O3 by using starch gel- |
| CN103204526B (en) * | 2012-01-15 | 2016-02-17 | 晟通科技集团有限公司 | A kind of method preparing alumina sol |
| CN105884372B (en) * | 2016-04-12 | 2018-11-13 | 武汉理工大学 | Organic network method synthesizes AlN ceramic powder method |
| CN106699138B (en) * | 2017-01-24 | 2019-10-25 | 山东倍辰新材料有限公司 | A kind of gel casting forming manufacture craft of ceramics scummer |
| CN114940886B (en) * | 2022-04-28 | 2023-09-05 | 浙江大学 | Nanometer alumina abrasive grain, preparation method and application thereof, and silicon carbide polishing solution containing abrasive grain |
| CN115676864A (en) * | 2022-10-25 | 2023-02-03 | 航天特种材料及工艺技术研究所 | Rapid preparation method and application of aluminum sol |
-
1993
- 1993-07-20 CN CN 93108450 patent/CN1031396C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006523178A (en) * | 2003-04-02 | 2006-10-12 | サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド | Nanoporous ultrafine alpha-alumina powder and sol-gel method for preparing the powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1085187A (en) | 1994-04-13 |
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