CN101974782A - Method of preparing alpha-Al2O3 crystal whisker by carbothermal reduction - Google Patents
Method of preparing alpha-Al2O3 crystal whisker by carbothermal reduction Download PDFInfo
- Publication number
- CN101974782A CN101974782A CN2010105503066A CN201010550306A CN101974782A CN 101974782 A CN101974782 A CN 101974782A CN 2010105503066 A CN2010105503066 A CN 2010105503066A CN 201010550306 A CN201010550306 A CN 201010550306A CN 101974782 A CN101974782 A CN 101974782A
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- China
- Prior art keywords
- silicon
- sio
- whisker
- dioxide
- crystal whisker
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000009467 reduction Effects 0.000 title claims abstract description 13
- 239000013078 crystal Substances 0.000 title abstract 5
- 229910052594 sapphire Inorganic materials 0.000 title abstract 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010881 fly ash Substances 0.000 claims abstract description 5
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 19
- 238000006722 reduction reaction Methods 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003832 thermite Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 230000002829 reductive effect Effects 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 238000007323 disproportionation reaction Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- -1 fly ash Chemical compound 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a method of preparing a metallic silicon and an alpha-Al2O3 crystal whisker by carbothermal reduction, which employs materials containing silicon dioxide and aluminum oxide (e.g., fly ash, bauxite and red mud) as raw materials, and carbon as a reducing agent. An elemental silicon and the alpha-Al2O3 crystal whisker are obtained by controlling the temperature of a high temperature furnace at 1200-2000 DEG C for the reduction of materials, then condensing these materials at 500-1000 DEG C. The alpha-Al2O3 crystal whisker obtained after silicon separation has a uniform diameter of 2-5 microns, a length of 100-200 microns and a length/diameter ratio of 20-100. The method has short technological process, low cost and high yield. The alpha-Al2O3 crystal whisker prepared by the method of the invention has excellent comprehensive performances such as high specific strength, high specific modulus and high temperature oxidation resistance, and is mainly used for high performance composite materials, in particular for high temperature structural ceramics.
Description
Technical field
The present invention relates to carbothermic method and prepare α-Al
2O
3The whisker technology belongs to technical field of material.
Background technology
α-Al
2O
3Whisker has superior over-all propertieies such as high specific strength, high ratio modulus and high-temperature oxidation resistant, be high performance composite especially high temperature resistant structure ceramics get a good chance of one of strengthening agent with potentiality. along with high temperature is used developing rapidly of ceramic base and the research of metal matrix metal whisker composite, people are urgent day by day to the demand of the high-strength whisker of high-temperature oxidation resistant, to α-Al
2O
3The discussion of whisker synthesis technique also becomes a focus in the domestic and international association area.
α-Al
2O
3Whisker is synthetic to mainly contain following several method at present: (1) metallic aluminium reacts with the wet hydrogen fluidisation, and the growth temperature of whisker is 1350 ℃, but owing to the nucleation aggregation of particles, and radially Unstable Growth or polycrystalline are piled up growth easily to produce whisker; (2) founding-in-situ reaction, the growth temperature of whisker are 900 ℃; (3) with α-Al
2O
3Ultrafine powder and nanometer alpha-Al
2O
3Powder is a raw material, introduces an amount of NaO and MgO, goes out β-Al at 1500 ℃ of following thermal treatment growth in situ
2O
3Whisker; (4) adopt Al
2O
3, AlN and N
2Be raw material, the utilization chemical Vapor deposition process is at 1500 ℃ of preparation α-Al
2O
3Whisker.The traditional preparation process method exists deficiencies such as ingredient requirement height, preparation cost height and diameter of whiskers are inhomogeneous.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide a kind of carbothermic method to prepare α-Al
2O
3The method of whisker, the α-Al that utilizes the inventive method to make
2O
3Whisker, its diameter Distribution differs less, 5 big μ m, 2 little μ m, the length of whisker is 100 μ m～00 μ m, length-to-diameter ratio is approximately 20～100, to satisfy the needs of the high-strength whisker of high-temperature oxidation resistant.
Technical scheme of the present invention is, the material and the carbonaceous reducing agent of any content silicon-dioxide and aluminium sesquioxide carried out pre-treatment, can reach purpose of the present invention by operations such as carbothermic reduction, cooling disproportionation reaction, thermite reductions then.
The feature of the inventive method is that preparation section is as follows:
A, pre-treatment wear into fine powder below 50～80 orders separately with the material of any content silicon-dioxide and aluminium sesquioxide and carbonaceous reducing agent, proportioning by mass ratio=12: 0.5～20 of material and carbonaceous reducing agent is prepared burden, mix, briquetting, and place the interior crucible of process furnace;
B, carbothermic reduction are controlled at 1200～2000 ℃ with temperature in the stove, and following reaction takes place in crucible:
C+SiO
2＝SiO↑+CO↑
2C+Al
2O
3＝Al
2O↑+2CO↑
Generate SiO gas and Al
2O gas, the reaction times is 5～75 minutes;
SiO gas and Al that C, cooling disproportionation reaction process B generate
2In the process that O gas rises in crucible, along with temperature is reduced between 700 ℃～1000 ℃, disproportionation reaction takes place:
2SiO＝Si+SiO
2
3Al
2O＝4Al+Al
2O
3
Generate α-Al
2O
3Nucleus and metallic aluminium, Pure Silicon Metal and silicon-dioxide;
D, thermite reduction are reduced to 500 ℃～700 ℃ with the temperature of process furnace, metallic aluminium that operation C generated and silicon-dioxide generation thermite reduction reaction:
Al+SiO
2＝Si+Al
2O
3
Generate Al
2O
3, last at the α-Al that is generated
2O
3Crystallization is α-Al on the nucleus
2O
3Whisker.
Above the said material that contains silicon-dioxide and aluminium sesquioxide be fuel-burning power plant flyash, a kind of in bauxite or the red mud, said carbonaceous reducing agent is a kind of in charcoal, refinery coke or the coal.
Compare with existing technology is arranged, the present invention has following advantage and positively effect.
1, technology simply is that the technical process that the present invention of core technology can be designed to as shown in Figure 1 just can prepare α-Al with the carbothermic reduction
2O
3Whisker.
2, raw material fuel-burning power plant biomass fuel ashing, power plant fly ash and the silicon dioxide mine of high this technology use of economic benefit are cheap, and have solved environmental issue.The carbonaceous reducing agent low price obtain easily, and technical process is simple, has saved a large amount of processing steps, and the consumption of the energy reduces greatly, thereby can increase economic efficiency widely.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
The invention will be further described with embodiment below.
Embodiment 1
Use certain fuel-burning power plant flyash (contain silicon-dioxide and be 23wt%) to be raw material as 50wt%, aluminium sesquioxide, charcoal is a reductive agent, wear into 50 purpose fine powders separately, mass ratio with 12: 1.5 is prepared burden, mix, briquetting, adding the interior temperature of thermal control stove is 2000 ℃, reacted 5 minutes, and obtained SiO gas and Al
2O gas, this gas rises in crucible, and obtains condensation, when temperature drops to 1000 ℃, is generated as silicon, silicon-dioxide, aluminium and α-Al
2O
3Nucleus, when temperature dropped to 700 ℃, aluminium that is generated and silicon-dioxide generation thermite reduction generated α-Al
2O
3Whisker.Resultant α-Al
2O
3Diameter of whiskers distributes and differs less, is 3 μ m, and the length of whisker is 180 μ m greatly, and length-to-diameter ratio is approximately 60.
Embodiment 2
Use bauxite (contain silicon-dioxide and be 52wt%) to be raw material as 21wt%, aluminium sesquioxide, refinery coke is a reductive agent, wear into 60 purpose fine powders separately, mass ratio with 12: 0.5 is prepared burden, mix, briquetting, adding the interior temperature of thermal control stove is 1200 ℃, reacted 7 minutes, and obtained SiO gas and Al
2O gas, this gas rises in crucible, and obtains condensation, when temperature drops to 700 ℃, is generated as silicon, silicon-dioxide, aluminium and aluminium sesquioxide, and when temperature dropped to 500 ℃, aluminium that is generated and silicon-dioxide generation thermite reduction generated α-Al
2O
3Whisker.Resultant α-Al
2O
3Diameter of whiskers distributes and differs less, is 4 μ m, and the length of whisker is 190 μ m, and length-to-diameter ratio is 48.
Embodiment 3
Use red mud (contain silicon-dioxide and be 6.3wt%) to be that raw material, coal are reductive agent, wear into 80 purpose fine powders separately as 18wt%, aluminium sesquioxide, mass ratio with 12: 20 is prepared burden, and mixes briquetting, adding the interior temperature of thermal control stove is 1700 ℃, reacts 6 minutes, obtains SiO gas and Al
2O gas, this gas rises in crucible, and obtains condensation, when temperature drops to 750 ℃, is generated as silicon, silicon-dioxide, aluminium and aluminium sesquioxide, and when temperature dropped to 600 ℃, aluminium that is generated and silicon-dioxide generation thermite reduction generated α-Al
2O
3Whisker.Resultant α-Al
2O
3Diameter of whiskers distributes and differs less, is 2.5 μ m, and the length of whisker is 170 μ m, and length-to-diameter ratio is 68.
Claims (2)
1. a carbothermic method prepares α-Al
2O
3The method of whisker is characterized in that preparation section is as follows:
A, pre-treatment wear into fine powder below 50～80 orders separately with the material of any content silicon-dioxide and aluminium sesquioxide and carbonaceous reducing agent, proportioning by mass ratio=12: 0.5～20 of material and carbonaceous reducing agent is prepared burden, mix, briquetting, and place the interior crucible of process furnace;
B, carbothermic reduction are controlled at 1200～2000 ℃ with temperature in the stove, and following reaction takes place in crucible:
C+SiO
2＝SiO↑+CO↑
2C+Al
2O
3＝Al
2O↑+2CO↑
Generate SiO gas and Al
2O gas, the reaction times is 5～75 minutes;
SiO gas and Al that C, cooling disproportionation reaction process B generate
2In the process that O gas rises in crucible, along with temperature is reduced between 700 ℃～1000 ℃, disproportionation reaction takes place:
2SiO＝Si+SiO
2
3Al
2O＝4Al+Al
2O
3
Generate α-Al
2O
3Nucleus and metallic aluminium, Pure Silicon Metal and silicon-dioxide;
D, thermite reduction are reduced to 500 ℃～700 ℃ with the temperature of process furnace, metallic aluminium that operation C generated and silicon-dioxide generation thermite reduction reaction:
Al+SiO
2＝Si+Al
2O
3
Generate Al
2O
3, last at the α-Al that is generated
2O
3Crystallization is α-Al on the nucleus
2O
3Whisker.
2. according to the method for claim 1, it is characterized in that the said material that contains silicon-dioxide and aluminium sesquioxide is a fuel-burning power plant flyash, a kind of in bauxite or the red mud, said carbonaceous reducing agent is a kind of in charcoal, refinery coke or the coal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010550306.6A CN101974782B (en) | 2010-11-19 | 2010-11-19 | Method of preparing alpha-Al2O3 crystal whisker by carbothermal reduction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010550306.6A CN101974782B (en) | 2010-11-19 | 2010-11-19 | Method of preparing alpha-Al2O3 crystal whisker by carbothermal reduction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101974782A true CN101974782A (en) | 2011-02-16 |
| CN101974782B CN101974782B (en) | 2013-01-02 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010550306.6A Expired - Fee Related CN101974782B (en) | 2010-11-19 | 2010-11-19 | Method of preparing alpha-Al2O3 crystal whisker by carbothermal reduction |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106392099A (en) * | 2016-06-08 | 2017-02-15 | 昆明理工大学 | Preparation method of aluminum oxide/aluminum compounded micro-fine powder |
| RU2732661C1 (en) * | 2019-12-10 | 2020-09-22 | Федеральное государственное бюджетное научное учреждение "Федеральный исследовательский центр "Красноярский научный центр Сибирского отделения Российской академии наук" (ФИЦ КНЦ СО РАН, КНЦ СО РАН) | METHOD OF PRODUCING POROUS WHISKERS α-Al2O3 USING LEAD-ZINC PRODUCTION WASTES |
| CN114606571A (en) * | 2022-04-02 | 2022-06-10 | 陕西理工大学 | Alumina whisker prepared from blast furnace slag and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109106A (en) * | 2007-07-25 | 2008-01-23 | 中国科学院青海盐湖研究所 | Process for producing aluminum oxide crystal whisker |
| CN101338448A (en) * | 2008-08-12 | 2009-01-07 | 中国科学院青海盐湖研究所 | Hydrothermal preparation method for aluminum oxide whiskers at low temperature |
| CN101660204A (en) * | 2009-09-09 | 2010-03-03 | 中国科学院青海盐湖研究所 | Preparation method of hexagonal piece aluminum oxide whisker material |
-
2010
- 2010-11-19 CN CN201010550306.6A patent/CN101974782B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109106A (en) * | 2007-07-25 | 2008-01-23 | 中国科学院青海盐湖研究所 | Process for producing aluminum oxide crystal whisker |
| CN101338448A (en) * | 2008-08-12 | 2009-01-07 | 中国科学院青海盐湖研究所 | Hydrothermal preparation method for aluminum oxide whiskers at low temperature |
| CN101660204A (en) * | 2009-09-09 | 2010-03-03 | 中国科学院青海盐湖研究所 | Preparation method of hexagonal piece aluminum oxide whisker material |
Non-Patent Citations (4)
| Title |
|---|
| 《Journal of materials science》 19870430 hayashi,t,etc Growth of Al2O3 whiskers by vapor-phase reactions 1305-1309 第22卷, 第4期 2 * |
| 《Journal of the american ceramic society》 20030831 Deng cheng ji,etc Fabrication of Single-Crystal ┌-Al2O3 Nanorods by Displacement Reactions 1385-1388 第86卷, 第8期 2 * |
| 《现代化工》 20071130 李洁等 氧化铝晶须的研究进展 129-132 第27卷, 第增刊（2）期 2 * |
| 《陶瓷学报》 20090930 艾桃桃 Al2O3 晶须的原位合成与形成机理研究 290-294 第30卷, 第3期 2 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106392099A (en) * | 2016-06-08 | 2017-02-15 | 昆明理工大学 | Preparation method of aluminum oxide/aluminum compounded micro-fine powder |
| RU2732661C1 (en) * | 2019-12-10 | 2020-09-22 | Федеральное государственное бюджетное научное учреждение "Федеральный исследовательский центр "Красноярский научный центр Сибирского отделения Российской академии наук" (ФИЦ КНЦ СО РАН, КНЦ СО РАН) | METHOD OF PRODUCING POROUS WHISKERS α-Al2O3 USING LEAD-ZINC PRODUCTION WASTES |
| CN114606571A (en) * | 2022-04-02 | 2022-06-10 | 陕西理工大学 | Alumina whisker prepared from blast furnace slag and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN101974782B (en) | 2013-01-02 |
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