CN101723682A - Process for preparing alumina-based continuous fiber with sol-gel method - Google Patents
Process for preparing alumina-based continuous fiber with sol-gel method Download PDFInfo
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- CN101723682A CN101723682A CN200910219248A CN200910219248A CN101723682A CN 101723682 A CN101723682 A CN 101723682A CN 200910219248 A CN200910219248 A CN 200910219248A CN 200910219248 A CN200910219248 A CN 200910219248A CN 101723682 A CN101723682 A CN 101723682A
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Abstract
The invention discloses a process for preparing alumina-based continuous fiber with a sol-gel method. The process comprises the following steps of: adding aluminium nitrate and one or a plurality of kinds of carboxylic acids with the carbon number of 2 to 24 to distilled water; ensuring the mixture to react in the condition of continuous stirring under a certain temperature to obtain transparent carboxylate aluminium gel; adding a certain amount of solvent to the carboxylate aluminium gel, and adding a certain amount of silicon-contained additives and superpolymer spinning additives to obtain an alumina-based fiber precursor solution; concentrating the solution to obtain spinnable alumina-based fiber precursor sol; placing the concentrated sol to a liquid storage tank with a spray head, and spinning by adopting a dry method or a wet method to obtain alumina-based continuous fiber protofilament containing organic matters; and drying and sintering the protofilament to obtain the alumina-based continuous fiber. The alumina-based continuous fiber obtained by adopting the invention can be used for reinforcement of composite materials so as to further enhance the strength and toughness of the materials and improve the heat resistance of the materials, and is widely applied in the fields of aerospace, automobiles, and the like.
Description
Technical field
The present invention relates to a kind of preparation technology that can be used as the continuous aluminium oxide base fiber of winding, lamination or other two-dimentional 3 D weavings.
Background technology
Sapphire whisker is a kind of of high-performance inorganic fiber.It is with Al
2O
3Be main component, contain other additive metal oxide, as SiO
2And B
2O
3Deng.Sapphire whisker has the thermotolerance and the high temperature oxidation resistance of high strength, high-modulus, excellence, compares with other fiber, can keep its excellent intensity under higher temperature.Sapphire whisker has forms such as long fibre, short fiber, whisker, can make multiple shapes such as cloth, band, rope, is widely used in high-tech areas such as space flight, aviation, automobile, electric power.The sapphire whisker good surface activity is easy to and metal, Ceramic Composite, can be used for making fibre reinforced metal-based and ceramic matric composite; It is little to have thermal conductivity, and thermal expansivity is low, advantages such as good thermal shock, can be used for improving ceramic matrix toughness, increase resistance to impact shock.
Alumina-based continuous fiber is a kind of ceramic fiber that utilizes dry-spinning or wet spinning spining technology to make.Compare with alumina short fibre, it can twine, be woven into two dimension or three-dimensional fiber preform, the enhancing body that is used for matrix material, and then improve the resistance toheat that the strength of materials and flexible while do not reduce material, be widely used in fields such as aerospace, automobiles.
The classical production process of alumina-based continuous fiber has high-temperature fusion spin processes, collosol and gel spin processes and mixed solution spin processes.The high-temperature fusion spin processes is to contain the alumina powder jointed of partial oxidation silicon, under the situation of adding a small amount of additive, and as magnesium oxide, boron oxide, heat makes the mixed powder fusion, and the melt wire drawing after the fusing is obtained alumina based fibre.The mixed solution spinning is that aluminum oxide and silica powder body and function organic binder bond are deployed into the slip with finite concentration and viscosity, makes the alumina based fibre raw silk by the method for pushing, and high temperature sintering obtains alumina based fibre then.But the common drawback of these two kinds of methods is that melt temperature or sintering temperature are higher.
The sol-gel method spinning technique have mixed-scale little, mix, have low advantage of burning till temperature.。Document [Journal of the European Ceramic Society, 1998,18:1879～1884] adopt aluminum nitrate+aluminum isopropylate respectively, aluminum chloride+aluminium powder and aluminum nitrate+aluminium powder are as the aluminium source, do the silicon source with tetraethoxy and silicon sol, utilize the hydrolytic polymerization of aluminum isopropylate and tetraethoxy or the viscosity that the reaction of aluminium powder under acidic conditions improves spinning colloidal sols stoste, adjust aluminum-containing raw material and silicon-containing material ratio, colloidal sol stoste is concentrated the colloidal sol that obtains having spinning property in certain temperature, obtain fiber precursor with crystal pulling method, by drying, obtain mullite fiber at 1100 ℃ of sintering.Document [CeramicsInternational, 1999,25:539～543; Materials Letters, 2002,57:87～93] then utilize traditional sol gel process, by adding silicon sol, adopt and get rid of a technology, made the polycrystalline alumina fiber reticulated structure of high aluminium content.
The method that above technology adopted is to utilize the hydrolytic-polymeric reaction of aluminum isopropylate and the positive own ester of silicic acid as the way that improves viscosity; perhaps utilize the viscosity of the aluminium powder reaction under acidic conditions raising solution; the blending process complexity; wayward by the viscosity that reaction is regulated, be unfavorable for the large-scale production of alumina based fibre.
By utilizing high molecular polymer can improve the spinning property of colloidal sol, take need not or use less the operational path of aluminum isopropylate and the positive own ester of silicic acid.Document [Materials Chemistry and Physics, 2004,83:54～59] utilize methylcellulose gum to make spin finish aid, with aluminum chloride as the aluminium source, it is 500 microns that the colloidal sol for preparing is pressed through diameter, and length-to-diameter ratio is 10 nozzle acquisition sapphire whisker base substrate, solidifies in the 2-Virahol, with the evaporation of 2-Virahol, last sintering obtains and makes sapphire whisker then.Document [Journal of the European Ceramic Society, 2000,20:2543～2549] then to have introduced with lactic acid or polyvinyl alcohol and done the technology that spin finish aid prepares alumina based fibre, the fiber that lactic acid and aluminium colloidal sol reaction generation Aluctyl make has preferable performance.But do spin finish aid with polyvinyl alcohol, it is big to burn till fiber weakness.Document [Journal of the European Ceramic Society, 2006,26:2611～2617] utilize Natvosol as spin finish aid, in alumina sol, add magnesium nitrate, with syringe alumina based fibre is expressed in the ammoniacal liquor and solidifies, burn till through drying at room temperature and 1600 ℃ then, made and contain magnesian alumina based fibre.But it is higher that the shortcoming of these methods is sintering temperatures.
Summary of the invention
The novel process that the purpose of this invention is to provide a kind of preparing alumina-based continuous fiber with sol-gel method of low cost of manufacture.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of technology of preparing alumina-based continuous fiber with sol-gel method comprises the steps:
(1) preparation of ALUMINUM CARBOXYLIC colloidal sol: in distilled water, add organic acid and aluminum nitrate.Aluminum nitrate and organic acid mol ratio are 1: 0.5-5, and the mol ratio of aluminum nitrate and water is 1: 10-30; Mixture solution under 40-100 ℃, continuous stirring condition, is reacted and prepared ALUMINUM CARBOXYLIC colloidal sol in 4-36 hour; Described organic acid is that carbon atom quantity is the carboxylic acid of 2-24;
(2) preparation of precursor sol: solvent and silicon-containing additive in the ALUMINUM CARBOXYLIC colloidal sol that step (1) obtains make Al in the solution
2O
3, SiO
2Mol ratio is 1: 0-2, Al in the solution
2O
3+ SiO
2, the solvent molar ratio is 10-30, adds the 0-5% high molecular polymer spin finish aid of aluminum nitrate quality again, mix precursor sol; Wherein solvent is one or more in water, alcohol, the acetone, and silicon-containing additive is a kind of in tetraethoxy, silicon sol, water-soluble silicon oil, the silane;
(3) step (2) gained precursor sol is concentrated under 40-100 ℃ of condition;
(4) step (3) is concentrated the reservoir that the colloidal sol that obtains is put into the band shower nozzle, adopt dry method or wet-spinning to obtain containing organic alumina-based continuous fiber precursor;
(5) the fiber precursor drying that step (4) is obtained is heated to 600 ℃ then and sloughs organism, then is warming up to 1000-1400 ℃ and burns till, and insulation 0.5-2h finally obtains the polycrystal alumina base continuous fibers.
In the such scheme, the carbon atom quantity in the described step (1) be the carboxylic acid of 2-24 be acetic acid, citric acid, oxalic acid, tartrate, caproic acid, sad, capric acid, lactic acid one or more.The high molecular polymer spin finish aid is a kind of in polyvinyl butyral acetal, polyvinyl alcohol, polyvinylpyrrolidone, macrogol, the polyacrylic acid in the described step (2).
The drying of described step (5) is that condition is 40-100 ℃ of down insulation 1-48 hour, and described to slough organic temperature rise rate be 0.5-5 ℃/min.The described temperature rise rate that burns till is 5-10 ℃/min.
Characteristics of the present invention are to utilize aluminum nitrate, organic acid to be raw material, the solution of preparation aluminium under certain temperature and time conditions.Aluminum nitrate and organic acid easily form the organic acid complex compound, and polycondensation easily takes place in this experimental system organic acid, helps the formation of linear molecule.In aluminum solutions, add the silicon source, obtain the aluminium colloidal sol that contains Si, obtain alumina-based continuous fiber, can overcome with the too high shortcoming of aluminium-alcohol salt cost through spinning, drying, sintering circuit with spinning property by control to solution heat-up time, Heating temperature.
According to method of the present invention, form by adjusting prescription, available alumina based fibre contain mullite mutually and aluminum oxide mutually, the biphase ratio changes with the ratio of aluminum oxide and silicon oxide, physicochemical property are stablized.Preparing resulting alumina-based continuous fiber diameter is 5-50 μ m, has good intensity, maximum strength is 250MPa, and can be wrapped on the guide roller, the densification of fiber section can be satisfied special service requirements, this fiber can be used for the enhancing body in the matrix material, and then improve the strength of materials and toughness, the time improve the resistance toheat of material, be widely used in fields such as aerospace, automobiles.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
Table 1 has been listed 16 embodiment the first step technologies that are numbered 1-16: determine aluminum nitrate, water, organic acid kind and add-on according to the different embodiment of table 1, and the preparation condition of definite ALUMINUM CARBOXYLIC colloidal sol, prepare ALUMINUM CARBOXYLIC colloidal sol.
The preparation of table 1. ALUMINUM CARBOXYLIC colloidal sol
Table 2 has been listed second and third step process condition of table 1 embodiment: add solvent, silicon-containing material, spin finish aid according to the different embodiment of table 2 in ALUMINUM CARBOXYLIC colloidal sol, prepare the alumina based fibre precursor sol according to the concentrated condition of table 2.The 4th step, put in the reservoir of band shower nozzle concentrating the back precursor sol, adopt dry method or wet-spinning to obtain containing organic alumina-based continuous fiber precursor.
The preparation of table 2. alumina based fibre precursor sol
Table 3 has been listed the 5th step process condition of table 1 embodiment: obtain alumina based fibre according to fiber drying, sintering process in the table 3, the diameter and the tensile strength of the continuous aluminium oxide base fiber of each embodiment are shown in table 4.
Table 3. fiber drying, sintering process
The performance of table 4. alumina based fibre
| Diameter (μ m) | Tensile strength (MPa) | |
| Embodiment 1 | ??20-40 | ??180±10 |
| Embodiment 2 | ??10-30 | ??170±10 |
| Embodiment 3 | ??10-25 | ??200±10 |
| Embodiment 4 | ??10-35 | ??210±10 |
| Embodiment 5 | ??5-20 | ??220±10 |
| Embodiment 6 | ??6-25 | ??230±20 |
| Embodiment 7 | ??8-30 | ??240±20 |
| Embodiment 8 | ??15-40 | ??180±20 |
| Embodiment 9 | ??15-50 | ??170±20 |
| Diameter (μ m) | Tensile strength (MPa) | |
| Embodiment 10 | ??15-30 | ??250±10 |
| Embodiment 11 | ??5-20 | ??250±10 |
| Embodiment 12 | ??5-30 | ??250±20 |
| Embodiment 13 | ??15-40 | ??210±10 |
| Embodiment 14 | ??15-50 | ??240±20 |
| Embodiment 15 | ??20-50 | ??150±20 |
| Embodiment 16 | ??10-30 | ??200±10 |
As can be seen from Table 4, the controllable diameter of the continuous aluminium oxide base fiber of the inventive method preparation, intensity is higher; And have good toughness, and can be wrapped on the guide roller, can satisfy special service requirements.
Claims (6)
1. the technology of a preparing alumina-based continuous fiber with sol-gel method is characterized in that, comprises the steps:
(1) preparation of ALUMINUM CARBOXYLIC colloidal sol: in distilled water, add organic acid and aluminum nitrate.Aluminum nitrate and organic acid mol ratio are 1: 0.5-5, and the mol ratio of aluminum nitrate and water is 1: 10-30; Mixture solution under 40-100 ℃, continuous stirring condition, is reacted and prepared ALUMINUM CARBOXYLIC colloidal sol in 4-36 hour; Described organic acid is that carbon atom quantity is the carboxylic acid of 2-24;
(2) preparation of precursor sol: solvent and silicon-containing additive in the ALUMINUM CARBOXYLIC colloidal sol that step (1) obtains make Al in the solution
2O
3, SiO
2Mol ratio is 1: 0-2, Al in the solution
2O
3+ SiO
2, the solvent molar ratio is 10-30, adds the 0-5% high molecular polymer spin finish aid of aluminum nitrate quality again, mix precursor sol; Wherein solvent is one or more in water, alcohol, the acetone, and silicon-containing additive is a kind of in tetraethoxy, silicon sol, water-soluble silicon oil, the silane;
(3) step (2) gained precursor sol is concentrated under 40-100 ℃ of condition;
(4) step (3) is concentrated the reservoir that the colloidal sol that obtains is put into the band shower nozzle, adopt dry method or wet-spinning to obtain containing organic alumina-based continuous fiber precursor;
(5) the fiber precursor drying that step (4) is obtained is heated to 600 ℃ then and sloughs organism, then is warming up to 1000-1400 ℃ and burns till, and insulation 0.5-2h finally obtains the polycrystal alumina base continuous fibers.
2. the technology of preparing alumina-based continuous fiber with sol-gel method as claimed in claim 1, it is characterized in that, the carbon atom quantity in the described step (1) be the carboxylic acid of 2-24 be acetic acid, citric acid, oxalic acid, tartrate, caproic acid, sad, capric acid, lactic acid one or more.
3. the technology of preparing alumina-based continuous fiber with sol-gel method as claimed in claim 1, it is characterized in that the high molecular polymer spin finish aid is a kind of in polyvinyl butyral acetal, polyvinyl alcohol, polyvinylpyrrolidone, macrogol, the polyacrylic acid in the described step (2).
4. the technology of preparing alumina-based continuous fiber with sol-gel method as claimed in claim 1 is characterized in that, the drying of described step (5) is that condition is to be incubated 1-48 hour under 40-100 ℃.
5. the technology of preparing alumina-based continuous fiber with sol-gel method as claimed in claim 1 is characterized in that, described to slough organic temperature rise rate be 0.5-5 ℃/min.
6. the technology of preparing alumina-based continuous fiber with sol-gel method as claimed in claim 1 is characterized in that, the described temperature rise rate that burns till is 5-10 ℃/min.
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Cited By (13)
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| CN102011215A (en) * | 2010-10-15 | 2011-04-13 | 陕西理工学院 | Process for preparing yttrium aluminum garnet-based continuous fibers through sol-gel method |
| CN102070326A (en) * | 2010-11-30 | 2011-05-25 | 西安交通大学 | Preparation process of multi-element composite alumina-based continuous fibers |
| CN102225863A (en) * | 2011-04-12 | 2011-10-26 | 陕西理工学院 | Preparation method of alumina-based composite continuous fibers |
| CN102344287A (en) * | 2011-07-13 | 2012-02-08 | 陕西理工学院 | Technology for preparing cordierite-based continuous fiber by using sol-gel method |
| CN102351516A (en) * | 2011-07-06 | 2012-02-15 | 西安交通大学 | Method for preparing alumina-based continuous fibers by using SiO2 nano powder raw material |
| CN103160954A (en) * | 2011-12-13 | 2013-06-19 | 洛阳新巨能高热技术有限公司 | Preparation method of alumina polycrystalline fiber |
| CN103757750A (en) * | 2014-01-09 | 2014-04-30 | 天津工业大学 | Preparation method of alumina-based continuous fibers |
| CN104884690A (en) * | 2012-10-31 | 2015-09-02 | 电气化学工业株式会社 | Alumina-based fibrous mass, process for producing same, and use |
| CN107723496A (en) * | 2017-08-28 | 2018-02-23 | 中国兵器科学研究院宁波分院 | The preparation method of Al-Si metal matrix composite |
| CN108395216A (en) * | 2018-04-10 | 2018-08-14 | 中南大学 | A kind of ceramics and its preparation method and application with mullite structure |
| CN110376816A (en) * | 2019-07-16 | 2019-10-25 | 西安交通大学 | Self-powered tungsten oxide base electrochromic device based on aluminium ion hydrogel and preparation method thereof |
| CN111235644A (en) * | 2020-03-18 | 2020-06-05 | 山东鲁阳浩特高技术纤维有限公司 | Spinning solution for preparing mullite fiber and application thereof |
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| CN102011215A (en) * | 2010-10-15 | 2011-04-13 | 陕西理工学院 | Process for preparing yttrium aluminum garnet-based continuous fibers through sol-gel method |
| CN102070326A (en) * | 2010-11-30 | 2011-05-25 | 西安交通大学 | Preparation process of multi-element composite alumina-based continuous fibers |
| CN102070326B (en) * | 2010-11-30 | 2013-05-22 | 西安交通大学 | Preparation process of multi-element composite alumina-based continuous fibers |
| CN102225863A (en) * | 2011-04-12 | 2011-10-26 | 陕西理工学院 | Preparation method of alumina-based composite continuous fibers |
| CN102351516A (en) * | 2011-07-06 | 2012-02-15 | 西安交通大学 | Method for preparing alumina-based continuous fibers by using SiO2 nano powder raw material |
| CN102344287A (en) * | 2011-07-13 | 2012-02-08 | 陕西理工学院 | Technology for preparing cordierite-based continuous fiber by using sol-gel method |
| CN103160954A (en) * | 2011-12-13 | 2013-06-19 | 洛阳新巨能高热技术有限公司 | Preparation method of alumina polycrystalline fiber |
| CN104884690A (en) * | 2012-10-31 | 2015-09-02 | 电气化学工业株式会社 | Alumina-based fibrous mass, process for producing same, and use |
| JPWO2014069589A1 (en) * | 2012-10-31 | 2016-09-08 | デンカ株式会社 | Alumina fiber assembly, its production method and use |
| US9827553B2 (en) | 2012-10-31 | 2017-11-28 | Denka Company Limited | Alumina-based fibrous mass, process for producing same, and use |
| CN103757750A (en) * | 2014-01-09 | 2014-04-30 | 天津工业大学 | Preparation method of alumina-based continuous fibers |
| CN107723496A (en) * | 2017-08-28 | 2018-02-23 | 中国兵器科学研究院宁波分院 | The preparation method of Al-Si metal matrix composite |
| CN107723496B (en) * | 2017-08-28 | 2019-11-01 | 中国兵器科学研究院宁波分院 | The preparation method of Al-Si metal matrix composite |
| CN108395216A (en) * | 2018-04-10 | 2018-08-14 | 中南大学 | A kind of ceramics and its preparation method and application with mullite structure |
| CN110376816A (en) * | 2019-07-16 | 2019-10-25 | 西安交通大学 | Self-powered tungsten oxide base electrochromic device based on aluminium ion hydrogel and preparation method thereof |
| CN110376816B (en) * | 2019-07-16 | 2021-01-15 | 西安交通大学 | Self-powered tungsten oxide-based electrochromic device based on aluminum ion hydrogel and preparation method thereof |
| CN111235644A (en) * | 2020-03-18 | 2020-06-05 | 山东鲁阳浩特高技术纤维有限公司 | Spinning solution for preparing mullite fiber and application thereof |
| CN111235644B (en) * | 2020-03-18 | 2022-03-04 | 山东鲁阳浩特高技术纤维有限公司 | Spinning solution for preparing mullite fiber and application thereof |
| CN112409004A (en) * | 2020-11-12 | 2021-02-26 | 上海榕融新材料科技有限公司 | Preparation method of slurry for alumina continuous fiber reinforced ceramic composite material |
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Application publication date: 20100609 |