CN100417620C - Process for preparing zirconium oxide ceramic continuous fibre - Google Patents
Process for preparing zirconium oxide ceramic continuous fibre Download PDFInfo
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- CN100417620C CN100417620C CNB2005100450146A CN200510045014A CN100417620C CN 100417620 C CN100417620 C CN 100417620C CN B2005100450146 A CNB2005100450146 A CN B2005100450146A CN 200510045014 A CN200510045014 A CN 200510045014A CN 100417620 C CN100417620 C CN 100417620C
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Abstract
The present invention relates to a method for preparing zirconium oxide (ZrO2) ceramic continuous fibre, which belongs to the field of inorganic non-metallic material. The present invention has the main content that the zirconium oxychloride and the yttrium nitrate are used as raw material; organic compounds such as one or two or more than two mixtures in sucrose, dextrose and fruit sugar or citric acid are taken as additives; precursor colloidal sol is prepared by electrolysis, then spinnable precursor colloidal sol is obtained by aging the colloidal sol, xerogel fibre is obtained after dried by filature and is sintered by high temperature, and the zirconium oxide ceramic continuous fibre is prepared. The present invention solves the prior art existing defects of low solid content, big volume shrinkage in the sintering process, poor fibre compactness, high raw material cost, etc. The present invention has the advantages that ZroCl2.8H2O, Y (NO3) 3.6H2O, the sucrose and the dextrose or the citric acid are used as the raw material, the spinnable precursor colloidal sol is prepared by an electrolytic method, the technological process is easy to control, the raw material is easy to get, the cost is low, the present invention belongs to the environment friendly type technique and has easy industrial production, the homogeneity and the compactness of the obtained zirconium oxide ceramic continuous fibre are good, and the tensile strength of the fibre is high.
Description
(1) technical field
The present invention relates to a kind of zirconium white (ZrO
2) preparation method of ceramic continuous fibre, belong to field of inorganic nonmetallic material.
(2) background technology
Zirconium oxide ceramic continuous fibre has high temperature resistant, high strength, good toughness and characteristic such as corrosion-resistant, be excellent high-temperature corrosion resistance and redox fiber reinforced material, there is important use to be worth in various fields, it is the indispensable critical material of some products or equipment, as: 1. be used for ultrahigh-temperature heat treatment furnace thermofin as the ultrahigh-temperature lagging material, using zirconium oxide ceramic continuous fibre enhanced zirconium white/zirconia composite ceramics can make the high temperature furnace fire resistant material weight reduce by 90% (complete machine weight reduces 60%), energy-conservation 40%, heat-up rate improves 2/3, improves 6～8 times work-ing life; 2. be used for the alkaline battery separator material, the zirconia ceramics cloth that uses the zirconium oxide ceramic continuous fibre woven cloth to replace the organic fabric impregnation sintering to form is made Ni-H
2Battery diaphragm can improve the stability of battery, 5～6 times of prolongs lifes, the ZYK-15 series Ni-H of the U.S.
2Alkaline cell has adopted the zirconium oxide ceramic continuous fibre woven cloth to finish update; 3. the matrix material that makes of zirconium oxide ceramic continuous fibre can be used as high-temperature-resistant filtering material, and aqueous alkali filtering material and support of the catalyst etc. are as molten steel strainer and high alkali liquid strainer; 4. zirconium oxide ceramic continuous fibre also can be used for fuel cell and high tension battery barrier film matrix material, the various wear parts of preparation oil-field oil pumper etc., the high-temperature component fiber reinforced material of space vehicle power system, make function/structure-integrated device with other functional fibre blending, preparation high temperature oxygen detector (the tubular zirconium-oxide strongthener of strength and thermal shock resistant) etc.
There are U.S., day, Ying Dengguo in the country of at present existing commodity zirconium oxide ceramic continuous fibre, can produce zirconium oxide ceramic continuous fibre as U.S. Zicar Zirconia company, 3M company, Britain ICI company and Japanese Toshiba Corporation etc.The method for preparing zirconium oxide ceramic continuous fibre has: (1) pickling process: organic fibre floods in zirconium salt solution continuously, sintering in air then, remove organism and obtain Zirconium oxide fibre, stable employing calcium oxide, magnesium oxide or the yttrium oxide of zirconic tetragonal phase structure.Although this method technology is simple, zirconia content is low in the presoma, the organic component content height, and volumetric shrinkage is big in sintering process, and the organism decomposition causes the intercrystalline space more, thereby fibre strength is lower.(2) hybrid system: the acetic acid zirconium mixes with organic polymer soln, adds the Zirconium powder that particle diameter is about 100nm, and CSV concentrated solution viscosity was 80～90 handkerchief seconds, was pressed through spinning jet then and obtained the gel continuous fibre, obtained zirconium oxide ceramic continuous fibre behind the sintering.This method technology is simple, but has shortcomings such as solid content is low, the sintering process volumetric shrinkage big, fiber compactness difference equally.(3) colloidal sol spin processes: 1. methyl ethyl diketone complex system methyl ethyl diketone is as additive, and the zirconium alkoxide hydrolytic polymerization obtains the poly-zirconium oxygen alkane colloidal sol of fibrous long-chain, pulls out fiber.Fiber thermal treatment obtains zirconium oxide ceramic continuous fibre.2. methyl aceto acetate complex system zirconium oxychloride and methyl aceto acetate are raw material, the synthetic polymer sol that contains the ZrOZr long-chain in the presence of triethylamine.Spinning obtains gelled fibre, and the thermal treatment gelled fibre obtains zirconium oxide ceramic continuous fibre.3. acetic acid zirconium and formic acid zirconium system acetic acid zirconium colloidal sol under certain condition evaporation concentration obtain being suitable for stringy thickness colloidal sol, spinning obtains gelled fibre, obtains zirconium oxide ceramic continuous fibre after the sintering processes.As the more sol-gel system of above report, can obtain the continuous zirconia fiber that compactness is good, intensity is high, but often contain material poisonous, that contaminative is arranged in the organism of material cost height, use.
(3) summary of the invention
In order to solve low, the shortcomings such as the sintering process volumetric shrinkage big, fiber compactness is poor, material cost height of solid content that prior art exists, the present invention proposes a kind of preparation high strength, low-cost zirconia ceramics fiber preparation method continuously.
Of the present inventionly to the effect that realize by following technical scheme:
Utilize zirconium oxychloride and Yttrium trinitrate as raw material, get organic compound such as sucrose, glucose, in fructose or the citric acid one or both or two or more mixture make precursor sol as additive through electrolysis, and colloidal sol is through the aging spinning property precursor sol that obtains then, after through the spinning drying, obtain the xerogel fiber, high temperature sintering xerogel fiber makes zirconium oxide ceramic continuous fibre, and concrete preparation process is as follows:
(1) preparation of spinning property precursor sol
Press ZrOCl
28H
2O is 1.45～1.60: 1 with the ratio of pure water weight, with ZrOCl
28H
2The water-soluble zirconium oxychloride aqueous solution that obtains of O is pressed mass ratio ZrOCl
28H
2O: Y (NO
3)
36H
2O=10～16: 1 adds Y (NO in zirconium oxychloride aqueous solution
3)
36H
2O, then with solution at 40 ℃ of following heating in water bath, and add organic additive, organic additive can be one or both or the two or more mixture in sucrose, glucose, fructose or the citric acid, wherein presses mass ratio ZrOCl
28H
2O: sucrose=4～6: 1, ZrOCl
28H
2O: glucose or fructose=10～12: 1, ZrOCl
28H
2O: citric acid=2～6: 1, the mixed additive ratio fully stirs and makes its dissolving this interval adjustment, add Glacial acetic acid then in solution, wherein the mass ratio of zirconium oxychloride and Glacial acetic acid is 1.3～5.4: 1, uses agitator continuously stirring 1～2 hour, naturally cooling, Cl is removed in electrolysis then
-, at room temperature be aged to viscosity and reach 10-100 handkerchief second, obtain the spinning property precursor sol;
(2) utilize the dry-spinning technology that the spinning property precursor sol that is worth is carried out spinning, make gelled fibre;
(3) again gelled fibre being put into tube furnace heats, be warming up to 400 ℃～600 ℃ by 0.5 ℃～1 ℃/minute speed, constant temperature 1～2 hour, be warming up to 1200 ℃～1380 ℃ by 〉=100 ℃/minute speed then, constant temperature is 10 minutes again, be quickly cooled to below 1000 ℃, reduce to room temperature more naturally, obtain zirconium oxide ceramic continuous fibre.
Utilize the inventive method to make continuous zirconia fiber, wherein ZrO
2The crystal formation of fiber is a tetragonal phase structure, and Fibre diameter is 7～10 μ m, and tensile strength is 2.4～2.7GPa.
Though the preparation method that the present invention proposes belongs to electrolysis and the sol-gel method preparation ZrO that combines
2Continuous fibre, but compare with existing sol-gel process, its advantage is to utilize zirconium oxychloride (ZrOCl
28H
2O), sucrose, glucose, fructose or citric acid are made raw material, prepare sol-gel process with electrolytic method and control easily, raw material is easy to get, and is with low cost, is easy to suitability for industrialized production, the advantages of nontoxic raw materials of using in addition, nonstaining property gas is emitted in the entire treatment process, belongs to environmentally friendly technology.Utilizing the thing of the continuous zirconia fiber that the inventive method obtains is tetragonal phase structure mutually, and the ceramic continuous fibre homogeneity is good, and continuous fibre compactness is good, the tensile strength height.
In a word, it is simple to operation that the present invention has technology, and product performance are stable, advantages such as compliance with environmental protection requirements.
(4) embodiment
Embodiment 1
In 1.45: 1 ratios with 29g ZrOCl
28H
2O is dissolved in the 20g water and obtains ZrOCl
2The aqueous solution is to ZrOCl
2Add 2.9gY (NO in the aqueous solution
3)
36H
2O, then with solution at 40 ℃ of following heating in water bath, in the aqueous solution, add 7.25g sucrose, and fully stir and make its dissolving, in solution, add the 22g Glacial acetic acid then, continue to stir 2 hours with agitator, naturally cooling, Cl is removed in electrolysis then
-, at room temperature be aged to viscosity and be 10 handkerchief seconds, obtain spinning property zirconium white precursor sol, carry out spinning with the dry-spinning technology then and make gelled fibre, drying is put into tube furnace with gelled fibre again, heat, be warming up to 400 ℃ by 0.5 ℃/component velocity, constant temperature 1 hour is warming up to 1200 ℃ by 100 ℃/component velocity then, constant temperature is 10 minutes again, below the fast cooling to 1000 ℃, naturally cooling is reduced to room temperature then, obtains ZrO
2Continuous fibre.The crystal formation of fiber is a tetragonal phase structure, Fibre diameter 7 μ m, and tensile strength is 2.4GPa.
Embodiment 2
In 1.60: 1 ratios with 32g ZrOCl
28H
2O is dissolved in the 20g water and obtains ZrOCl
2The aqueous solution is to ZrOCl
2Add 2gY (NO in the aqueous solution
3)
36H
2O, then with solution at 40 ℃ of following heating in water bath, in the aqueous solution, add 5.4g sucrose, and fully stir and make its dissolving, in solution, add the 6g Glacial acetic acid then, continue to stir 2 hours with agitator, naturally cooling, Cl is removed in electrolysis then
-, at room temperature be aged to viscosity and be 100 handkerchief seconds, obtain spinning property zirconium white precursor sol, carry out spinning with the dry-spinning technology then and make gelled fibre, drying is put into tube furnace with gelled fibre again, heat, be warming up to 600 ℃ by 1 ℃/component velocity, constant temperature 2 hours is warming up to 1380 ℃ by 400 ℃/component velocity then, constant temperature is 10 minutes again, below the fast cooling to 1000 ℃, naturally cooling is reduced to room temperature then, obtains ZrO
2Continuous fibre.The crystal formation four directions phase and the monocline phase structure of fiber, wherein the four directions is about 70% mutually, and monocline is about 30% mutually, Fibre diameter 9 μ m, tensile strength is 2.6GPa.
Embodiment 3
In 1.45: 1 ratios with 29g ZrOCl
28H
2O is dissolved in the 20g water and obtains ZrOCl
2The aqueous solution is to ZrOCl
2Add 2.9gY (NO in the aqueous solution
3)
36H
2O, then with solution at 40 ℃ of following heating in water bath, in the aqueous solution, add 2.9g glucose, and fully stir and make its dissolving, in solution, add the 22g Glacial acetic acid then, continue to stir 2 hours with agitator, naturally cooling, Cl is removed in electrolysis then
-, at room temperature be aged to viscosity and be 10 handkerchief seconds, obtain spinning property zirconium white precursor sol, carry out spinning with the dry-spinning technology then and make gelled fibre, drying is put into tube furnace with gelled fibre again, heat, be warming up to 400 ℃ by 0.5 ℃/component velocity, constant temperature 1 hour is warming up to 1200 ℃ by 100 ℃/component velocity then, constant temperature is 10 minutes again, below the fast cooling to 1000 ℃, naturally cooling is reduced to room temperature then, obtains ZrO
2Continuous fibre.The crystal formation of fiber is a tetragonal phase structure, Fibre diameter 8 μ m, and tensile strength is 2.5GPa.
Embodiment 4
In 1.60: 1 ratios with 32g ZrOCl
28H
2O is dissolved in the 20g water and obtains ZrOCl
2The aqueous solution is to ZrOCl
2Add 2gY (NO in the aqueous solution
3)
36H
2O, then with solution at 40 ℃ of following heating in water bath, in the aqueous solution, add 2.7g glucose or fructose, and fully stir and make its dissolving, in solution, add the 6g Glacial acetic acid then, continue to stir 2 hours with agitator, naturally cooling, Cl is removed in electrolysis then
-, at room temperature be aged to viscosity and be 100 handkerchief seconds, obtain spinning property zirconium white precursor sol, carry out spinning with the dry-spinning technology then and make gelled fibre, drying is put into tube furnace with gelled fibre again, heat, be warming up to 600 ℃ by 1 ℃/component velocity, constant temperature 2 hours is warming up to 1380 ℃ by 400 ℃/component velocity then, constant temperature is 10 minutes again, below the fast cooling to 1000 ℃, naturally cooling is reduced to room temperature then, obtains ZrO
2Continuous fibre.The crystal formation four directions phase and the monocline phase structure of fiber, wherein the four directions is about 70% mutually, and monocline is about 30% mutually, Fibre diameter 10 μ m, tensile strength is 2.6GPa.
Embodiment 5
In 1.45: 1 ratios with 29g ZrOCl
28H
2O is dissolved in the 20g water and obtains ZrOCl
2The aqueous solution is to ZrOCl
2Add 2.9gY (NO in the aqueous solution
3)
36H
2O, then with solution at 40 ℃ of following heating in water bath, in the aqueous solution, add the 14.5g citric acid, and fully stir and make its dissolving, in solution, add the 22g Glacial acetic acid then, continue to stir 2 hours with agitator, naturally cooling, Cl is removed in electrolysis then
-, at room temperature be aged to viscosity and be 10 handkerchief seconds, obtain spinning property zirconium white precursor sol, carry out spinning with the dry-spinning technology then and make gelled fibre, drying is put into tube furnace with gelled fibre again, heat, be warming up to 400 ℃ by 0.5 ℃/component velocity, constant temperature 1 hour is warming up to 1200 ℃ by 100 ℃/component velocity then, constant temperature is 10 minutes again, below the fast cooling to 1000 ℃, naturally cooling is reduced to room temperature then, obtains ZrO
2Continuous fibre.The crystal formation of fiber is a tetragonal phase structure, Fibre diameter 8 μ m, and tensile strength is 2.4GPa.
Embodiment 6
In 1.60: 1 ratios with 32g ZrOCl
28H
2O is dissolved in the 20g water and obtains ZrOCl
2The aqueous solution is to ZrOCl
2Add 2gY (NO in the aqueous solution
3)
36H
2O, then with solution at 40 ℃ of following heating in water bath, in the aqueous solution, add the 5.3g citric acid, and fully stir and make its dissolving, in solution, add the 6g Glacial acetic acid then, continue to stir 2 hours with agitator, naturally cooling, Cl is removed in electrolysis then
-, at room temperature be aged to viscosity and be 100 handkerchief seconds, obtain spinning property zirconium white precursor sol, carry out spinning with the dry-spinning technology then and make gelled fibre, drying is put into tube furnace with gelled fibre again, heat, be warming up to 600 ℃ by 1 ℃/component velocity, constant temperature 2 hours is warming up to 1380 ℃ by 400 ℃/component velocity then, constant temperature is 10 minutes again, below the fast cooling to 1000 ℃, naturally cooling is reduced to room temperature then, obtains ZrO
2Continuous fibre.The crystal formation four directions phase and the monocline phase structure of fiber, wherein the four directions is about 70% mutually, and monocline is about 30% mutually, Fibre diameter 10 μ m, tensile strength is 2.4GPa.
Embodiment 7
In 1.60: 1 ratios with 32gZrOCl
28H
2O is dissolved in the 20g water, obtains ZrOCl
2The aqueous solution is to ZrOCl
2The aqueous solution in add 2.5gY (NO
3)
36H
2O, then with solution at 40 ℃ of following heating in water bath, in the aqueous solution, add 5g sucrose and 10g citric acid, and fully stir and make its dissolving, in solution, add the 7g Glacial acetic acid, continue to stir 1h with agitator, Cl is removed in electrolysis under the room temperature then
-, at room temperature be aged to viscosity and be 57 handkerchief seconds, obtain spinning property zirconium white precursor sol, carry out spinning with the dry-spinning technology then and make gelled fibre, drying is put into tube furnace with gelled fibre again, heat, be warming up to 600 ℃ by 1 ℃/component velocity, constant temperature 2 hours is warming up to 1370 ℃ by 500 ℃/component velocity then, constant temperature is 10 minutes again, below the fast cooling to 1000 ℃, naturally cooling is reduced to room temperature then, obtains ZrO
2Continuous fibre.The crystal formation four directions phase and the monocline phase structure of fiber, wherein the four directions is about 85% mutually, and monocline is about 15% mutually, Fibre diameter 9 μ m, tensile strength is 2.6GPa.
Embodiment 8
Press 1.45: 1 with 29gZrOCl
28H
2O is dissolved in the 20g water, obtains ZrOCl
2The aqueous solution is to ZrOCl
2The aqueous solution in add 1.85gY (NO
3)
36H
2O, then with solution at 40 ℃ of following heating in water bath, in the aqueous solution, add 2.9g glucose, 2.6g fructose, 10g citric acid and fully stir and make its dissolving, add the 8g Glacial acetic acid then in the solution, continue to stir 1h with agitator, naturally cooling, Cl is removed in electrolysis under the room temperature then
-, at room temperature be aged to viscosity and be 48 handkerchief seconds, obtain spinning property zirconium white precursor sol, carry out spinning with the dry-spinning technology then and make gelled fibre, drying is put into tube furnace with gelled fibre again, heat, be warming up to 600 ℃ by 1 ℃/component velocity, constant temperature 2 hours is warming up to 1350 ℃ by 400 ℃/component velocity then, constant temperature is 10 minutes again, below the fast cooling to 1000 ℃, naturally cooling is reduced to room temperature then, obtains ZrO
2Continuous fibre.The crystal formation four directions phase and the monocline phase structure of fiber, wherein the four directions is about 70% mutually, and monocline is about 30% mutually, Fibre diameter 9 μ m, tensile strength is 2.5GPa.
Claims (2)
1. the preparation method of a zirconium oxide ceramic continuous fibre, it is characterized in that utilizing zirconium oxychloride and Yttrium trinitrate as raw material, get sucrose, glucose, one or both in fructose or the citric acid or two or more miscellany are made additive, make precursor sol through electrolysis, colloidal sol obtains the spinning property precursor sol through overaging then, again through obtaining the xerogel fiber, high temperature sintering xerogel fiber after the spinning drying, make zirconium oxide ceramic continuous fibre, concrete preparation process is as follows:
(1) preparation of spinning property precursor sol
Press ZrOCl
28H
2O is 1.45～1.60: 1 with the ratio of pure water weight, with ZrOCl
28H
2The water-soluble zirconium oxychloride aqueous solution that obtains of O is pressed mass ratio ZrOCl
28H
2O: Y (NO
3)
36H
2O=10～16: 1 adds Y (NO in zirconium oxychloride aqueous solution
3)
36H
2O, then with solution at 40 ℃ of following heating in water bath, and add organic additive, organic additive is one or both or the two or more mixture in sucrose, glucose, fructose or the citric acid, wherein presses mass ratio ZrOCl
28H
2O: sucrose=4～6: 1, ZrOCl
28H
2O: glucose or fructose=10～12: 1, ZrOCl
28H
2O: citric acid=2～6: 1, the mixed additive ratio fully stirs and makes its dissolving this interval adjustment, add Glacial acetic acid then in solution, wherein the mass ratio of zirconium oxychloride and Glacial acetic acid is 1.3～5.4: 1, uses agitator continuously stirring 1～2 hour, naturally cooling, Cl is removed in electrolysis then
-, at room temperature be aged to viscosity and reach 10-100 handkerchief second, obtain the spinning property precursor sol;
(2) make the spinning property precursor sol after, utilize the dry-spinning technology to carry out the spinning drying and make the xerogel fiber;
(3) again the xerogel fiber being put into tube furnace heats, be warming up to 400 ℃～600 ℃ by 0.5 ℃～1 ℃/minute speed, constant temperature 1～2 hour, be warming up to 1200 ℃～1380 ℃ by 〉=100 ℃/minute speed then, constant temperature is 10 minutes again, be quickly cooled to below 1000 ℃, reduce to room temperature more naturally, obtain zirconium oxide ceramic continuous fibre.
2. the preparation method of zirconium oxide ceramic continuous fibre according to claim 1 is characterized in that the thing of the zirconium oxide ceramic continuous fibre that makes is tetragonal phase structure mutually, and Fibre diameter is 7～10 μ m, and tensile strength is 2.4～2.7GPa.
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| CN101362649B (en) * | 2008-07-01 | 2011-02-09 | 北京师范大学 | Method for preparing electro spinning mesoporous zircite fiber film |
| CN102465357B (en) * | 2010-11-19 | 2013-10-02 | 山东鲁阳股份有限公司 | Preparation method of polycrystal zirconia fiber and zirconia/alumina composite fiber |
| CN103614809B (en) * | 2012-08-07 | 2015-07-29 | 山东大学 | The pressure resolver of poly-acetyl acetone zirconium precursor body fiber in zirconia crystal fiber preparation |
| CN102775143A (en) * | 2012-08-22 | 2012-11-14 | 安徽同和晶体新材料股份有限公司 | Method for preparing fully-stabilized tetragonal-phase zirconia crystal fibers |
| CN103451851B (en) * | 2013-08-21 | 2016-05-11 | 东华大学 | A kind of preparation method of pliable and tough high-strength zirconia nano fibrous membrane |
| CN104357954B (en) * | 2014-10-15 | 2017-05-10 | 南华大学 | Auxiliary preparation process of spinnable and weavable long continuous zirconia fiber |
| CN106012105B (en) * | 2016-07-26 | 2018-06-08 | 苏州大学 | A kind of method that air bubble spinning prepares zirconia nanopowder fiber |
| CN111996825B (en) * | 2020-08-24 | 2022-04-12 | 山东大学 | Zirconium oxide continuous fiber braided rope and preparation method thereof |
| CN112521614B (en) * | 2020-11-19 | 2021-09-21 | 华南理工大学 | Water-soluble zirconium oxide precursor and preparation method and application thereof |
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