CN103757749A - Preparation method for zirconia crystal fiber - Google Patents
Preparation method for zirconia crystal fiber Download PDFInfo
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- CN103757749A CN103757749A CN201310688860.4A CN201310688860A CN103757749A CN 103757749 A CN103757749 A CN 103757749A CN 201310688860 A CN201310688860 A CN 201310688860A CN 103757749 A CN103757749 A CN 103757749A
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Abstract
The invention discloses a preparation method for a zirconia crystal fiber. The preparation method comprises the following steps: preparing zirconium acetate and yttrium nitrate so as to obtain a spinnable zirconium acetate colloid; then allowing the spinnable zirconium acetate colloid to pass through a high-speed centrifugation fiber throwing machine so as to obtain a zirconium-containing gel fiber; and carrying out heat treatment so as to obtain the zirconia crystal fiber with a diameter of 3 to 6 (mu m) and stable performance. The zirconia crystal fiber has high purity, good strength, a small diameter, low thermal conductivity, long-time high temperature resistance and better stability.
Description
Technical field
The present invention relates to a kind of preparation method of crystal of zirconium oxide fiber.
Background technology
The heat insulation performance of Zirconium oxide fibre has the features such as unit weight is little, thermal conductivity is low, the heat-resisting height of aerobic environment (2500 ℃ still can keep good fibre morphology in atmosphere), and determine that thus it has huge application demand in national defence hard-core technology and advanced civilian industry, therefore, the development of extraordinary crystal fibre and application are one of modern material science and technology important development directions.
Due to the low viscosity characteristics of zirconic high-melting-point and melt, can not adopt the melting throwing method as alumina silicate and high alumina ceramic fiber, and can only adopt precursor process to prepare, general with having support methods, inorganic salts method at present.
Support methods is by after entering the inorfils such as the organic fibers such as artificial silk or charcoal fiber by dipping containing inorganic salts (as zirconium nitrate, the zirconium oxychloride) aqueous solution of zirconium, this " loading precursor fibre " is placed in to specific atmosphere carries out pyrolysis heat-treat (burning till) again after hydrocarbon, carbon part decomposes, carrier fibre is fully oxidized, zirconates changes into zirconia, the final Zirconium oxide fibre that keeps fibrillation microstructure that obtains.
Inorganic salts method is to take water-soluble zirconates as raw material, add a certain amount of water soluble polymer organic matter to make mixed liquor, after filtration, add stabilizing agent, heating is concentrated to suitable viscosity (100～350Pas), fibration under specific humidity and temperature condition, fibration can adopt spray silk, wire drawing and rotation to get rid of the methods such as silk, and fibrillation obtains Zirconium oxide fibre after dry burning till at a certain temperature.
Above method all relates to a large amount of ethanol, methyl alcohol, inflammable and explosive and the toxic organic compound such as acetylacetone,2,4-pentanedione is as solvent and participate in building-up process, and expects that from former obtaining fibroblast gel all needs the above synthesis procedure of three steps, causes production technology danger, operation is loaded down with trivial details and benefit is low.And the Zirconium oxide fibre of preparing is uneven in aspect quality levels such as purity, stability, intensity, diameters.
Summary of the invention
The object of this invention is to provide that a kind of production cycle is shorter, purity is high, intensity good, diameter is thin, thermal conductivity is low, the better crystal of zirconium oxide fiber of long-time heat-resistant stable performance.
The technical solution used in the present invention is: a kind of preparation method of crystal of zirconium oxide fiber, and step is as follows:
(1) preparation of spinnability acetic acid colloidal zirconia
By acetic acid zirconium, be 1:0.045～0.228 with the ratio of yttrium nitrate weight, fully stir it is mixed, then under 45 ℃～75 ℃ conditions, be concentrated into viscosity and reach 8～25Pa.s, make presoma acetic acid zirconium colloidal sol, finally under 15 ℃ ~ 45 ℃ conditions, be aged to 60～100Pa.s, obtain spinnability acetic acid colloidal zirconia;
(2) moulding of gelatinous fibre:
The above-mentioned spinnability acetic acid colloidal zirconia making is obtained containing zirconium gelatinous fibre through high speed centrifugation tumbling machine;
(3) heat treatment of crystal of zirconium oxide fiber:
First by above-mentioned putting into high-temperature roller kiln stove and heat containing zirconium gelatinous fibre of making, with the speed of 1.5～2 ℃/min, be warming up to 550 ℃, constant temperature 1
; Secondly the speed with 5～10 ℃/min is warming up to 1050 ℃, then constant temperature 1
; Then be quickly cooled to room temperature, obtaining diameter is 3～6
the crystal of zirconium oxide fiber of stable performance.
As a further improvement on the present invention, the spinnability acetic acid colloidal zirconia of spinnability colloid for obtaining by aqueous systems sol-gel process in step (2).
As a further improvement on the present invention, the working environment of the high speed centrifugation tumbling machine in step (2) answers constant temperature at 20～35 ℃.
As a further improvement on the present invention, the rotating speed of high speed centrifugation tumbling machine is between 10000～13000r/min.
As a further improvement on the present invention, the high-temperature roller kiln stove using in step (3) is to heat by electric energy.
As a further improvement on the present invention, the crystalline phase of crystal of zirconium oxide fiber is that Tetragonal and Emission in Cubic mix phase, and can accomplish single-phase.
The invention has the beneficial effects as follows: by raw material acetic acid zirconium and yttrium nitrate, preparation, the moulding of gelatinous fibre, three steps of the heat treatment of crystal of zirconium oxide fiber through aqueous systems one-step synthesis sol-gel process spinnability acetic acid colloidal zirconia, can make the crystal of zirconium oxide fiber of stable performance, this explained hereafter raw material only needs two kinds, colloid preparation only needs one-step synthesis, and the colloid purity that makes is high, quality is good.Therefore adopt that this kind of method technique production cycle simpler, product is shorter, fiber product intensity is better.
The specific embodiment
A preparation method for crystal of zirconium oxide fiber, step is as follows:
(1) preparation of spinnability acetic acid colloidal zirconia
By acetic acid zirconium, be 1:0.045～0.228 with the ratio of yttrium nitrate weight, fully stir it is mixed, then under 45 ℃～75 ℃ conditions, be concentrated into viscosity and reach 8～25Pa.s, make presoma acetic acid zirconium colloidal sol, finally under 15 ℃ ~ 45 ℃ conditions, be aged to 60～100Pa.s, obtain spinnability acetic acid colloidal zirconia;
(2) moulding of gelatinous fibre:
The above-mentioned spinnability acetic acid colloidal zirconia making is obtained containing zirconium gelatinous fibre through high speed centrifugation tumbling machine;
(3) heat treatment of crystal of zirconium oxide fiber:
First by above-mentioned putting into high-temperature roller kiln stove and heat containing zirconium gelatinous fibre of making, with the speed of 1.5～2 ℃/min, be warming up to 550 ℃, constant temperature 1
; Secondly the speed with 5～10 ℃/min is warming up to 1050 ℃, then constant temperature 1
; Then be quickly cooled to room temperature, obtaining diameter is 3～6
the crystal of zirconium oxide fiber of stable performance.
As a further improvement on the present invention, the spinnability acetic acid colloidal zirconia of spinnability colloid for obtaining by aqueous systems sol-gel process in step (2).
As a further improvement on the present invention, the working environment of the high speed centrifugation tumbling machine in step (2) answers constant temperature at 20～35 ℃.
As a further improvement on the present invention, the rotating speed of high speed centrifugation tumbling machine is between 10000～13000r/min.
As a further improvement on the present invention, the high-temperature roller kiln stove using in step (3) is to heat by electric energy.
Embodiment 1:
7.2g yttrium nitrate is poured in 100g acetic acid zirconium liquid and stirred, fully stir it is uniformly dissolved, then under 45 ℃ of conditions, be concentrated into viscosity and reach 8Pa.s, make presoma acetic acid zirconium colloidal sol, finally presoma acetic acid zirconium colloidal sol is aged to 60Pa.s under 15 ℃ of conditions, obtains spinnability acetic acid colloidal zirconia.Spinnability acetic acid colloidal zirconia is got rid of to an equipment through high speed centrifugation to be obtained containing zirconium gelatinous fibre. and will put into high-temperature roller kiln stove containing zirconium gelatinous fibre and heat, by the speed of 1.5 ℃/min, be warming up to 550 ℃, constant temperature 1 hour, then the speed of 5 ℃/min is warming up to 1050 ℃, constant temperature is 1 hour again, be quickly cooled to room temperature, obtain crystal of zirconium oxide fiber.The crystal formation of fiber is tetragonal phase structure, fibre diameter approximately 6 μ m.
Embodiment 2:
11.2g yttrium nitrate is poured in 100g acetic acid zirconium liquid and stirred, fully stir it is uniformly dissolved, then under 55 ℃ of conditions, be concentrated into viscosity and reach 12Pa.s, make presoma acetic acid zirconium colloidal sol, finally presoma acetic acid zirconium colloidal sol is aged to 70Pa.s under 20 ℃ of conditions, obtains spinnability acetic acid colloidal zirconia.Spinnability acetic acid colloidal zirconia is got rid of to an equipment through high speed centrifugation to be obtained containing zirconium gelatinous fibre. and will put into high-temperature roller kiln stove containing zirconium gelatinous fibre and heat, by the speed of 1.6 ℃/min, be warming up to 550 ℃, constant temperature 1 hour, then the speed of 6 ℃/min is warming up to 1050 ℃, constant temperature is 1 hour again, be quickly cooled to room temperature, obtain crystal of zirconium oxide fiber.The crystal formation of fiber is Tetragonal and Emission in Cubic structure, and wherein, in the product of gained, Tetragonal accounts for 50% of product quality, and Emission in Cubic accounts for 50% of product quality mutually, fibre diameter approximately 5 μ m.
Embodiment 3:
15.2g yttrium nitrate is poured in 100g acetic acid zirconium liquid and stirred, fully stir it is uniformly dissolved, then under 60 ℃ of conditions, be concentrated into viscosity and reach 15Pa.s, make presoma acetic acid zirconium colloidal sol, finally presoma acetic acid zirconium colloidal sol is aged to 80Pa.s under 25 ℃ of conditions, obtains spinnability acetic acid colloidal zirconia.Spinnability acetic acid colloidal zirconia is got rid of to an equipment through high speed centrifugation to be obtained containing zirconium gelatinous fibre. and will put into high-temperature roller kiln stove containing zirconium gelatinous fibre and heat, by the speed of 1.7 ℃/min, be warming up to 550 ℃, constant temperature 1 hour, then the speed of 7 ℃/min is warming up to 1050 ℃, constant temperature is 1 hour again, be quickly cooled to room temperature, obtain crystal of zirconium oxide fiber.The crystal formation of fiber is Emission in Cubic structure, fibre diameter approximately 4 μ m.
Embodiment 4:
7.2g yttrium nitrate is poured in 100g acetic acid zirconium liquid and stirred, fully stir it is uniformly dissolved, then under 65 ℃ of conditions, be concentrated into viscosity and reach 18Pa.s, make presoma acetic acid zirconium colloidal sol, finally presoma acetic acid zirconium colloidal sol is aged to 90Pa.s under 30 ℃ of conditions, obtains spinnability acetic acid colloidal zirconia.Spinnability acetic acid colloidal zirconia is got rid of to an equipment through high speed centrifugation to be obtained containing zirconium gelatinous fibre. and will put into high-temperature roller kiln stove containing zirconium gelatinous fibre and heat, by the speed of 1.8 ℃/min, be warming up to 550 ℃, constant temperature 1 hour, then the speed of 8 ℃/min is warming up to 1050 ℃, constant temperature is 1 hour again, be quickly cooled to room temperature, obtain crystal of zirconium oxide fiber.The crystal formation of fiber is tetragonal phase structure, fibre diameter approximately 4 μ m.
Embodiment 5:
11.2g yttrium nitrate is poured in 100g acetic acid zirconium liquid and stirred, fully stir it is uniformly dissolved, then under 70 ℃ of conditions, be concentrated into viscosity and reach 21Pa.s, make presoma acetic acid zirconium colloidal sol, finally presoma acetic acid zirconium colloidal sol is aged to 100Pa.s under 35 ℃ of conditions, obtains spinnability acetic acid colloidal zirconia.Spinnability acetic acid colloidal zirconia is got rid of to an equipment through high speed centrifugation to be obtained containing zirconium gelatinous fibre. and will put into high-temperature roller kiln stove containing zirconium gelatinous fibre and heat, by the speed of 1.9 ℃/min, be warming up to 550 ℃, constant temperature 1 hour, then the speed of 9 ℃/min is warming up to 1050 ℃, constant temperature is 1 hour again, be quickly cooled to room temperature, obtain crystal of zirconium oxide fiber.The crystal formation of fiber is Tetragonal and Emission in Cubic structure, and wherein, in the product of gained, Tetragonal accounts for 50% of product quality, and Emission in Cubic accounts for 50% of product quality mutually, fibre diameter approximately 3 μ m.
Embodiment 6:
15.2g yttrium nitrate is poured in 100g acetic acid zirconium liquid and stirred, fully stir it is uniformly dissolved, then under 75 ℃ of conditions, be concentrated into viscosity and reach 25Pa.s, make presoma acetic acid zirconium colloidal sol, finally presoma acetic acid zirconium colloidal sol is aged to 100Pa.s under 45 ℃ of conditions, obtains spinnability acetic acid colloidal zirconia.Spinnability acetic acid colloidal zirconia is got rid of to an equipment through high speed centrifugation to be obtained containing zirconium gelatinous fibre. and will put into high-temperature roller kiln stove containing zirconium gelatinous fibre and heat, by the speed of 2 ℃/min, be warming up to 550 ℃, constant temperature 1 hour, then the speed of 10 ℃/min is warming up to 1050 ℃, constant temperature is 1 hour again, be quickly cooled to room temperature, obtain crystal of zirconium oxide fiber.The crystal formation of fiber is Emission in Cubic structure, fibre diameter approximately 3 μ m.
Claims (6)
1. a preparation method for crystal of zirconium oxide fiber, is characterized in that adopting following steps:
(1) preparation of spinnability acetic acid colloidal zirconia
By acetic acid zirconium, be 1:0.045～0.228 with the ratio of yttrium nitrate weight, fully stir it is mixed, then under 45 ℃～75 ℃ conditions, be concentrated into viscosity and reach 8～25Pa.s, make presoma acetic acid zirconium colloidal sol, finally under 15 ℃ ~ 45 ℃ conditions, be aged to 60～100Pa.s, obtain spinnability acetic acid colloidal zirconia;
(2) moulding of gelatinous fibre:
The above-mentioned spinnability acetic acid colloidal zirconia making is obtained containing zirconium gelatinous fibre through high speed centrifugation tumbling machine;
(3) heat treatment of crystal of zirconium oxide fiber:
First by above-mentioned putting into high-temperature roller kiln stove and heat containing zirconium gelatinous fibre of making, with the speed of 1.5～2 ℃/min, be warming up to 550 ℃, constant temperature 1
; Secondly the speed with 5～10 ℃/min is warming up to 1050 ℃, then constant temperature 1
; Then be quickly cooled to room temperature, obtaining diameter is 3～6
the crystal of zirconium oxide fiber of stable performance.
2. the preparation method of a kind of crystal of zirconium oxide fiber according to claim 1, is characterized in that: the spinnability acetic acid colloidal zirconia of spinnability colloid for obtaining by aqueous systems sol-gel process in step (2).
3. the preparation method's of a kind of crystal of zirconium oxide fiber according to claim 1 preparation method, is characterized in that: the working environment of the high speed centrifugation tumbling machine in described step (2) answers constant temperature at 20～35 ℃.
4. the preparation method of a kind of crystal of zirconium oxide fiber according to claim 3, is characterized in that: the rotating speed of described high speed centrifugation tumbling machine is between 10000～13000r/min.
5. the preparation method of a kind of crystal of zirconium oxide fiber according to claim 1, is characterized in that: the high-temperature roller kiln stove using in described step (3) is to heat by electric energy.
6. the preparation method of a kind of crystal of zirconium oxide fiber according to claim 1, is characterized in that: the crystalline phase of described crystal of zirconium oxide fiber is that Tetragonal and Emission in Cubic mix phase, and can accomplish single-phase.
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| CN201310688860.4A CN103757749A (en) | 2013-12-17 | 2013-12-17 | Preparation method for zirconia crystal fiber |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104141181A (en) * | 2014-07-22 | 2014-11-12 | 南京理工宇龙新材料科技有限公司 | Preparation method for ZrO2 fiber with SiO2 doped |
| CN106117560A (en) * | 2016-07-19 | 2016-11-16 | 安徽同和晶体新材料股份有限公司 | A kind of preparation method of the aqueous solution being polymerized hydroxyacetic acid zirconium |
| CN106637510A (en) * | 2017-01-10 | 2017-05-10 | 安徽同和晶体新材料股份有限公司 | Preparation method of zirconium oxide fibers |
| CN114836850A (en) * | 2022-05-17 | 2022-08-02 | 哈尔滨工业大学 | Hollow zirconia fiber and template-free preparation method thereof |
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| JPH04100921A (en) * | 1990-08-17 | 1992-04-02 | Nippon Shokubai Co Ltd | Production of zirconia-based fiber |
| CN1459418A (en) * | 2003-06-10 | 2003-12-03 | 山东大学 | Method and equipment of preparing high performance zirconium oxide continuous fiber |
| CN102557628A (en) * | 2011-12-29 | 2012-07-11 | 山东大学 | Flexible yttrium stable zirconium oxide ceramic fiber and preparation method thereof |
| CN103193480A (en) * | 2013-03-11 | 2013-07-10 | 绍兴市圣诺超高温晶体纤维材料有限公司 | Preparation method of high-performance zirconia ceramic fibers |
| CN103408292A (en) * | 2013-07-26 | 2013-11-27 | 山东大学 | Preparation method for alumina-zirconia ceramic fiber |
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2013
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Patent Citations (5)
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|---|---|---|---|---|
| JPH04100921A (en) * | 1990-08-17 | 1992-04-02 | Nippon Shokubai Co Ltd | Production of zirconia-based fiber |
| CN1459418A (en) * | 2003-06-10 | 2003-12-03 | 山东大学 | Method and equipment of preparing high performance zirconium oxide continuous fiber |
| CN102557628A (en) * | 2011-12-29 | 2012-07-11 | 山东大学 | Flexible yttrium stable zirconium oxide ceramic fiber and preparation method thereof |
| CN103193480A (en) * | 2013-03-11 | 2013-07-10 | 绍兴市圣诺超高温晶体纤维材料有限公司 | Preparation method of high-performance zirconia ceramic fibers |
| CN103408292A (en) * | 2013-07-26 | 2013-11-27 | 山东大学 | Preparation method for alumina-zirconia ceramic fiber |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104141181A (en) * | 2014-07-22 | 2014-11-12 | 南京理工宇龙新材料科技有限公司 | Preparation method for ZrO2 fiber with SiO2 doped |
| CN106117560A (en) * | 2016-07-19 | 2016-11-16 | 安徽同和晶体新材料股份有限公司 | A kind of preparation method of the aqueous solution being polymerized hydroxyacetic acid zirconium |
| CN106117560B (en) * | 2016-07-19 | 2017-05-17 | 安徽同和晶体新材料股份有限公司 | Preparation method of aqueous solution of ployhydroxy zirconium acetate |
| CN106637510A (en) * | 2017-01-10 | 2017-05-10 | 安徽同和晶体新材料股份有限公司 | Preparation method of zirconium oxide fibers |
| CN106637510B (en) * | 2017-01-10 | 2018-12-11 | 安徽同和晶体新材料股份有限公司 | A kind of preparation method of Zirconium oxide fibre |
| CN114836850A (en) * | 2022-05-17 | 2022-08-02 | 哈尔滨工业大学 | Hollow zirconia fiber and template-free preparation method thereof |
| CN114836850B (en) * | 2022-05-17 | 2023-08-04 | 哈尔滨工业大学 | Hollow zirconia fiber and template-free preparation method thereof |
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