CN1137297C - Process for preparing aluminium oxide-zirconium oxide fibres - Google Patents
Process for preparing aluminium oxide-zirconium oxide fibres Download PDFInfo
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- CN1137297C CN1137297C CNB011111860A CN01111186A CN1137297C CN 1137297 C CN1137297 C CN 1137297C CN B011111860 A CNB011111860 A CN B011111860A CN 01111186 A CN01111186 A CN 01111186A CN 1137297 C CN1137297 C CN 1137297C
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- aluminium
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Abstract
The present invention relates to a method for preparing aluminium oxide-zirconium oxide fibers. Water solubility inorganic aluminum salt, water solubility inorganic zirconium salt and metallic aluminium are used as principal raw materials, and distilled water is used as a solvent. Under a reflux condition, homogeneous and transparent sol is prepared by the methods of hydrolysis and aggregation. Eligible water soluble polymers are added in the sol and are used as a spinning assisting agent. After the mixture of the sol and the spinning assisting agent is concentrated, thread spinning original liquid which has eligible flow performance is obtained. The thread spinning original liquid is spun into precursor fibers which are further thermally treated to convert the precursors of zluminum oxide and zirconium oxide into the aluminum oxide and the zirconium oxide. Thus, the aluminum oxide-zirconium oxide fibers of the present invention are obtained. The present invention has the advantage of simple technology, and the performance of the prepared aluminum oxide-zirconium oxide fibers is homogeneous and stable.
Description
The present invention relates to a kind of preparation method of inorfil, relate in particular to a kind of preparation method who contains zirconia and alumina fibre.
Alumina fibre be from last century the seventies begin to develop abroad a kind of comparatively rapidly fiber.Because alumina fibre has good chemical inertness, the excellent high-temperature mechanical property, higher specific surface and low a series of performances such as thermal conductivity, as the high temperature insulating acoustic material, catalyst base, and Metal Substrate, ceramic matric composite reinforcing agent, alumina fibre has purposes widely.Especially in the last few years along with the continuous development and the application of fiber reinforcement matrix (resin, metal and pottery etc.) performance composite, alumina fibre received the concern of material circle more, and its performance has also been had higher requirement.The improvement that the manufacturing of external alumina fibre is also only paid attention to technical recipe and route by the seventies changes into gradually more payes attention to various oxides and heteroatomic interpolation at present, and these additives are the most frequently used silicon, and other have zirconium, phosphorus, hafnium, yttrium etc.By the interpolation of these materials, can not only improve the intensity of alumina fibre, and can give some other excellent properties of alumina fibre such as high-temperature creep resistance etc.CN1035479 and ZL98109101 have reported to be silica is introduced in the silicon source in the pure alumina fiber method with the ethyl orthosilicate respectively.According to studies show that in a large number, because the toughening effect of zirconic tetragonal structure, zirconia can effectively suppress grain growth in the existence of alumina fibre, thereby improves fiber high temperature intensity.U.S.Pat.No.5,002,906 has reported the preparation method of a kind of aluminium oxide-Zirconium oxide fibre of U.S. Du Pont company invention.This method makes alumina powder jointed and hydroxy chlorination aluminium at 30 ℃～60 ℃ polymerization reaction take places earlier, then adds zirconium saline solution, the blend spinning liquid that is grouped into by these three kinds of one-tenth again through concentrate, spinning and heat treatment obtains aluminium oxide-Zirconium oxide fibre.Because the introducing of zirconium is the way that adopts mechanical mixture in above-mentioned preparation process, so wherein the mixing of aluminium and zirconium is difficult for reaching evenly, and this spinning solution concentrate and spinning process in be easy to generate doubtful glue and foam, make its character very unstable.For controlling the generation of these unfavorable factors, said process needs at lower temperature conditions, or even is lower than under the situation of room temperature and carries out, thereby has increased the complexity of whole preparation process, finally also can have influence on the uniform and stable of fibre property.
It is simple to the purpose of this invention is to provide a kind of technology, the preparation method of aluminium oxide-Zirconium oxide fibre that fibre property is uniform and stable.
The object of the present invention is achieved like this, is main raw material with water-soluble inorganic aluminium salt, water-soluble inorganic zirconates and metallic aluminium, is solvent with distilled water, under refluxad makes the colloidal sol of homogeneous transparent by hydrolysis, polymerization.In this colloidal sol, add suitable water soluble polymer as spinning-aid agent, after concentrating, make spinning solution with suitable rheological property.This spinning solution is spun into precursor fibre through blowing process.Precursor fibre makes aluminium oxide, zirconia presoma be converted into aluminium oxide and zirconia through further heat treatment again, thereby finally obtains aluminium oxide-Zirconium oxide fibre of the present invention.
The preparation method of aluminium oxide-Zirconium oxide fibre provided by the invention comprises the steps:
(1) water-soluble inorganic aluminium salt, metallic aluminium and water-soluble inorganic zirconates are measured with oxide respectively, its oxide mass ratio is 1: 1～6.5: 0.2～1, water-soluble inorganic aluminium salt and water-soluble inorganic zirconates are dissolved in the distilled water of 1～5 times of quality in proportion, through stirring or after mild heat dissolves two kinds of inorganic salts fully, add metallic aluminium in proportion, after temperature is to react 5～20 hours under 90 ℃～110 ℃ counterflow conditions, filter rapidly, obtain water white aluminium oxide-Zirconium oxide fibre precursor sol;
(2) with aluminium oxide: the ratio of high molecular weight water soluble polymer=100: 0.2～20, in colloidal sol, add high molecular weight water soluble polymer as spinning-aid agent, after making it be dissolved in colloidal sol fully, in temperature is to concentrate under 30 ℃～80 ℃ conditions, and obtaining viscosity is the spinning solution of 10～40 pools (20 ℃);
(3) spinning solution is poured into liquid tank in the device for spinning, control air pressure is 0.05～0.5MPa, hydraulic pressure is 0.01～0.1MPa, keep the liquid flow path direction to become 20 °～60 ° angles with airflow direction, being 15 ℃～40 ℃ in temperature is under 20%～80% condition above-mentioned spinning solution to be jetted fibre with relative humidity, obtains precursor fibre of the present invention;
(4) precursor fibre at first under being 100 ℃～150 ℃ condition, temperature is sloughed part fiber contained humidity, in 250 ℃～350 ℃ the low temperature oven that is connected with nitrogen, handled 10～90 minutes then, last roasting 10～60 minutes under 900 ℃～1200 ℃ the temperature conditions in air atmosphere obtains product of the present invention.
Above-mentioned aluminium salt is water-soluble inorganic aluminium salt such as aluminium chloride, aluminum nitrate, aluminum acetate, aluminum sulfate, chloroacetic acid aluminium.
Above-mentioned zirconates is water-soluble inorganic zirconates such as basic zirconium chloride, zirconium oxyacetate, zirconyl nitrate, zirconium nitrate, zirconium sulfate.
Above-mentioned metallic aluminium is that purity is 99.5%～99.99% aluminium flake, aluminium foil, aluminium powder etc.
Above-mentioned high molecular weight water soluble polymer is the straight chain polymer polymer such as polyvinyl acetate of polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, polyvinyl acetate, partial hydrolysis, and its molecular weight is 103～107.
The present invention has following advantage:
(1) by making aluminium oxide and the hydrolytic-polymeric reaction of zirconia presoma fellowship guarantee the even distribution in the spinning solution system of aluminium atom and zirconium atom.Infrared spectrum analysis to precursor sol is found, except having the Al-OH and Al-OH-Al that forms owing to Al (III) hydrolytic polymerization, also have ZrO, ZrOH, explanation is introduced zirconic method with the present invention can make the inorganic zirconates of presoma participate in hydrolytic-polymeric reaction, zirconium is uniformly distributed in the inorganic heterochain macromolecule, thereby realizes the even mixing of aluminium atom and zirconium atom.
(2) in the precursor sol forming process, can not produce the destabilizing factor that gel and foam etc. are unfavorable for forming high-performance fiber.
(3) do not have any special process requirement to concentrating, guaranteed the operability and the simplification of whole fiber production process with spinning process.
(4) aluminium oxide that makes-Zirconium oxide fibre performance is uniform and stable.
Embodiments of the invention are as follows:
Embodiment 1
(1) with 120.7 gram AlCl
36H
2O (analyzing pure) and 80.2 gram ZrOCl
28H
2O is dissolved in 600 ml distilled waters, pouring into and being added with 81.2 gram purity is in the round-bottomed flask of 99.5% metal aluminium flake, in temperature is to reflux 10 hours under 96 ℃ of conditions, filters and obtains Al/Cl than the water white aluminium oxide-Zirconium oxide fibre precursor sol that is 1.98;
(2) adding molecular weight in above-mentioned colloid is 600,000 polyethylene glycol oxide 1g, through stirring after dissolving fully, in 50 ℃ down heating concentrate, obtaining viscosity is the homogeneous transparent spinning solution of 20 pools (20 ℃);
(3) above-mentioned spinning solution is poured in the liquid tank of device for spinning, control air pressure is 0.2MPa, hydraulic pressure is 0.02MPa, keep liquid flow path direction and airflow direction into about 30 °, in temperature be 20 ℃ and relative humidity be jet under 75% the condition diameter 3～6 μ m evenly, the precursor fibre of bright, no slag ball;
(4) above-mentioned precursor fibre at first under being 110 ℃ condition, temperature is sloughed part fiber institute water content, in 290 ℃ the low temperature oven that is connected with nitrogen, handled 60 minutes then, remove partial organic substances, 900 ℃ of following roastings 45 minutes in air at last obtain aluminium oxide-Zirconium oxide fibre.
Embodiment 2
(1) with 187.6 gram Al (NO
3)
39H
2O (analyzing pure) and 33.2 gram ZrO (NO
3)
22H
2O is dissolved in 500 ml distilled waters, and pouring into and being added with 67.7 gram purity is in the round-bottomed flask of 99.99% metal aluminum foil, is to reflux 20 hours under 90 ℃ of conditions in temperature, filters and obtains water white aluminium oxide-Zirconium oxide fibre precursor sol;
(2) adding molecular weight in above-mentioned colloid is 300,000 polyethylene glycol oxide 2g, through stirring after dissolving fully, in 35 ℃ down heating concentrate, obtaining viscosity is the homogeneous transparent spinning solution of 22 pools (20 ℃);
(3) above-mentioned spinning solution is poured in the liquid tank of device for spinning, control air pressure is 0.3MPa, and hydraulic pressure is 0.01MPa, keeps liquid flow path direction and airflow direction into about 20 °, and being 20 ℃ in temperature is to jet precursor fibre under 80% the condition with relative humidity;
(4) above-mentioned precursor fibre at first under being 120 ℃ condition, temperature is sloughed part fiber institute water content, in 260 ℃ the low temperature oven that is connected with nitrogen, handled 90 minutes then, remove partial organic substances, 1000 ℃ of following roastings 20 minutes in air at last obtain aluminium oxide-Zirconium oxide fibre of the present invention.
Embodiment 3
(1) with 375.2 gram Al (NO
3)
39H
2O (analyzing pure) and 20.1 gram ZrOCl
28H
2O is dissolved in 1000 ml distilled waters, and pouring into and being added with 53.9 gram purity is in the round-bottomed flask of 99.5% metal aluminium flake, is to reflux 10 hours under 100 ℃ of conditions in temperature, filters and obtains water white aluminium oxide-Zirconium oxide fibre precursor sol;
(2) adding molecular weight in above-mentioned colloid is 20000 polyethylene glycol 5g, through stirring after dissolving fully, in 40 ℃ down heating concentrate, obtaining viscosity is the homogeneous transparent spinning solution of 18 pools (20 ℃);
(3) above-mentioned spinning solution is poured in the liquid tank of device for spinning, control air pressure is 0.15MPa, and hydraulic pressure is 0.03MPa, keeps liquid flow path direction and airflow direction into about 40 °, and being 25 ℃ in temperature is to jet precursor fibre under 50% the condition with relative humidity;
(4) above-mentioned precursor fibre at first under being 130 ℃ condition, temperature is sloughed part fiber institute water content, in 320 ℃ the low temperature oven that is connected with nitrogen, handled 45 minutes then, remove partial organic substances, 1100 ℃ of following roastings 15 minutes in air at last obtain aluminium oxide-Zirconium oxide fibre of the present invention.
Embodiment 4
(1) with 375.2 gram Al (NO
3)
39H
2O (analyzing pure) and 33.5 gram Zr (NO
3)
45H
2O is dissolved in 1000 ml distilled waters, and pouring into and being added with 74.5 gram purity is in the round-bottomed flask of 99.5% metal aluminium flake, is to reflux 8 hours under 105 ℃ of conditions in temperature, filters and obtains water white aluminium oxide-Zirconium oxide fibre precursor sol;
(2) add 1788 polyvinyl alcohol 10g in above-mentioned colloid, through adding thermal agitation after dissolving fully, heating is concentrated down in 70 ℃, and obtaining viscosity is the homogeneous transparent spinning solution of 25 pools (20 ℃);
(3) above-mentioned spinning solution is poured in the liquid tank of device for spinning, control air pressure is 0.4MPa, and hydraulic pressure is 0.01MPa, keeps liquid flow path direction and airflow direction into about 30 °, and being 30 ℃ in temperature is to jet precursor fibre under 60% the condition with relative humidity;
(4) above-mentioned precursor fibre at first under being 110 ℃ condition, temperature is sloughed part fiber institute water content, in 295 ℃ the low temperature oven that is connected with nitrogen, handled 60 minutes then, remove partial organic substances, 1200 ℃ of following roastings 10 minutes in air at last obtain aluminium oxide-Zirconium oxide fibre of the present invention.
Embodiment 5
(1) with 333.2 gram Al (SO
4)
318H
2O (analyzing pure) and 36 gram Zr (SO
4)
24H
2O is dissolved in 800 ml distilled waters, and pouring into and being added with 74.5 gram purity is in the round-bottomed flask of 99.5% metal aluminium flake, is to reflux 6 hours under 110 ℃ of conditions in temperature, filters and obtains water white aluminium oxide-Zirconium oxide fibre precursor sol;
(2) add 1799 polyvinyl alcohol 5g in above-mentioned colloid, through adding thermal agitation after dissolving fully, heating is concentrated down in 80 ℃, and obtaining viscosity is the homogeneous transparent spinning solution of 30 pools (20 ℃);
(3) above-mentioned spinning solution is poured in the liquid tank of device for spinning, control air pressure is 0.5MPa, and hydraulic pressure is 0.03MPa, keeps liquid flow path direction and airflow direction into about 60 °, and being 25 ℃ in temperature is to jet precursor fibre under 75% the condition with relative humidity;
(4) above-mentioned precursor fibre at first under being 120 ℃ condition, temperature is sloughed part fiber institute water content, in 350 ℃ the low temperature oven that is connected with nitrogen, handled 15 minutes then, remove partial organic substances, 1200 ℃ of following roastings 10 minutes in air at last obtain aluminium oxide-Zirconium oxide fibre of the present invention.
Claims (5)
1. the preparation method of an aluminium oxide-Zirconium oxide fibre is characterized in that the preparation method comprises the steps:
(1) water-soluble inorganic aluminium salt, metallic aluminium and water-soluble inorganic zirconates are measured with oxide respectively, its oxide mass ratio is 1: 1～6.5: 0.2～1, water-soluble inorganic aluminium salt and water-soluble inorganic zirconates are dissolved in the distilled water of 1～5 times of quality in proportion, through stirring or after mild heat dissolves two kinds of inorganic salts fully, add metallic aluminium in proportion, after temperature is to react 5～20 hours under 90 ℃～110 ℃ counterflow conditions, filter rapidly, obtain water white aluminium oxide-Zirconium oxide fibre precursor sol;
(2) with aluminium oxide: the part by weight of high molecular weight water soluble polymer=100: 0.2～20, in colloidal sol, add high molecular weight water soluble polymer as spinning-aid agent, after making it be dissolved in colloidal sol fully, in temperature is to concentrate under 30 ℃～80 ℃ conditions, and obtaining 20 ℃ of following viscosity is the spinning solution of 10～40 pools;
(3) spinning solution is poured into liquid tank in the device for spinning, control air pressure is 0.05～0.5MPa, hydraulic pressure is 0.01～0.1MPa, keep the liquid flow path direction to become 20 °～60 ° angles with airflow direction, being 15 ℃～40 ℃ in temperature is under 20%～80% condition above-mentioned spinning solution to be jetted fibre with relative humidity, obtains precursor fibre of the present invention;
(4) precursor fibre at first under being 100 ℃～150 ℃ condition, temperature is sloughed part fiber contained humidity, in 250 ℃～350 ℃ the low temperature oven that is connected with nitrogen, handled 10～90 minutes then, last roasting 10～60 minutes under 900 ℃～1200 ℃ the temperature conditions in air atmosphere obtains product of the present invention.
2. the preparation method of a kind of aluminium oxide-Zirconium oxide fibre as claimed in claim 1 is characterized in that described aluminium salt is aluminium chloride, aluminum nitrate, aluminum acetate, aluminum sulfate or chloroacetic acid aluminium.
3. the preparation method of a kind of aluminium oxide-Zirconium oxide fibre as claimed in claim 1 is characterized in that described zirconates is basic zirconium chloride, zirconium oxyacetate, zirconyl nitrate, zirconium nitrate or zirconium sulfate.
4. the preparation method of a kind of aluminium oxide-Zirconium oxide fibre as claimed in claim 1 is characterized in that described metallic aluminium is that purity is 99.5%～99.99% aluminium flake, aluminium foil or aluminium powder.
5. the preparation method of a kind of aluminium oxide-Zirconium oxide fibre as claimed in claim 1, it is characterized in that described high molecular weight water soluble polymer is the polyvinyl acetate of polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, polyvinyl acetate or partial hydrolysis, its molecular weight is 10
3～10
7
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011111860A CN1137297C (en) | 2001-04-09 | 2001-04-09 | Process for preparing aluminium oxide-zirconium oxide fibres |
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|---|---|---|---|
| CNB011111860A CN1137297C (en) | 2001-04-09 | 2001-04-09 | Process for preparing aluminium oxide-zirconium oxide fibres |
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| CN1137297C true CN1137297C (en) | 2004-02-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101185817B (en) * | 2007-12-12 | 2010-12-08 | 天津工业大学 | Method for preparing nano alumina fiber film material |
| CN104086201A (en) * | 2014-07-22 | 2014-10-08 | 南京理工宇龙新材料科技有限公司 | High-purity alumina fiber and preparation method thereof |
| CN104178822B (en) * | 2014-07-30 | 2016-08-24 | 东华大学 | Flexible inorganic fibrous material and preparation method thereof |
| CN107266081B (en) * | 2017-07-28 | 2020-11-24 | 山东大学 | Preparation method of alumina-zirconia composite ceramic continuous fiber |
| CN111074379B (en) * | 2019-12-26 | 2022-06-03 | 山东鲁阳浩特高技术纤维有限公司 | Alumina-zirconia composite short fiber and preparation method thereof |
| CN111646816A (en) * | 2020-05-11 | 2020-09-11 | 昆山柔维环境科技有限公司 | Zirconia-alumina composite fiber aerogel material and preparation method thereof |
| CN115231901A (en) * | 2022-06-23 | 2022-10-25 | 东华大学 | Preparation method of uniform and stable ceramic precursor sol |
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