CN1170018C - Method for preparing aluminium oxide-silicon oxide fibre - Google Patents
Method for preparing aluminium oxide-silicon oxide fibre Download PDFInfo
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- CN1170018C CN1170018C CNB021021848A CN02102184A CN1170018C CN 1170018 C CN1170018 C CN 1170018C CN B021021848 A CNB021021848 A CN B021021848A CN 02102184 A CN02102184 A CN 02102184A CN 1170018 C CN1170018 C CN 1170018C
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Abstract
The present invention relates to a preparation method for aluminum oxide and silicon oxide fibers. Water solubility inorganic aluminum 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 precursor sol of the aluminum oxide is obtained by hydrolysis, and a certain amount of silicides and water solubility macromolecules used as a spinning assisting agent are added in the precursor sol. After the mixture of the precursor sol and the spinning assisting agent is concentrated, thread spinning original liquid having eligible flow performance is obtained. The thread spinning original liquid is spun into precursor fibers by a blowing method, and the precursor fibers are further thermally treated in nitrogen atmosphere, which enables aluminum oxide and silicon oxide precursors to convert into aluminum oxide and silicon oxide. Thus, the aluminum oxide and silicon oxide fibers of the present invention can be finally obtained. The present invention has the characteristics of low cost, simple process, controllability of nitrogen flow quantity and temperature rising program, homogeneous and stable fiber quality, etc.
Description
Technical field:
The present invention relates to a kind of preparation method of inorfil, relate in particular to a kind of preparation method of the aluminium oxide-silicon oxide fibre as Metal Substrate, ceramic matric composite reinforcing material.
Background technology:
Alumina fibre is to begin to develop abroad a kind of comparatively rapidly fiber from nineteen seventies.Because alumina fibre has good chemical inertness, higher specific surface and low a series of performances such as thermal conductivity are as 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 excellent high-temperature mechanical property received the concern of material circle more, and its performance has also been had higher requirement.With silica SiO
2Be acknowledged as the effective ways that improve the alumina fibre elevated temperature strength as the crystalline phase inhibitor, therefore, in alumina fibre reinforcing material field, the various countries scholar generally concentrates on the preparation technology and the performance study thereof of aluminium oxide-silicon oxide fibre.CN1035479 and ZL98109101.6 have reported the preparation method of two kinds of different alumina fibre-silicon oxide fibres respectively.In these two patents, the method for hydrothermal treatment consists has all been adopted in the fiber post processing, promptly in steam atmosphere heat treated to remove component to be decomposed.The alumina fibre that is obtained by this hydro-thermal treatment method has abundant internal surface area and a large amount of holes, thus these holes do the time spent and can become center of stress and cause fibrous fracture being subjected to external force, thereby be not suitable for doing reinforcing material and use.
Summary of the invention:
The purpose of this invention is to provide a kind of low-porosity, have the preparation method of the aluminium oxide-silicon oxide fibre of high strength and modulus.
The object of the present invention is achieved like this, is main raw material with water-soluble inorganic aluminium salt and metallic aluminium, is solvent with distilled water, under refluxad makes the alumina precursor colloidal sol of homogeneous transparent by hydrolysis, polymerization.In this colloidal sol, add a certain amount of silicide and, after concentrated, make spinning solution with suitable rheological property as the water soluble polymer of spinning-aid agent.This spinning solution is spun into precursor fibre through blowing process.Precursor fibre makes aluminium oxide and silica presoma be converted into aluminium oxide and silica through further heat treatment in nitrogen atmosphere again, thereby finally obtains aluminium oxide-silicon oxide fibre of the present invention.
The preparation method of aluminium oxide-silicon oxide fibre provided by the invention comprises the steps:
(1) water-soluble inorganic aluminium salt and metallic aluminium are scaled alumina content respectively, the weight ratio of the aluminium oxide that the two is contained is 1: 1～6.5; In the distilled water with molten sub 1～5 times of quality of inorganic aluminate, add metallic aluminium according to the above ratio, after temperature is to react 5～20 hours under 90 ℃～120 ℃ counterflow conditions, filter rapidly, obtain water white alumina precursor colloidal sol;
(2) water-soluble silication thing is scaled silica content, 1wt%～the 50wt% that accounts for alumina content with silica is a benchmark, adds silicide in alumina precursor colloidal sol, must fully mix when adding silicide, gelatin phenomenon does not take place, and obtains the sial complex sol;
(3) with the alumina content be benchmark, in the sial complex sol, add 0.2～20% high molecular weight water soluble polymer as spinning-aid agent, after making it be dissolved in colloidal sol fully, be to concentrate under 30～80 ℃ of conditions in temperature, obtaining viscosity is the spinning solution of 10～40 pools (20 ℃);
(4) be 0.02～0.5MPa with spinning solution at air pressure, hydraulic pressure is 0.01～0.1MPa, spray silk liquid flow path direction and airflow direction angle are 20～60 °, and it is to jet fibre under 20～80% conditions with relative humidity that temperature is 15～40 ℃, obtains precursor fibre of the present invention;
(5) be under the condition of 10～500ml/min at nitrogen flow, heating rate with 0.5～10 ℃/min, rise to 100 ℃～150 ℃ constant temperature 10 minutes～120 minutes earlier, be warming up to 250 ℃～350 ℃ and constant temperature then 10 minutes～120 minutes, at last in air atmosphere with the heating rate of 0.5 ℃/min～10 ℃/min, be warming up to 900 ℃～1200 ℃ and constant temperature 10 minutes～120 minutes, and obtained aluminium oxide-silicon oxide fibre of the present invention.
Aforesaid aluminium salt is water-soluble inorganic aluminium salt such as aluminium chloride, aluminum nitrate, aluminum acetate, aluminum sulfate, chloroacetic acid aluminium.
Aforesaid silicide is an ethyl orthosilicate, commercial water-soluble organic silicon surfactant etc.
Aforesaid metallic aluminium is that purity is 99.5%～99.99% aluminium flake, aluminium foil, aluminium powder etc.
Aforesaid 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 10
3～10
7
The present invention has following advantage:
(1) owing in the precursor fibre heat treatment process, adopts nitrogen atmosphere, avoid the reaming effect of steam, can obviously reduce specific fiber surface, reduced inner hole, increase substantially fibre strength, thereby be more suitable for requirement in reinforcing material by the alumina fibre of this manufactured;
(2) this process is simple, and nitrogen flow and heating schedule are controlled, and fiber quality is uniform and stable.
The specific embodiment:
Embodiment 1
1. with 120.7 gram AlCl
36H
2O (analyzing pure) is dissolved in 600 ml distilled waters, and pouring into and being added with 81.2 gram purity is in the round-bottomed flask of 99.5% metal aluminium flake, is to reflux 10 hours under 96 ℃ of conditions in temperature, filters and obtains Al/Cl than the water white chlorine oxygen aluminium colloidal sol that is 1.98;
2. get 30 gram ethanol, 15.2 gram ethyl orthosilicates add in the above-mentioned colloid, and under 50 ℃ of heating conditions stirring and refluxing 2 hours, filter and obtain transparent aluminium silicon composite sol;
3. in above-mentioned aluminium silicon composite sol, add molecular weight and be 600,000 polyethylene glycol oxide 0.9g, through stirring after dissolving fully, in 40 ℃ down heating concentrate, obtaining viscosity is the homogeneous transparent spinning solution of 20 pools (20 ℃);
4. 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;
5. whole process all adopts the heating rate of 2 ℃/min, be that heated at constant temperature was sloughed part fiber institute water content in 60 minutes under 110 ℃ of conditions in temperature at first with above-mentioned precursor fibre, the control flow is that 40ml/min feeds steam, is warming up to 290 ℃ and constant temperature again 60 minutes, removes partial organic substances.900 ℃ of following roastings 45 minutes in air at last obtain aluminium oxide-silicon oxide fibre.Adopting day AUTOGRAPH WinAG material property testing machine of island proper Tianjin company, is that 2mm/min tests fibre tensile strength and elastic modelling quantity with the rate of extension, and intensity is 482.2MPa, and modulus is 32.1GPa, and specific surface is 200m
2/ g.
Embodiment 2
1. colloidal sol preparation and spinning process are with embodiment 1.
2. the precursor fibre Technology for Heating Processing is as follows: whole process all adopts the heating rate of 2 ℃/min, the control flow is that 40ml/min feeds nitrogen, be that constant temperature was sloughed part fiber institute water content in 60 minutes under 110 ℃ of conditions with above-mentioned precursor fibre in temperature earlier, be warming up to 290 ℃ and constant temperature again 60 minutes, and removed partial organic substances.900 ℃ of following roastings 45 minutes in air at last obtain aluminium oxide-silicon oxide fibre of the present invention.Adopting day AUTOGRAPH WinAG material property testing machine of island proper Tianjin company, is that 2mm/min tests fibre tensile strength and elastic modelling quantity with the rate of extension, and intensity is 1092.9MPa, and modulus is 87.4GPa, and specific surface is 20m
2/ g.
Embodiment 3
1. with 375.2 gram Al (NO
3)
39H
2O (analyzing pure) is dissolved in 1000 ml distilled waters, and pouring into and being added with 100 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 alumina precursor colloidal sol;
2. get U.S. Air Products ﹠amp; DC5604 organic silicon surfactant 10 gram of Chemicals company and molecular weight are that 600,000 polyethylene glycol oxide 0.9g adds in the above-mentioned colloid and makes its even mixing, in 40 ℃ down heating concentrate, obtain viscosity and be 25 and moor the homogeneous transparent spinning solution of (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. whole process all adopts the heating rate of 1 ℃/min, the control flow is that 60ml/min feeds nitrogen, is that constant temperature was sloughed part fiber institute water content in 45 minutes under 130 ℃ of conditions in temperature earlier, was warming up to 300 ℃ and constant temperature again 90 minutes, remove partial organic substances above-mentioned precursor fibre.950 ℃ of following roastings 30 minutes in air at last obtain aluminium oxide-silicon oxide fibre of the present invention.Adopting day AUTOGRAPH WinAG material property testing machine of island proper Tianjin company, is that 2mm/min tests fibre tensile strength and elastic modelling quantity with the rate of extension, and intensity is 1420.2MPa, and modulus is 113.6GPa.
Embodiment 4
1. with 375.2 gram Al (NO
3)
39H
2O (analyzing pure) 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 99.9% metal aluminum foil, is to reflux 8 hours under 105 ℃ of conditions in temperature, filters and obtains water white alumina precursor colloidal sol;
2. the DC193 organic silicon surfactant 15g and the 10g spinning-aid agent polyvinyl alcohol 1788 that in above-mentioned colloid, add Dow Coming company, through adding thermal agitation after dissolving fully, heating is concentrated down in 60 ℃, and 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 0.4MPa, 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. the control flow is that 56ml/min feeds nitrogen, earlier above-mentioned precursor fibre is heated to 140 ℃ and constant temperature with the heating rate of 2 ℃/min and sloughed part fiber institute water content in 30 minutes, be warming up to 285 ℃ and constant temperature 60 minutes with the heating rate of 1.5 ℃/min again, remove partial organic substances.Heating rate with 2 ℃/min is warming up to 1000 ℃ of following roastings 30 minutes in air at last, obtains aluminium oxide-silicon oxide fibre of the present invention.Adopting day AUTOGRAPH WinAG material property testing machine of island proper Tianjin company, is that 2mm/min tests fibre tensile strength and elastic modelling quantity with the rate of extension, and intensity is 1437.9MPa, and modulus is 143.8GPa.
Embodiment 5
1. with 333.2 gram Al (SO
4)
318H
2O (analyzing pure) is dissolved in 800 ml distilled waters, and pouring into and being added with 67.7 gram purity is in the round-bottomed flask of 99.5% metal aluminium flake, is to reflux 5 hours under 120 ℃ of conditions in temperature, filters and obtains water white alumina precursor colloidal sol;
2. get U.S. Air Products ﹠amp; DC5604 organic silicon surfactant 5 gram of Chemicals company and molecular weight are that 300,000 polyethylene glycol oxide 3g adds in the above-mentioned colloid and makes its even mixing, in 40 ℃ down heating concentrate, obtain viscosity and be 25 and moor the homogeneous transparent spinning solution of (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. the control flow is that 100ml/min feeds nitrogen, earlier above-mentioned precursor fibre is heated to 110 ℃ and constant temperature with the heating rate of 2 ℃/min and sloughed part fiber institute water content in 60 minutes, be warming up to 300 ℃ and constant temperature 45 minutes with the heating rate of 1 ℃/min again, remove partial organic substances.Heating rate with 1.5 ℃/min is warming up to 850 ℃ of roastings 30 minutes in air at last, obtains aluminium oxide-silicon oxide fibre of the present invention.Adopting day AUTOGRAPH WinAG material property testing machine of island proper Tianjin company, is that 2mm/min tests fibre tensile strength and elastic modelling quantity with the rate of extension, and intensity is 1013.8MPa, and modulus is 74.4GPa.
Claims (5)
1. the preparation method of an aluminium oxide-silicon oxide fibre is characterized in that the preparation method comprises the steps:
(1) water-soluble inorganic aluminium salt and metallic aluminium are scaled alumina content respectively, the weight ratio of the aluminium oxide that the two is contained is 1: 1～6.5, inorganic aluminate is dissolved in the distilled water of 1～5 times of quality, add metallic aluminium according to the above ratio, after temperature is to react 5～20 hours under 90 ℃～120 ℃ counterflow conditions, filter rapidly, obtain water white alumina precursor colloidal sol;
(2) water-soluble silication thing is scaled silica content, 1wt%～the 50wt% that accounts for alumina content with silica is a benchmark, adds silicide in alumina precursor colloidal sol, must fully mix when adding silicide, gelatin phenomenon does not take place, and obtains the sial complex sol;
(3) with the alumina content be benchmark, in the sial complex sol, add 0.2～20wt% high molecular weight water soluble polymer as spinning-aid agent, after making it be dissolved in colloidal sol fully, be to concentrate under 30～80 ℃ of conditions in temperature, obtaining under 20 ℃ of temperature viscosity is the spinning solutions of 10～40 pools;
(4) be 0.02～0.5MPa with spinning solution at air pressure, hydraulic pressure is 0.01～0.1MPa, spray silk liquid flow path direction and airflow direction angle are 20～60 °, and it is to jet fibre under 20～80% conditions with relative humidity that temperature is 15～40 ℃, obtains precursor fibre of the present invention;
(5) be under the condition of 10～500ml/min at nitrogen flow, heating rate with 0.5～10 ℃/min, rise to 100 ℃～150 ℃ constant temperature 10 minutes～120 minutes earlier, be warming up to 250 ℃～350 ℃ and constant temperature then 10 minutes～120 minutes, at last in air atmosphere with the heating rate of 0.5 ℃/min～10 ℃/min, be warming up to 900 ℃～1200 ℃ and constant temperature 10 minutes～120 minutes, and obtained aluminium oxide-silicon oxide fibre of the present invention.
2. the preparation method of a kind of aluminium oxide-silicon 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 water-soluble inorganic aluminium salt.
3. the preparation method of a kind of aluminium oxide-silicon oxide fibre as claimed in claim 1 is characterized in that described silicide is ethyl orthosilicate or commercial water-soluble organic silicon surfactant.
4. the preparation method of a kind of aluminium oxide-silicon 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-silicon oxide fibre as claimed in claim 1, it is characterized in that described high molecular weight water soluble polymer is the polyvinyl acetate straight chain polymer polymer of polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, polyvinyl acetate or partial hydrolysis, its molecular weight is 10
3～10
7
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021021848A CN1170018C (en) | 2002-01-21 | 2002-01-21 | Method for preparing aluminium oxide-silicon oxide fibre |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021021848A CN1170018C (en) | 2002-01-21 | 2002-01-21 | Method for preparing aluminium oxide-silicon oxide fibre |
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|---|---|
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| CN1170018C true CN1170018C (en) | 2004-10-06 |
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|---|---|---|---|
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381225B (en) * | 2008-10-10 | 2013-04-24 | 厦门大学 | Continuous aluminium oxide base ceramic fibre preparation method |
| CN103757750A (en) * | 2014-01-09 | 2014-04-30 | 天津工业大学 | Preparation method of alumina-based continuous fibers |
| CN104005115B (en) * | 2014-06-17 | 2016-05-04 | 山东大学 | A kind of preparation method of ceramic alumina fiber |
| DE102016125182A1 (en) * | 2016-12-21 | 2018-06-21 | Groz-Beckert Kg | Process for producing fibers and nonwovens by solution blow spinning and nonwoven fabric made therewith |
| CN108539147B (en) * | 2018-03-21 | 2021-01-12 | 同济大学 | Preparation method and application of lithium ion battery negative electrode material SiO @ Al @ C |
| CN110078486A (en) * | 2019-04-29 | 2019-08-02 | 江苏辉迈粉体科技有限公司 | A kind of preparation method of quartz fibre |
| CN111574204A (en) * | 2020-05-20 | 2020-08-25 | 国装新材料技术(江苏)有限公司 | Alumina ceramic aerogel fiber and sol-gel spinning preparation method thereof |
| CN111663201B (en) * | 2020-05-27 | 2022-07-19 | 中铝山东有限公司 | Method for producing alumina fiber by using sodium-silicon slag and alumina fiber |
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2002
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