CN115896980A - Preparation method of aluminum-zirconium composite spinning solution, precursor fiber and zirconia-alumina composite short fiber - Google Patents
Preparation method of aluminum-zirconium composite spinning solution, precursor fiber and zirconia-alumina composite short fiber Download PDFInfo
- Publication number
- CN115896980A CN115896980A CN202211435557.9A CN202211435557A CN115896980A CN 115896980 A CN115896980 A CN 115896980A CN 202211435557 A CN202211435557 A CN 202211435557A CN 115896980 A CN115896980 A CN 115896980A
- Authority
- CN
- China
- Prior art keywords
- aluminum
- zirconium
- spinning solution
- hydroxide
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 128
- 238000009987 spinning Methods 0.000 title claims abstract description 103
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 239000002243 precursor Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 44
- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 41
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 27
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 claims abstract description 25
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004327 boric acid Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000003980 solgel method Methods 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 24
- -1 aluminum zirconium carboxylate Chemical class 0.000 claims description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 24
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims 1
- 238000005520 cutting process Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000000578 dry spinning Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 238000007664 blowing Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 20
- 238000002156 mixing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- VCRLKNZXFXIDSC-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[Al+3].[Zr+4] VCRLKNZXFXIDSC-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- FMXLGOWFNZLJQK-UHFFFAOYSA-N hypochlorous acid;zirconium Chemical compound [Zr].ClO FMXLGOWFNZLJQK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- 229910006636 γ-AlOOH Inorganic materials 0.000 description 1
Images
Landscapes
- Inorganic Fibers (AREA)
Abstract
The invention provides a preparation method of an aluminum zirconium composite spinning solution, precursor fibers and zirconia-alumina composite short fibers. The preparation method of the aluminum-zirconium composite spinning solution comprises the following steps: the aluminum-zirconium composite spinning solution is prepared by taking aluminum hydroxide, zirconium hydroxide, organic carboxylic acid, yttrium acetate and boric acid as raw materials through a sol-gel method. The invention takes zirconium hydroxide, aluminum hydroxide and organic carboxylic acid as main raw materials and does not contain Cl ‑ 、SO4 2‑ 、NO 3 ‑ Plasma, no substances influencing the environment are generated in the production process; the invention directly takes aluminum hydroxide and zirconium hydroxide as main raw materials to prepare the aluminum-zirconium composite spinning solution, andcompared with the technology for respectively preparing the aluminum sol and the zirconium sol, the technology greatly reduces the process complexity and is easier for industrial production; compared with the existing centrifugal spinning or blowing technology, the dry spinning short-cutting technology can be used for short-cutting the precursor fiber to any length within 1-50cm according to the requirement, and the diameter and the length of the fiber after heat treatment are more uniform.
Description
Technical Field
The invention relates to the technical field of composite fibers, and particularly relates to a preparation method of an aluminum-zirconium composite spinning solution, precursor fibers and zirconia-alumina composite short fibers.
Background
The zirconia-alumina composite fiber has high temperature resistance, and can fully utilize the functions of phase change toughening and microcrack toughening of zirconia to improve the toughness and strength of alumina. Therefore, the performance of the zirconia-alumina composite fiber is better than that of the pure alumina or zirconia ceramic fiber, the service temperature of the zirconia-alumina composite fiber is higher than that of the alumina ceramic fiber, and the bending strength and the fracture toughness of the zirconia-alumina composite fiber are higher than those of the zirconia ceramic fiber. In view of the excellent properties of the zirconia-alumina composite fiber, researchers have conducted extensive research. For example, patent No. CN102465357B reports a preparation method of a polycrystalline zirconia fiber and a zirconia/alumina composite fiber, in which zirconium carbonate and hydrochloric acid are used as raw materials, and a zirconium chlorohydroxide sol is prepared by refluxing; adding aluminum sol, phase stabilizer, grain growth inhibitor and water-soluble polymer assistant, distilling under reduced pressure to obtain zirconium-aluminum composite spinning solution, centrifugally spinning or spray spinning to obtain gel fiber, and heat treating to obtain zirconium oxide/aluminum oxide composite fiber. For example, patent No. CN111074379B reports a method for preparing alumina-zirconia composite short fibers, which includes heating and refluxing aluminum powder, hydrochloric acid and water to obtain polyaluminum chloride sol, adding zirconium oxychloride solution and mixing to obtain zirconium-aluminum gel, spinning to form fibers to obtain precursor fibers, and performing heat treatment to obtain alumina-zirconia composite short fibers. For example, fu Chaodeng is prepared by preparing alumina-zirconia precursor fiber spinning solution by sol-gel method using aluminum powder, hydrochloric acid, zirconium acetate and zirconium oxychloride as raw materials and polyvinyl alcohol as spinning auxiliary agent, and preparing gel fiber by high-speed centrifugal spinning machine (see: material: zirconium acetate and zirconium oxychloride as spinning auxiliary agent)Material guide B2015,29,68). The three methods all adopt centrifugal spinning or blowing spinning technology, and the prepared fiber has uneven diameter and many defects. The patent No. CN107266081B reports a preparation method of an alumina-zirconia composite ceramic continuous fiber, the method utilizes alumina sol containing Al13 colloidal particles, gamma-AlOOH nano dispersion liquid, zirconium acetate, yttrium nitrate and polyvinyl alcohol (PVA) to prepare spinnable precursor sol, adopts a dry spinning technology to prepare gel fiber, and obtains the alumina-zirconia composite ceramic continuous fiber through heat treatment. In the method, the alumina sol is prepared from aluminum powder, aluminum chloride, aluminum sulfate, aluminum nitrate and the like, and Cl - 、SO4 2- 、NO 3 - The existence of plasma causes great environmental pollution in the fiber heat treatment process. The above-mentioned preparation methods have certain problems and disadvantages, and thus further improvement and development of the preparation methods are required.
Disclosure of Invention
The invention provides an aluminum zirconium composite spinning solution, a precursor fiber, a zirconia-alumina composite short fiber and a preparation method, and the specific scheme is as follows:
the preparation method of the aluminum-zirconium composite spinning solution comprises the steps of taking aluminum hydroxide, zirconium hydroxide, organic carboxylic acid, yttrium acetate and boric acid as raw materials, and preparing the aluminum-zirconium composite spinning solution by a sol-gel method.
Further, mixing organic carboxylic acid and water, adding aluminum hydroxide, performing first condensation reflux at 70-95 ℃, adding zirconium hydroxide, and continuing condensation reflux; cooling and filtering to obtain aluminum zirconium carboxylate sol, adding yttrium acetate, boric acid and polyvinyl alcohol into the aluminum zirconium carboxylate sol, and carrying out reduced pressure distillation to obtain the aluminum zirconium composite spinning solution.
Further, the molar ratio of the aluminum hydroxide to the organic carboxylic acid is 1:1-2.5; the molar ratio of aluminum hydroxide to water is 1:10-20 parts of; the molar ratio of the aluminum hydroxide to the zirconium hydroxide is 10-25:1; the molar ratio of zirconium hydroxide to yttrium acetate is 15-50:1; the molar ratio of the aluminum hydroxide to the boric acid is 28-108:1.
furthermore, the addition amount of the polyvinyl alcohol is 0.2 to 1.4 weight percent of the total mass of the raw materials.
Further, the organic carboxylic acid is one or more of formic acid, acetic acid, oxalic acid, malonic acid and citric acid.
Furthermore, the time of the first condensation reflux is 8-10h, and the time of adding the zirconium hydroxide to continue the condensation reflux is 10-30min.
Further, the temperature of reduced pressure distillation is 40-50 ℃, and the distillation is carried out until the viscosity is 300-800 Pa.s.
An aluminum zirconium composite spinning solution is prepared by the preparation method of the aluminum zirconium composite spinning solution.
A preparation method of precursor fiber comprises the steps of carrying out vacuum defoaming on the aluminum-zirconium composite spinning solution, then spinning the spinning solution, and obtaining the precursor fiber after drafting, filament falling and short cutting.
Further, the spinning solution is spun at an ambient temperature of 20 to 30 ℃ and a relative humidity of 15 to 35%.
Further, spinning the spinning solution by using a metering pump, wherein the flow rate of the metering pump is 30-60cc/min.
Further, the precursor fiber with the diameter of 12-20 microns and the length of 1-50cm is obtained after drafting, filament falling and chopping.
Furthermore, the aperture of a spinneret plate used for spinning is 0.1-0.12mm, and the number of holes is 1000-2000.
A precursor fiber is prepared by a preparation method of the precursor fiber.
A preparation method of zirconia-alumina composite short fiber comprises the steps of placing the precursor fiber in a muffle furnace, slowly heating to 100-150 ℃, and then preserving heat for 0.5-1h; then slowly heating to 600-700 ℃, and preserving heat for 0.5-1h at the temperature; finally, the temperature is increased to 1200-1400 ℃, and the temperature is kept for 0.5-2h at the temperature, so as to prepare the zirconia-alumina composite short fiber.
Further, the temperature is raised to 100-150 ℃ at the speed of 0.1-1.0 ℃/min, to 600-700 ℃ at the speed of 0.5-3.0 ℃/min, and to 1200-1400 ℃ at the speed of 5-10 ℃/min.
A zirconia-alumina composite short fiber is prepared by the preparation method of the zirconia-alumina composite short fiber.
Due to the adoption of the technical scheme, the invention has the beneficial technical effects that:
1. the invention takes zirconium hydroxide, aluminum hydroxide and organic carboxylic acid as main raw materials and does not contain Cl - 、SO4 2- 、NO 3 - Plasma, no substances which influence the environment are generated in the production process.
2. Compared with the existing centrifugal spinning or blowing technology, the dry spinning chopping technology adopted by the invention can chop the precursor fiber to any length within 1-50cm according to the requirement, and the diameter and the length of the fiber after heat treatment are more uniform.
3. The invention directly takes the aluminum hydroxide and the zirconium hydroxide as main raw materials to prepare the aluminum zirconium composite spinning solution, and compared with the prior art which respectively prepares the aluminum sol and the zirconium sol, the process complexity is greatly reduced.
Drawings
FIG. 1 is a photograph of zirconia-alumina composite staple fibers prepared in example 3 of the present invention;
fig. 2 is an SEM image of zirconia-alumina composite short fibers of example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of an aluminum zirconium composite spinning solution, which is prepared by taking aluminum hydroxide, zirconium hydroxide, organic carboxylic acid, yttrium acetate and boric acid as raw materials through a sol-gel method. The invention takes zirconium hydroxide, aluminum hydroxide and organic carboxylic acid as main raw materials and does not contain Cl - 、SO4 2- 、NO 3 - Plasma, no influence on environment in the production processThe substance of (1).
Specifically, mixing organic carboxylic acid and water, adding aluminum hydroxide, performing condensation reflux at 70-95 ℃ for 8-10h, adding zirconium hydroxide, and continuing to perform condensation reflux for 10-30min; cooling and filtering to obtain aluminum zirconium carboxylate sol, adding yttrium acetate, boric acid and polyvinyl alcohol into the aluminum zirconium carboxylate sol, and carrying out reduced pressure distillation to obtain the aluminum zirconium composite spinning solution. The boric acid is added in the invention to reduce the growth of crystal grains, improve the toughness of the fiber, and also can reduce the crystal phase transformation temperature and the heat treatment temperature. The yttrium acetate is added to stabilize the zirconium oxide in tetragonal phase, avoid fiber volume cracking during heat treatment, inhibit grain growth and improve fiber compactness. The temperature of condensation reflux is 70-95 ℃, when the temperature of condensation reflux is lower than 70 ℃, aluminum hydroxide, zirconium oxide and organic carboxylic acid do not react, transparent and spinnable spinning solution cannot be obtained, when the temperature of condensation reflux exceeds 95 ℃, white precipitate can be generated, and the spinning solution cannot be formed by distillation after filtration. The condensation reflux has the functions of concentration and purification, and the aluminum zirconium carboxylate sol is obtained after two times of condensation reflux in the preparation process of the aluminum zirconium composite spinning solution. The selection of the adding time of the zirconium hydroxide is crucial, the thermal stability of the reaction product of the zirconium hydroxide and the organic carboxylic acid is poor, and if the aluminum hydroxide and the zirconium hydroxide are added simultaneously, white precipitate is generated and the spinning solution cannot be formed.
In specific examples, the molar ratio of aluminum hydroxide to organic carboxylic acid is 1:1-2.5; when the molar ratio of the aluminum hydroxide to the organic carboxylic acid is 1: in the range of 1 to 2.5, the aluminum hydroxide reacts with the organic carboxylic acid to form linear Al oligomers, which is also critical for spinnability of the dope. Further preferably, the molar ratio of aluminium hydroxide to organic carboxylic acid is 1:2.
the molar ratio of aluminum hydroxide to water is 1:10-20 parts of; too high or too low a molar ratio of aluminum hydroxide to water can affect the pH of the aluminum hydroxide solution and, in turn, the reaction of the aluminum hydroxide with the organic carboxylic acid. Further preferably, the molar ratio of aluminum hydroxide to water is 1:12.
the molar ratio of the aluminum hydroxide to the zirconium hydroxide is 10-25:1; the ratio corresponds to the incorporation of different amounts of zirconium hydroxide, and the different ratios of zirconium oxide to aluminum oxide in the final fiber result in inconsistent mechanical or thermal properties of the fiber. Experiments prove that the molar ratio of the aluminum hydroxide to the zirconium hydroxide is 18:1, the resulting fiber has the best properties.
The molar ratio of zirconium hydroxide to yttrium acetate is 15-50:1; the molar ratio of zirconium hydroxide to yttrium acetate influences the doping amount of yttrium acetate, and yttrium acetate is a stabilizer of a zirconia crystal phase, and the dosage of yttrium acetate influences the phase change stability of tetragonal zirconia in the fiber; too much or too little yttrium acetate does not act as a stabilizer. Preferably, the molar ratio of zirconium hydroxide to yttrium acetate is 16:1.
the molar ratio of the aluminum hydroxide to the boric acid is 28-108:1. when the using amount of the boric acid is too high, the mechanical property of the final fiber is influenced; when the amount of the boric acid is too low, the boric acid cannot play a role of a sintering aid. Preferably, the molar ratio of aluminium hydroxide to boric acid is 36:1.
specifically, the addition amount of the polyvinyl alcohol is 0.2-1.4wt% of the total mass of the raw materials. The polyvinyl alcohol is a spinning auxiliary agent, spinning is facilitated, and the spinnability of the spinning solution cannot be improved due to the fact that too little polyvinyl alcohol is used; too much polyvinyl alcohol causes a large amount of void-type defects in the fibers, and the polyvinyl alcohol is optimally added in an amount of 1.0wt%.
Specifically, the organic carboxylic acid is one or more of formic acid, acetic acid, oxalic acid, malonic acid and citric acid. The organic carboxylic acid reacts with aluminum hydroxide and zirconium hydroxide to produce a homogeneous transparent aluminum zirconium carboxylate sol, with formic acid, oxalic acid, and acetic acid being the most effective.
Specifically, the temperature of reduced pressure distillation is 40-50 ℃, and the distillation is carried out until the viscosity is 300-800 Pa.s. When the temperature of reduced pressure distillation is lower than 40 ℃, the reaction efficiency is low, and the stability of the spinning solution is influenced; the temperature of the reduced pressure distillation is higher than 50 ℃, gelation of the spinning solution is accelerated, and a transparent and spinnable spinning solution cannot be obtained.
The viscosity of the spinning solution is measured by a rotational rheometer, and the viscosity is used as an index to indirectly explain the spinnability of the spinning solution; spinning solutions outside this viscosity range cannot be used to produce staple fibers using dry spinning chopping processes.
The invention also provides a preparation method of the precursor fiber, which comprises the steps of carrying out vacuum defoaming on the aluminum-zirconium composite spinning solution, and spinning the spinning solution under the conditions that the ambient temperature is 20-30 ℃ and the relative humidity is 15-35%. Spinning the spinning solution by using a metering pump, wherein the flow rate of the metering pump is 30-60cc/min, and obtaining precursor fiber after drafting, filament falling and short cutting. And drawing, shredding and chopping to obtain precursor fiber with the diameter of 12-20 microns and the length of 1-50 cm. Specifically, the drafted precursor fiber is cut off by a pair of scissors with adjustable frequency before falling into a plate, the fiber diameter can be adjusted by adjusting the drafting rate, and the fiber length can be adjusted by adjusting the frequency of the scissors.
Wherein the diameter of the spinneret plate used for spinning is 0.1-0.12mm, and the number of holes is 1000-2000. The aperture of the spinneret plate is lower than 0.1mm, so that the spinning pressure is extremely high, and the current equipment cannot meet the requirement; above 0.12mm, the resulting fiber diameter is large. The metering pump is used for inputting the spinning solution into the spinneret plate in a quantitative and constant-pressure mode, and the spinning filament bundle can be ensured to be uniform by the aid of the flow of 30-60cc/min.
Preparing zirconia-alumina composite short fiber by using the precursor fiber, and specifically, putting the precursor fiber into a muffle furnace, heating to 100-150 ℃ at the speed of 0.1-1.0 ℃/min, and preserving heat at the temperature for 0.5-1h; heating to 600-700 deg.C at a rate of 0.5-3.0 deg.C/min, and maintaining at the temperature for 0.5-1h; finally, the temperature is increased to 1200-1400 ℃ at the speed of 5-10 ℃/min, and the temperature is kept for 0.5-2h at the temperature, so that the zirconia-alumina composite short fiber is prepared. And carrying out high-temperature heat treatment on the precursor fiber, and heating and preserving the temperature of the precursor fiber for three times to obtain the boron-containing zirconia-alumina composite short fiber with uniform diameter and length. The third heating adopts different heating rates, the first stage mainly removes the solvent in the fiber, and the temperature needs to be slowly raised; the second stage is a ceramic process, mainly removes organic substances in the fiber, and has moderate heating rate; the third stage is crystallization, mainly the transformation of crystal form, and needs rapid temperature rise.
Morphology of the zirconia-alumina composite staple fiber can be seen in fig. 1 and 2, and fig. 1 and 2 provide photographs and scanned pictures of the zirconia-alumina composite staple fiber (taking example 3 as an example).
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of zirconia-alumina composite short fiber comprises the following steps:
(1) Preparation of the spinning dope
Fully dissolving 6mol of oxalic acid, 1.5mol of acetic acid and 60mol of water, uniformly mixing, and then adding 3mol of aluminum hydroxide; condensing and refluxing for 10h at the temperature of 95 ℃; adding 0.3mol of zirconium hydroxide; continuously condensing and refluxing for 30min; cooling and filtering to obtain uniform and transparent aluminum zirconium carboxylate sol; adding 0.02mol of yttrium acetate, 0.15mol of boric acid and 0.99mol of polyvinyl alcohol into the aluminum zirconium carboxylate sol, and distilling at 50 ℃ under reduced pressure until the viscosity is 800 Pa.s to prepare the spinnable aluminum zirconium composite spinning solution.
(2) Preparation of precursor fiber
Pouring the aluminum-zirconium composite spinning solution prepared in the step (1) into a material tank, defoaming in vacuum for 10min, spinning the spinning solution by using a metering pump under the conditions that the ambient temperature is 30 ℃ and the relative humidity is 35%, wherein the flow of the metering pump is 60cc/min, and obtaining precursor fibers by drawing, filament falling and short cutting devices.
(3) High temperature heat treatment
Putting the precursor fiber prepared in the step (2) into a muffle furnace, heating to 150 ℃ at the speed of 1 ℃/min, and preserving heat for 1h at the temperature; then heating to 700 ℃ at the speed of 3 ℃/min, and preserving the heat for 1h at the temperature; and finally, heating to 1400 ℃ at the speed of 10 ℃/min, and preserving the heat for 2h at the temperature to obtain the boron-containing zirconium oxide-aluminum oxide composite short fiber with uniform diameter and length.
Example 2
A preparation method of zirconia-alumina composite short fiber comprises the following steps:
(1) Preparation of the spinning dope
Fully dissolving 3mol of oxalic acid and 30mol of water, uniformly mixing, and then adding 3mol of aluminum hydroxide; condensing and refluxing for 8h at 70 ℃; adding 0.12mol of zirconium hydroxide; continuously condensing and refluxing for 10min; cooling and filtering to obtain uniform and transparent aluminum zirconium carboxylate sol; adding 0.0024mol of yttrium acetate, 0.028mol of boric acid and 0.07mol of polyvinyl alcohol into the aluminum zirconium carboxylate sol, and distilling at 40 ℃ under reduced pressure until the viscosity is 300 Pa.s to prepare spinnable aluminum zirconium composite spinning solution;
(2) Preparation of precursor fiber
Pouring the aluminum-zirconium composite spinning solution prepared in the step (1) into a material tank, defoaming in vacuum for 5min, spinning the spinning solution by using a metering pump under the conditions that the ambient temperature is 20 ℃ and the relative humidity is 15%, wherein the flow of the metering pump is 30cc/min, and obtaining precursor fibers by drawing, filament falling and short cutting devices.
(3) High temperature heat treatment
Putting the precursor fiber prepared in the step (2) into a muffle furnace, heating to 100 ℃ at the speed of 0.1 ℃/min, and preserving heat for 0.5h at the temperature; then raising the temperature to 600 ℃ at the speed of 0.5 ℃/min, and preserving the heat for 0.5h at the temperature; finally, the temperature is raised to 1200 ℃ at the speed of 5 ℃/min, and the temperature is kept at the temperature for 0.5h, so that the boron-containing zirconium oxide-aluminum oxide composite short fiber with uniform diameter and length is obtained.
Example 3
A preparation method of zirconia-alumina composite short fiber comprises the following steps:
(1) Preparation of the spinning dope
Fully dissolving 2mol of formic acid, 2mol of acetic acid, 2mol of oxalic acid and 36mol of water, uniformly mixing, and then adding 3mol of aluminum hydroxide; condensing and refluxing for 9h at 85 ℃; adding 0.17mol of zirconium hydroxide; continuously condensing and refluxing for 20min; cooling and filtering to obtain uniform and transparent aluminum zirconium carboxylate sol; adding 0.01mol of yttrium acetate, 0.083mol of boric acid and 0.45mol of polyvinyl alcohol into the aluminum zirconium carboxylate sol, and distilling at 40 ℃ under reduced pressure until the viscosity is 300 Pa.s to prepare spinnable aluminum zirconium composite spinning solution;
(2) Preparation of precursor fiber
Pouring the aluminum-zirconium composite spinning solution prepared in the step (1) into a material tank, defoaming in vacuum for 8min, spinning the spinning solution by using a metering pump under the conditions that the ambient temperature is 25 ℃ and the relative humidity is 20%, wherein the flow of the metering pump is 50cc/min, and obtaining precursor fibers by drawing, filament falling and short cutting devices.
(3) High temperature heat treatment
Putting the precursor fiber prepared in the step (2) into a muffle furnace, heating to 125 ℃ at the speed of 0.5 ℃/min, and preserving heat for 0.75h at the temperature; then the temperature is raised to 650 ℃ at the speed of 2 ℃/min, and the temperature is kept for 0.75h; and finally, heating to 1300 ℃ at the speed of 8 ℃/min, and preserving the heat for 1h at the temperature to obtain the boron-containing zirconium oxide-aluminum oxide composite short fiber with uniform diameter and length.
Example 4
A preparation method of zirconia-alumina composite short fiber comprises the following steps:
(1) Preparation of the spinning dope
Fully dissolving 5.9mol of oxalic acid, 1.6mol of acetic acid and 42mol of water, uniformly mixing, and then adding 3mol of aluminum hydroxide; condensing and refluxing for 10 hours at the temperature of 70 ℃; adding 0.3mol of zirconium hydroxide; continuously condensing and refluxing for 10min; cooling and filtering to obtain uniform and transparent aluminum zirconium carboxylate sol; adding 0.02mol of yttrium acetate, 0.036 mol of boric acid and 0.41mol of polyvinyl alcohol (PVA) into the aluminum zirconium carboxylate sol, and distilling at 40 ℃ under reduced pressure until the viscosity is 450Pa s to prepare an aluminum zirconium composite spinning solution with spinnability;
(2) Preparation of precursor fiber
Pouring the aluminum-zirconium composite spinning solution prepared in the step (1) into a material tank, defoaming in vacuum for 5min, spinning the spinning solution by using a metering pump under the conditions that the ambient temperature is 20 ℃ and the relative humidity is 15%, wherein the flow of the metering pump is 60cc/min, and obtaining precursor fibers with the diameter of 15 micrometers and the length of 1cm through drawing, filament falling and short cutting devices.
(3) High temperature heat treatment
Putting the precursor fiber prepared in the step (2) into a muffle furnace, heating to 100 ℃ at the speed of 0.1 ℃/min, and preserving heat for 0.5h at the temperature; then raising the temperature to 600 ℃ at the speed of 0.5 ℃/min, and preserving the heat at the temperature for 0.5 ℃; and finally, heating to 1200 ℃ at the speed of 5 ℃/min, and preserving heat for 2 hours at the temperature to obtain the boron-containing zirconium oxide-aluminum oxide composite short fiber with uniform diameter and length.
Example 5
A preparation method of zirconia-alumina composite short fiber comprises the following steps:
(1) Preparation of the spinning dope
Fully dissolving 0.4mol of formic acid, 1.4mol of oxalic acid, 1.6mol of citric acid and 30mol of water, uniformly mixing, and then adding 3mol of aluminum hydroxide; condensing and refluxing for 8h at the temperature of 95 ℃; adding 0.12mol of zirconium hydroxide; continuously condensing and refluxing for 30min; cooling and filtering to obtain uniform and transparent aluminum zirconium carboxylate sol; adding 0.008mol of yttrium acetate, 0.083mol of boric acid and 0.08mol of polyvinyl alcohol (PVA) into the aluminum zirconium carboxylate sol, and distilling at 50 ℃ under reduced pressure until the viscosity is 800 Pa.s to prepare spinnable aluminum zirconium composite spinning solution;
(2) Preparation of precursor fiber
Pouring the aluminum-zirconium composite spinning solution prepared in the step (1) into a material tank, defoaming in vacuum for 10min, spinning the spinning solution by using a metering pump under the conditions that the ambient temperature is 30 ℃ and the relative humidity is 35%, wherein the flow rate of the metering pump is 30cc/min, and obtaining precursor fibers with the diameter of 20 microns and the length of 50cm through drawing, filament falling and short cutting devices.
(3) High temperature heat treatment
Putting the precursor fiber prepared in the step (2) into a muffle furnace, heating to 150 ℃ at the speed of 1.0 ℃/min, and preserving heat for 1h at the temperature; then heating to 700 ℃ at the speed of 3.0 ℃/min, and preserving the heat for 1h at the temperature; finally, the temperature is raised to 1400 ℃ at the speed of 10 ℃/min, and the temperature is kept for 0.5h at the temperature, so that the boron-containing zirconia-alumina composite short fiber with uniform diameter and length is obtained.
Example 6
A preparation method of boron-containing zirconia-alumina composite short fiber comprises the following steps:
(1) Preparation of the spinning dope
Fully dissolving and uniformly mixing 1.6mol of formic acid, 1.6mol of acetic acid, 4.28mol of malonic acid and 60mol of water, and then adding 3mol of aluminum hydroxide; condensing and refluxing for 9h at 85 ℃; adding 0.24mol of zirconium hydroxide; continuously condensing and refluxing for 20min; cooling and filtering to obtain uniform and transparent aluminum zirconium carboxylate sol; adding 0.012mol of yttrium acetate, 0.106mol of boric acid and 0.54mol of polyvinyl alcohol (PVA) into the aluminum zirconium carboxylate sol, and distilling at 45 ℃ under reduced pressure until the viscosity is 300 Pa.s to prepare spinnable aluminum zirconium composite spinning solution;
(2) Preparation of precursor fiber
And (2) pouring the aluminum-zirconium composite spinning solution prepared in the step (1) into a material tank, defoaming for 8min in vacuum, spinning the spinning solution by adopting a metering pump under the conditions that the ambient temperature is 26 ℃ and the relative humidity is 22%, wherein the flow of the metering pump is 40cc/min, and obtaining precursor fibers with the diameter of 16 microns and the length of 30cm through drawing, filament falling and short cutting devices.
(3) High temperature heat treatment
Putting the precursor fiber prepared in the step (2) into a muffle furnace, heating to 120 ℃ at the speed of 0.6 ℃/min, and preserving heat for 0.6h at the temperature; then heating to 600 ℃ at the speed of 1.0 ℃/min, and preserving heat for 0.5h at the temperature; and finally, heating to 1300 ℃ at the speed of 10 ℃/min, and preserving the heat for 2h at the temperature to obtain the boron-containing zirconium oxide-aluminum oxide composite short fiber with uniform diameter and length.
Comparative example 1
A preparation method of zirconia-alumina composite short fiber comprises the following steps:
the other conditions were identical to those of example 3, except that: the zirconium hydroxide and aluminum hydroxide are added simultaneously. White precipitate is generated, and the spinning solution can be formed by distillation after filtration, but the spinnability is poor.
Comparative example 2
A preparation method of zirconia-alumina composite short fiber comprises the following steps:
the other conditions were identical to those of example 3, except that: fully dissolving 4mol of formic acid, 4mol of acetic acid, 4mol of malonic acid and 75mol of water, uniformly mixing, and then adding 3mol of aluminum hydroxide; condensing and refluxing for 9h at 85 ℃; adding 0.37mol of zirconium hydroxide; continuously condensing and refluxing for 20min; cooling and filtering to obtain uniform and transparent aluminum zirconium carboxylate sol; adding 0.04mol of yttrium acetate, 0.25mol of boric acid and 1.2mol of polyvinyl alcohol into the aluminum zirconium carboxylate sol, and distilling at 40 ℃ under reduced pressure until the viscosity is 300 Pa.s to prepare the spinnable aluminum zirconium composite spinning solution. The prepared spinning solution is transparent, but has poor spinnability. It can be seen that too much organic carboxylic acid is not favorable for the synthesis of the spinning dope.
Comparative example 3
A preparation method of zirconia-alumina composite short fiber comprises the following steps:
the other conditions were identical to those of example 3, except that: fully dissolving 1mol of formic acid, 0.5mol of acetic acid, 0.5mol of malonic acid and 20mol of water, uniformly mixing, and then adding 3mol of aluminum hydroxide; condensing and refluxing for 9h at 85 ℃; adding 0.1mol of zirconium hydroxide; continuously condensing and refluxing for 20min; cooling and filtering to obtain uniform and transparent aluminum zirconium carboxylate sol; adding 0.0015mol of yttrium acetate, 0.02mol of boric acid and 0.05mol of polyvinyl alcohol into the aluminum zirconium carboxylate sol, and distilling at 40 ℃ under reduced pressure until the viscosity is 300 Pa.s to prepare spinnable aluminum zirconium composite spinning solution. The prepared spinning solution is transparent, but has poor spinnability. It can be seen that too little organic carboxylic acid is detrimental to the synthesis of the dope.
Comparative example 4
A preparation method of zirconia-alumina composite short fiber comprises the following steps:
the other conditions were identical to those of example 3, except that: the temperature of the condensing reflux was 120 ℃. A large amount of white precipitate was produced which could not be distilled to form a spinning dope after filtration. It can be seen that the condensing reflux temperature is too high to facilitate the reaction of aluminum hydroxide and zirconium hydroxide with the organic carboxylic acid.
Comparative example 5
A preparation method of zirconia-alumina composite short fiber comprises the following steps:
the other conditions were identical to those of example 3, except that: the temperature of the condensing reflux was 60 ℃. A large amount of white precipitate was produced which could not be distilled to form a spinning dope after filtration. It can be seen that the condensing reflux temperature is too low to facilitate the reaction of aluminum hydroxide and zirconium hydroxide with the organic carboxylic acid.
Comparative example 6
A preparation method of zirconia-alumina composite short fiber comprises the following steps:
the other conditions were identical to those of example 3, except that: the final temperature of the heat treatment in the step (3) was 1150 ℃. The obtained fiber has a main crystal phase of t-ZrO2 and only a small amount of theta-Al 2O3; it can thus be seen that a change in the heat treatment temperature affects the formation of crystalline phases in the fibers.
Comparative example 7
A preparation method of zirconia-alumina composite short fiber comprises the following steps:
the other conditions were identical to those of example 3, except that: and (3) placing the precursor fiber prepared in the step (2) in a muffle furnace, heating to 1300 ℃ at the speed of 8 ℃/min, and preserving heat for 1h at the temperature. The prepared fiber was severely pulverized. It can be seen that too fast a rate of temperature increase is detrimental to the heat treatment of the fibers.
The experimental procedures of examples 1 to 6 and comparative examples 1 to 7 and the diameter and length of the obtained fiber were observed, and the results are shown in the following figures.
TABLE 1 Experimental phenomena or results of fiber diameter and length tests obtained for examples 1-6 and comparative examples 1-7
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The preparation method of the aluminum zirconium composite spinning solution is characterized in that the aluminum zirconium composite spinning solution is prepared by taking aluminum hydroxide, zirconium hydroxide, organic carboxylic acid, yttrium acetate and boric acid as raw materials through a sol-gel method.
2. The method for preparing the aluminum zirconium composite spinning solution according to claim 1, wherein the organic carboxylic acid and water are mixed, then the aluminum hydroxide is added, the mixture is condensed and refluxed for 8 to 10 hours at 70 to 95 ℃, then the zirconium hydroxide is added, and the condensation and reflux are continued for 10 to 30 minutes ； Cooling and filtering to obtain aluminum zirconium carboxylate sol, adding yttrium acetate, boric acid and polyvinyl alcohol into the aluminum zirconium carboxylate sol, and carrying out reduced pressure distillation to obtain the aluminum zirconium composite spinning solution.
3. The method of preparing an aluminum zirconium composite spinning solution according to claim 2, wherein the molar ratio of the aluminum hydroxide to the organic carboxylic acid is 1:1-2.5; the molar ratio of aluminum hydroxide to water is 1:10-20 parts of; the molar ratio of the aluminum hydroxide to the zirconium hydroxide is 10-25:1; the molar ratio of zirconium hydroxide to yttrium acetate is 15-50:1; the molar ratio of the aluminum hydroxide to the boric acid is 28-108:1.
4. the method of claim 2, wherein polyvinyl alcohol is added in an amount of 0.2 to 1.4wt% based on the total mass of the raw materials.
5. The method of claim 1, wherein the organic carboxylic acid is one or more of formic acid, acetic acid, oxalic acid, malonic acid, and citric acid.
6. The method of preparing an aluminum zirconium composite spinning solution according to claim 2, wherein the temperature of the reduced pressure distillation is 40 to 50 ℃, and the distillation is performed until the viscosity is 300 to 800 Pa-s.
7. The preparation method of the precursor fiber is characterized in thatIn that ， The aluminum zirconium composite spinning solution prepared by any one of claims 1 to 6 is defoamed in vacuum, then is spun under the conditions that the ambient temperature is 20 to 30 ℃ and the relative humidity is 15 to 35 percent, and is drawn, dropped and chopped to obtain precursor fibers.
8. The method of claim 7, wherein the spinning solution is spun by a metering pump, and the flow rate of the metering pump is 30 to 60cc/min.
9. A method for preparing zirconia-alumina composite short fiber is characterized in that precursor fiber prepared according to any one of claims 7 to 8 is placed in a muffle furnace, firstly, the temperature is slowly raised to 100-150 ℃, and then, the temperature is kept for 0.5-1h; then slowly heating to 600-700 ℃, and preserving heat for 0.5-1h at the temperature; finally, the temperature is increased to 1200-1400 ℃, and the temperature is kept for 0.5-2h at the temperature, so as to prepare the zirconia-alumina composite short fiber.
10. The method for preparing zirconia-alumina composite short fiber according to claim 9, characterized in that the temperature is raised to 100-150 ℃ at a rate of 0.1-1.0 ℃/min, to 600-700 ℃ at a rate of 0.5-3.0 ℃/min, and to 1200-1400 ℃ at a rate of 5-10 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211435557.9A CN115896980A (en) | 2022-11-16 | 2022-11-16 | Preparation method of aluminum-zirconium composite spinning solution, precursor fiber and zirconia-alumina composite short fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211435557.9A CN115896980A (en) | 2022-11-16 | 2022-11-16 | Preparation method of aluminum-zirconium composite spinning solution, precursor fiber and zirconia-alumina composite short fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115896980A true CN115896980A (en) | 2023-04-04 |
Family
ID=86493410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211435557.9A Pending CN115896980A (en) | 2022-11-16 | 2022-11-16 | Preparation method of aluminum-zirconium composite spinning solution, precursor fiber and zirconia-alumina composite short fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115896980A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4010233A (en) * | 1970-11-06 | 1977-03-01 | Bayer Aktiengesellschaft | Production of inorganic fibers |
| CN102181962A (en) * | 2010-09-30 | 2011-09-14 | 南京理工大学 | Method for preparing thin-diameter zirconium oxide fibers and fiber board thereof |
| CN111074379A (en) * | 2019-12-26 | 2020-04-28 | 山东鲁阳浩特高技术纤维有限公司 | Alumina-zirconia composite short fiber and preparation method thereof |
| CN111139552A (en) * | 2020-01-14 | 2020-05-12 | 山东鲁阳浩特高技术纤维有限公司 | Preparation method of alumina short fiber |
-
2022
- 2022-11-16 CN CN202211435557.9A patent/CN115896980A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4010233A (en) * | 1970-11-06 | 1977-03-01 | Bayer Aktiengesellschaft | Production of inorganic fibers |
| CN102181962A (en) * | 2010-09-30 | 2011-09-14 | 南京理工大学 | Method for preparing thin-diameter zirconium oxide fibers and fiber board thereof |
| CN111074379A (en) * | 2019-12-26 | 2020-04-28 | 山东鲁阳浩特高技术纤维有限公司 | Alumina-zirconia composite short fiber and preparation method thereof |
| CN111139552A (en) * | 2020-01-14 | 2020-05-12 | 山东鲁阳浩特高技术纤维有限公司 | Preparation method of alumina short fiber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102965764B (en) | Preparation method of aluminum oxide ceramic continuous fiber | |
| CN106927808B (en) | Preparation method of yttrium aluminum garnet continuous fibers | |
| CN102011215B (en) | Process for preparing yttrium aluminum garnet-based continuous fibers through sol-gel method | |
| CN107266081B (en) | Preparation method of alumina-zirconia composite ceramic continuous fiber | |
| CN102070326B (en) | Preparation process of multi-element composite alumina-based continuous fibers | |
| CN111074379B (en) | Alumina-zirconia composite short fiber and preparation method thereof | |
| WO2021159646A1 (en) | Lanthanide rare earth-organic polymer precursor, lanthanide rare earth oxide fiber, preparation method therefor and application thereof | |
| CN112195535B (en) | Precursor sol for continuous alumina fiber and application thereof | |
| CN110592724B (en) | Hf-Al-Si complex phase oxide ceramic fiber and preparation method thereof | |
| CN104141181A (en) | Preparation method for ZrO2 fiber with SiO2 doped | |
| CN109437862B (en) | Containing 1-5 wt% of B2O3Preparation method of alumina-based ceramic continuous fiber | |
| CN113957567B (en) | TiO 2 2 -SiO 2 Precursor sol spinning solution and preparation method of titanium-silicon composite oxide nanofiber | |
| CN108570725A (en) | A kind of melt spinning raw material of aluminium oxide continuous fiber, preparation method and aluminium oxide continuous fiber obtained | |
| CN105002601A (en) | Preparation method of polycrystalline Al2O3-Y3Al5O12 complex-phase fibers or pure YAG fibers | |
| CN101516803B (en) | Polycrystalline corundum fibers and method for the production thereof | |
| CN115896980A (en) | Preparation method of aluminum-zirconium composite spinning solution, precursor fiber and zirconia-alumina composite short fiber | |
| CN102180656B (en) | Technology for preparing alumina-based continuous fibers by using inorganic aluminum salts | |
| CN102775143A (en) | Method for preparing fully-stabilized tetragonal-phase zirconia crystal fibers | |
| CN114804894A (en) | Multi-element complex-phase micro-nano ceramic fiber and preparation method and application thereof | |
| CN1792805A (en) | Process for preparing yttrium aluminium garnet nano powder | |
| CN113968725B (en) | Al-Zr complex phase oxide continuous ceramic fiber and preparation method thereof | |
| CN102351516B (en) | Method for preparing alumina-based continuous fibers by using SiO2 nano powder raw material | |
| CN111074426A (en) | Alumina-zirconia composite fiber blanket and preparation method thereof | |
| CN111978550A (en) | Yttrium/aluminum-organic polymer precursor, yttrium aluminum garnet continuous fiber and preparation method | |
| CN115182074B (en) | Rare earth lanthanum oxide modified alumina-mullite fiber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |