CN112813537B - Rare earth zirconate inorganic fiber and preparation method thereof - Google Patents
Rare earth zirconate inorganic fiber and preparation method thereof Download PDFInfo
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- CN112813537B CN112813537B CN202110376424.8A CN202110376424A CN112813537B CN 112813537 B CN112813537 B CN 112813537B CN 202110376424 A CN202110376424 A CN 202110376424A CN 112813537 B CN112813537 B CN 112813537B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
Abstract
The invention relates to a rare earth zirconate inorganic fiber and a preparation method thereof. The preparation method comprises the steps of dissolving a zirconium source, a rare earth source, an organic ligand and a spinning auxiliary agent in a solvent according to a certain proportion to prepare rare earth zirconate precursor sol; obtaining rare earth zirconate precursor fiber by using the rare earth zirconate precursor sol through an electrostatic spinning method; and (3) carrying out heat treatment on the rare earth zirconate precursor fiber to prepare the rare earth zirconate inorganic fiber. The method has the advantages of wide raw material sources, stable and reliable sol and good spinnability, the obtained rare earth zirconate fiber is of a single-phase structure, the diameter of the fiber is 0.4-1.6 mu m, the flexibility and the form stability of the fiber are kept under the high temperature condition of room temperature to 1400 ℃, the crystalline phase stability of the fiber is kept between room temperature and 1600 ℃, and the method has application advantages in the fields of high temperature heat insulation, high temperature filtration and the like.
Description
Technical Field
The invention relates to a rare earth zirconate inorganic fiber and a preparation method thereof, belonging to the field of inorganic nonmetallic materials.
Background
In recent years, with the rapid development of economic society and the improvement of the requirements of China on energy conservation and emission reduction, higher requirements are put forward on the high-temperature heat-insulating property and the high-temperature durability of a heat-insulating material in the industrial field. The ceramic fiber is one of the key materials of the high-temperature heat-insulating material due to the advantages of light weight, high temperature resistance, low thermal conductivity, good corrosion resistance, good thermal shock resistance and the like. The development of ceramic fiber with low thermal conductivity, stable high-temperature structure and stable crystalline phase fully exerts the advantages of the thermophysical property and the fiber structure of the material, is applied to high-temperature and ultrahigh-temperature thermal protection engineering, and is an important direction for the development of the inorganic fiber at present.
The rare earth zirconate materials have the advantages of high melting point, low thermal conductivity, no phase change, sintering resistance and the like, become excellent candidate materials for high-temperature heat insulation materials, and are widely researched in the fields of high-temperature thermal barrier coatings, high-temperature refractory materials and the like, so that the rare earth zirconate fibers are excellent high-grade inorganic fiber materials from the perspective of thermophysical properties. For example, the invention patent CN103553596a reports a preparation method of rare earth lanthanum zirconate fiber, which mainly uses zirconium nitrate and lanthanum nitrate as metal sources, and citric acid as an organic ligand to prepare pyrochlore type lanthanum zirconate fiber with high temperature stability. Document "contamination of La2Zr2O7 ceramic fibers via electrospinning method using different La2O3The presursors proposes to use zirconyl acetate as zirconium source, lanthanum nitrate, lanthanum chloride and acetic acidLanthanum is used as a lanthanum source to prepare the lanthanum zirconate fiber, and the fiber shows excellent high-temperature stability and heat insulation performance. However, the zirconium source or lanthanum source adopted in the preparation method of the zirconate fibers does not have spinnability, further optimization is needed, in addition, the solid content of zirconate in the precursor has a space for improving, the research reports of the rare earth zirconate fibers are relatively less, and effective references cannot be provided for the comprehensive performance evaluation of the rare earth zirconate fibers.
Disclosure of Invention
In order to solve the problems of insufficient spinnability of the precursor, low solid content of zirconate in the precursor and insufficient research on other types of rare earth zirconate in the rare earth zirconate fiber, the invention provides the rare earth zirconate inorganic fiber and the preparation method thereof, which can further improve the spinnability of precursor sol, increase the solid content of the precursor fiber and provide a universal preparation method for the rare earth zirconate fiber.
The rare earth zirconate inorganic fiber prepared by the invention is of a single-phase structure, and the molecular formula is Re2Zr2O7(Re = Y, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, lu), the fiber diameter distribution is 0.4-1.6 μm, and the fiber flexibility and form stability are maintained under the high temperature condition of room temperature to 1400 ℃, and the crystal phase stability is maintained at the room temperature to 1600 ℃.
The technical scheme of the invention is as follows:
a preparation method of rare earth zirconate inorganic fiber comprises the following steps:
(a) Preparation of rare earth zirconate precursor sol
Adding a zirconium source and an organic ligand into a solvent with a mass ratio of solid to solvent =1 (0.8 to 3) according to a molar ratio of the zirconium source to the organic ligand =1 (0.5 to 1.5), and dissolving to obtain a zirconia precursor sol; under the conditions of heating and stirring at the temperature of 20-90 ℃, adding a rare earth source with the molar ratio of Zr to Re =1:1 into the zirconia precursor sol, and dissolving to prepare a rare earth zirconate sol; adding high molecular polymer with the mass fraction of 0.5-10% into the rare earth zirconate sol, and fully dissolving to prepare rare earth zirconate precursor sol;
(b) Preparation of rare earth zirconate precursor fiber by electrostatic spinning method
Performing electrostatic spinning on the rare earth zirconate precursor sol in the step (a) to prepare a rare earth zirconate precursor fiber, wherein the electrostatic spinning process condition is that the spinning distance is 8-40 cm, the spinning voltage is 4-50kV, the sol propelling speed is 0.8-3.6 mL/h, the ambient temperature is 10-45 ℃, and the ambient humidity is 10-65%;
(c) Preparation of rare earth zirconate inorganic fiber
Heating the rare earth zirconate precursor fiber prepared in the step (b) to 450-600 ℃ at a heating rate of 0.5-6 ℃/min under an atmospheric condition, and keeping the temperature for 0-4 h; and then heating to 1000-1400 ℃ at the heating rate of 0.5-10 ℃/min, and preserving the heat for 1-4 h to prepare the rare earth zirconate inorganic fiber.
Preferably, when the organic ligand is acetic acid, the zirconium source in step (a) is organic ligand =1: 0.8-1.2; when the organic ligand is glycol, the ratio of the zirconium oxychloride to the organic ligand =1: 0.6-1.0; when the organic ligand is acetylacetone or ethyl acetoacetate, the ratio of zirconium oxychloride to organic ligand =1: 0.8-1.0 in step (a).
Preferably, according to the present invention, the solvent in step (a) is water or absolute ethanol.
According to the invention, the mass ratio of solid to solvent in step (a) is preferably =1 (1.5 to 2).
According to the invention, the heating temperature in step (a) is preferably from 40 to 80 ℃.
Preferably according to the invention, the rare earth source of step (a) is a rare earth carbonate, a rare earth hydroxide or a rare earth oxide.
According to the invention, when the high molecular polymer in the step (a) is polyethylene oxide, the addition amount of the high molecular polymer is 0.8 to 2.0 percent of the mass fraction of the solution; when the high molecular polymer in the step (a) is polyvinylpyrrolidone, the addition amount of the high molecular polymer is 6 to 12 percent of the mass fraction of the solution; when the high molecular polymer in the step (a) is one of polymethyl methacrylate and polyvinyl alcohol or the combination of the polymethyl methacrylate and the polyvinyl alcohol, the adding amount of the high molecular polymer is 4~8 percent of the mass fraction of the solution.
Preferably according to the present invention, the electrospinning process conditions in step (b) are: the spinning distance is 16 to 24cm, the spinning voltage is 15 to 30kV, the sol propulsion speed is 1.2 to 2.5mL/h, the ambient temperature is 20 to 35 ℃, and the ambient humidity is 10 to 55%.
Preferably, according to the present invention, the atmosphere in step (c) is an air atmosphere.
The invention obtains the following excellent effects:
1. the invention has the advantages of simple process, low cost, stable and reliable sol, good spinnability, high solid content of zirconate, and easy spinning preparation and large-scale production.
2. The rare earth zirconate fiber prepared by the invention has low formation temperature of stable crystalline phase, 1200 ℃, and can keep stable crystalline phase from room temperature to 1600 ℃.
3. The diameter of the high-entropy zirconate fiber prepared by the invention is 0.5-1.5 μm, and the flexibility and the form integrity of the fiber can be kept at room temperature to 1400 ℃.
4. The invention can realize the preparation of a series of rare earth zirconate fibers and has great application prospect in the fields of high-temperature heat insulation, high-temperature filtration and the like.
Drawings
FIG. 1 is an XRD pattern of lanthanum zirconate fiber obtained in example 2 heat-treated to 1200 ℃.
FIG. 2 is an SEM photograph of the lanthanum zirconate fiber obtained in example 2 heat-treated to 1200 ℃.
FIG. 3 is an XRD pattern of lanthanum zirconate fibers obtained in example 3 heat-treated to 1200 ℃.
FIG. 4 is an SEM photograph of the lanthanum zirconate fibers obtained in example 3 heat-treated to 1200 ℃.
Detailed Description
The invention is further illustrated but not limited by the following examples of rare earth lanthanum zirconate in combination with the accompanying drawings.
The raw materials used in the examples are all commercially available raw materials.
Example 1:
a preparation method of rare earth lanthanum zirconate inorganic fiber comprises the following steps:
(a) Preparation of lanthanum zirconate precursor sol
Adding raw materials of zirconium oxychloride and glacial acetic acid into water with a mass ratio of solid to water of =1: 2 according to a molar ratio of zirconium oxychloride to glacial acetic acid of =1: 1.2, and dissolving to obtain a zirconium oxide precursor sol; under the condition of heating and stirring at 65 ℃, lanthanum hydroxide with the molar ratio of Zr to La =1 to 1 is added into the zirconia precursor sol, and the rare earth zirconate sol is prepared by dissolving; adding polyoxyethylene with the mass fraction of 1% into the rare earth zirconate sol, and fully dissolving to prepare a rare earth zirconate precursor sol;
(b) Preparation of rare earth zirconate precursor fiber by electrostatic spinning method
Preparing the rare earth zirconate precursor fiber from the rare earth zirconate precursor sol in the step (a) through electrostatic spinning, wherein the electrostatic spinning process condition is that the spinning distance is 16 cm, the spinning voltage is 16 kV, the sol propelling speed is 1.2 mL/h, the environmental temperature is 20-25 ℃, and the environmental humidity is 30-45%;
(c) Preparation of rare earth zirconate inorganic fiber
And (c) heating the rare earth zirconate precursor fiber prepared in the step (b) to 500 ℃ at the heating rate of 1 ℃/min under the atmosphere condition, then heating to 1200 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 2h to prepare the rare earth zirconate inorganic fiber.
Example 2:
as described in example 1, the molar ratio zirconium oxychloride glacial acetic acid =1: 1.2 was replaced with zirconium oxychloride glacial acetic acid =1:1, while the molar ratio Zr: la =1:1 lanthanum hydroxide was replaced with the molar ratio Zr: la =1:0.8 and the molar ratio Zr: la =1: 0.2 lanthanum acetate. The XRD pattern of the obtained lanthanum zirconate lower fiber is shown in fig. 1, and the SEM image of the obtained lanthanum zirconate fiber is shown in fig. 2.
Example 3:
as described in example 2, except that glacial acetic acid was replaced by acetylacetone. The XRD pattern of the obtained lanthanum zirconate lower fiber is shown in fig. 3, and the SEM image of the obtained lanthanum zirconate fiber is shown in fig. 4.
Example 4:
as described in example 2, except that glacial acetic acid was replaced with ethyl acetoacetate.
Example 5:
as described in example 2, except that glacial acetic acid was replaced with ethylene glycol.
Example 6:
as described in example 1, except that zirconium oxychloride was replaced with zirconyl nitrate.
Example 7:
as described in example 2, except that zirconium oxychloride was replaced with zirconium nitrate.
Example 8:
as described in example 1, except that lanthanum hydroxide was replaced with lanthanum oxide.
Example 9:
as described in example 1, except that lanthanum hydroxide was replaced with lanthanum carbonate.
Example 10:
as described in example 2, except that lanthanum acetate was replaced with lanthanum nitrate.
Example 11:
as described in example 2, except that lanthanum acetate was replaced with lanthanum chloride.
Example 12:
as described in example 1, except that 1% of the polyethylene oxide was replaced with 10% of polyvinylpyrrolidone.
The above description is only a preferred embodiment of the present invention, which is made by taking lanthanum zirconate as an example, and is not intended to limit the scope of the present invention. The invention is not intended to be exhaustive or exhaustive of other rare earth zirconate fibers because of its high versatility, and it is to be understood that any modifications and equivalents which fall within the spirit and scope of the present invention are intended to be included therein.
Claims (7)
1. The rare earth zirconate inorganic fiber is characterized in that the molecular formula of the zirconate inorganic fiber is Re2Zr2O7 (Re = Y, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu), the diameter of the fiber is 0.4-1.6 mu m, the fiber can keep flexibility and complete form under the high temperature condition of room temperature to 1400 ℃, and the crystal phase can be kept stable under the room temperature to 1600 ℃.
The rare earth zirconate inorganic fiber is obtained by the following steps:
(a) Preparation of rare earth zirconate precursor sol
Adding a zirconium source and an organic ligand into a solvent with the mass ratio of solid to solvent =1 (0.8-3) according to the molar ratio of zirconium source to organic ligand =1 (0.5-1.5), and dissolving to obtain a zirconia precursor sol; under the condition of heating and stirring at the temperature of 20-90 ℃, adding a rare earth source with the molar ratio of Zr to Re =1:1 into the zirconia precursor sol, and dissolving to prepare rare earth zirconate sol; adding high molecular polymer with the mass fraction of 0.5-10% into the rare earth zirconate sol, and fully dissolving to prepare rare earth zirconate precursor sol;
(b) Preparation of rare earth zirconate precursor fiber by electrostatic spinning method
Preparing the rare earth zirconate precursor fiber from the rare earth zirconate precursor sol obtained in the step (a) through electrostatic spinning, wherein the electrostatic spinning process conditions comprise that the spinning distance is 8-40 cm, the spinning voltage is 4-50 kV, the sol propelling speed is 0.8-3.6 mL/h, the ambient temperature is 10-45 ℃, and the ambient humidity is 10-65%;
(c) Preparation of rare earth zirconate inorganic fiber
Heating the rare earth zirconate precursor fiber prepared in the step (b) to 450-600 ℃ at a heating rate of 0.5-6 ℃/min under the atmosphere condition, and preserving the heat for 0-4 h; then heating to 1000-1400 ℃ at the heating rate of 0.5-10 ℃/min, and preserving the heat for 1-4 h to prepare the rare earth zirconate inorganic fiber.
2. The rare earth zirconate inorganic fiber of claim 1 wherein the source of zirconium in step (a) is one of zirconium oxychloride, zirconyl nitrate, zirconium nitrate, or combinations thereof.
3. The rare earth zirconate inorganic fiber of claim 1 wherein the organic ligand of step (a) is one of acetylacetone, acetic acid, ethylene glycol, ethyl acetoacetate, or combinations thereof.
4. The rare earth zirconate inorganic fiber of claim 1 wherein, when the organic ligand is acetic acid, the zirconium source of step (a) is from 0.6 to 2.0 organic ligand = 1; when the organic ligand is ethylene glycol, the zirconium oxychloride of the step (a) has the following structure that the organic ligand = 1; when the organic ligand is acetylacetone or ethyl acetoacetate, the ratio of zirconium oxychloride to organic ligand =1 in step (a) is 0.8 to 1.2.
5. The rare earth zirconate inorganic fiber of claim 1 wherein the rare earth source of step (a) is one of rare earth acetates, rare earth oxides, rare earth hydroxides, rare earth carbonates, rare earth nitrates, rare earth chlorides, rare earth acetylacetonates, or combinations thereof.
6. The rare earth zirconate inorganic fiber of claim 1, wherein the high molecular weight polymer of step (a) is one of polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, polyvinyl alcohol, or a combination thereof.
7. The rare earth zirconate inorganic fiber of claim 1 wherein the atmosphere in step (c) is one of air, water vapor, nitrogen, or combinations thereof.
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