CN113089135A - High-entropy zirconate inorganic fiber and preparation method thereof - Google Patents
High-entropy zirconate inorganic fiber and preparation method thereof Download PDFInfo
- Publication number
- CN113089135A CN113089135A CN202110376381.3A CN202110376381A CN113089135A CN 113089135 A CN113089135 A CN 113089135A CN 202110376381 A CN202110376381 A CN 202110376381A CN 113089135 A CN113089135 A CN 113089135A
- Authority
- CN
- China
- Prior art keywords
- entropy
- zirconate
- source
- fiber
- preparation
- 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.)
- Granted
Links
Images
Classifications
-
- 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
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention relates to a high-entropy zirconate inorganic fiber and a preparation method thereof. The preparation method comprises the steps of heating and dissolving zirconium basic carbonate, a calcium source, a strontium source, a barium source, glacial acetic acid and a spinning aid in a water solution according to a certain proportion to prepare high-entropy zirconate precursor sol; obtaining high-entropy zirconate precursor fiber by the high-entropy zirconate precursor sol through an electrostatic spinning method; and (3) preparing the high-entropy zirconate inorganic fiber by carrying out heat treatment on the high-entropy zirconate precursor fiber. The obtained sol is stable and good in spinnability, the obtained high-entropy zirconate fiber is a single-phase solid solution, the fiber diameter is 0.5-1.5 mu m, and the stable crystal phase and fiber form are kept under the condition of high temperature ranging from room temperature to 1400 ℃.
Description
Technical Field
The invention relates to a high-entropy zirconate inorganic fiber and a preparation method thereof, belonging to the field of inorganic non-metallic materials.
Background
Since the concept of high entropy proposed by Yuei and Cantor in alloy is expanded to ceramic by the initiatives of Rost in 2015, the high entropy ceramic material is used as a novel multi-principal element solid solution formed by multiple ceramic components in an equimolar ratio or a nearly equimolar ratio, and shows great application potential in the field of high temperature heat insulation by virtue of lower thermal conductivity, slow diffusion effect and more excellent performance.
The oxide inorganic fiber has the advantages of excellent high-temperature stability, oxidation resistance, corrosion resistance, light weight and the like, and has developed into one of the key materials in the field of high-temperature heat insulation. However, oxide fibers exist under high temperature use conditionsA common problem is brittleness and even dusting of the fibers due to grain growth. Therefore, a new approach for optimizing the microstructure of the oxide inorganic fiber and inhibiting the grain growth without reducing the high-temperature heat-insulating property of the fiber is sought, and is a problem to be solved urgently. While high-entropy ceramic structures have lower thermal conductivity, high structural stability and excellent performance, as described in the literature (La)0.2Ce0.2Nd0.2Sm0.2Eu0.2)2Zr2O7The study structure in A novel high-entropy ceramic with low thermal conductivity and trough grain growth rate shows that the high-entropy zirconate ceramic structure can show slow grain growth rate and lower thermal conductivity. Therefore, the high-entropy structure provides possibility for the structural optimization and the improvement of the heat insulation performance of the oxide inorganic fiber. However, although there is much research on high-entropy ceramics, there is no report on the preparation of high-entropy oxide fibers, and the lack of experience of preparation is a problem to be solved for applying high-entropy structures to the optimization of oxide inorganic fibers.
Disclosure of Invention
In order to solve the defects and shortcomings of the oxide fiber, a high-entropy structure is applied to structure optimization of the inorganic oxide fiber, the invention provides the high-entropy zirconate inorganic fiber and a preparation method thereof, and meanwhile, the high-entropy zirconate fiber provides a novel product for the high-temperature heat-insulating fiber.
The high-entropy zirconate inorganic fiber prepared by the invention is a single-phase solid solution with a molecular formula of (CaSrBa) ZrO3The fiber diameter is 0.5-1.5 μm, and the crystal phase and the fiber form are kept stable under the high temperature condition of room temperature to 1400 ℃.
The technical scheme of the invention is as follows:
a preparation method of high-entropy zirconate inorganic fiber comprises the following steps:
(a) preparation of high-entropy zirconate fiber precursor sol
Adding solid raw materials of basic zirconium carbonate, a calcium source, a strontium source and a barium source into the solid according to the element molar ratio of Zr to Ca to Sr to Ba = 3 to 1Water =1 (0.5-5), and adding Zr and CH in a molar ratio under the condition of heating and stirring at 10-90 DEG C3Dissolving glacial acetic acid (COOH = 1) (1.5-6) to prepare high-entropy zirconate sol; adding high-molecular polymer with the mass fraction of 0.1-10% into the high-entropy zirconate sol, and fully dissolving to prepare high-entropy zirconate fiber precursor sol;
(b) preparation of high-entropy zirconate precursor fiber by electrostatic spinning method
Preparing the high-entropy zirconate precursor fiber from the high-entropy zirconate fiber precursor sol obtained in the step (a) through electrostatic spinning, wherein the electrostatic spinning process condition is that the spinning distance is 4-30 cm, the spinning voltage is 8-50 kV, the sol propelling speed is 0.6-4.0 mL/h, the ambient temperature is 10-35 ℃, and the ambient humidity is 10-65%;
(c) preparation of high-entropy zirconate inorganic fiber
Heating the high-entropy zirconate precursor fiber prepared in the step (b) to 450-600 ℃ at a heating rate of 0.5-5 ℃/min under an atmosphere condition, and preserving the heat for 30-180 min; and then heating to 800-1200 ℃ at the heating rate of 1-10 ℃/min, and preserving the heat for 1-5 h to prepare the high-entropy zirconate inorganic fiber.
According to the invention, the mass ratio of solid to water in the step (a) is preferably =1 (1-2).
According to the invention, the heating temperature in the step (a) is preferably 45-60 ℃.
According to the invention, in step (a), when the calcium source, the strontium source and the barium source are all acetate, the glacial acetic acid in step (a) is added in a molar ratio of Zr to CH3COOH =1: 2; when one of the calcium source, the strontium source and the barium source is acetate, the glacial acetic acid added in the step (a) has the mol ratio of Zr to CH3COOH =1: 3.5; when two of the calcium source, the strontium source and the barium source are acetate, the molar ratio of the glacial acetic acid added in the step (a) is Zr to CH3COOH =1: 2.5; when none of the calcium source, the strontium source and the barium source is acetate, the glacial acetic acid added in the step (a) is Zr to CH in a molar ratio3COOH = 1: 4。
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 0.5-2.5% 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 5-10% 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 a combination thereof, the addition amount of the high molecular polymer is 4-8% 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 15-20 cm, the spinning voltage is 12-25 kV, the sol propelling speed is 1.2-3.0 mL/h, the ambient temperature is 20-35 ℃, and the ambient humidity is 10-50%.
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 simple process, low cost, stable and reliable sol, and is easy for spinning preparation and large-scale production.
2. The high-entropy zirconate fiber single-phase solid solution prepared by the invention has low forming temperature, a high-entropy structure can be obtained at 800 ℃, and the high-entropy structure can be kept stable at room temperature to 1400 ℃.
3. The diameter of the high-entropy zirconate fiber prepared by the invention is 0.5-1.5 μm, and the high-entropy zirconate fiber can keep stable crystalline phase and complete fiber form at 1400 ℃.
4. The high-entropy zirconate fiber prepared by the invention is a brand-new inorganic oxide fiber material, and has great application prospect in the field of high-temperature heat insulation and preservation.
Drawings
FIG. 1 is the XRD pattern of the high entropy zirconate fiber obtained in example 1 heat treated to 1200 ℃.
FIG. 2 is an SEM image of the high entropy zirconate fibers obtained in example 1 heat treated to 1200 ℃.
FIG. 3 is a diagram showing the elemental distributions of Ca (a), Sr (b), Ba (c), and Zr (d) in the zirconia fiber obtained in example 1 heat-treated to 1200 ℃.
Detailed Description
The present invention will be further described by way of examples, but not limited thereto, with reference to the accompanying drawings.
The raw materials used in the examples are all commercially available raw materials.
Example 1:
a preparation method of high-entropy zirconate inorganic fiber comprises the following steps:
(a) preparation of high-entropy zirconate fiber precursor sol
Adding solid raw materials of basic zirconium carbonate, calcium acetate, strontium acetate and barium acetate into water with the mass ratio of solid to water =1:1 according to the element molar ratio of Zr to Ca to Sr to Ba = 3 to 1, and adding Zr to CH with the molar ratio under the condition of heating and stirring at 60 DEG C3Dissolving glacial acetic acid with COOH =1: 2 to prepare high-entropy zirconate sol; adding polyoxyethylene with the mass fraction of 1% into the high-entropy zirconate sol, and fully dissolving to prepare the high-entropy zirconate fiber precursor sol;
(b) preparation of high-entropy zirconate precursor fiber by electrostatic spinning method
Preparing the high-entropy zirconate precursor fiber from the high-entropy zirconate fiber precursor sol obtained in the step (a) through electrostatic spinning, wherein the electrostatic spinning process condition is that the spinning distance is 15cm, the spinning voltage is 15kV, the sol propelling speed is 1.2mL/h, the ambient temperature is 20-25 ℃, and the ambient humidity is 30-45%;
(c) preparation of high-entropy zirconate inorganic fiber
Heating the high-entropy zirconate precursor fiber prepared in the step (b) to 600 ℃ at the heating rate of 1 ℃/min under the atmosphere condition, and preserving the heat for 30 min; then heating to 1200 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 2h to prepare the high-entropy zirconate inorganic fiber. The XRD (X-ray diffraction) pattern of the crystal phase test result of the prepared high-entropy zirconate fiber is shown in figure 1, the SEM (scanning Electron microscope) result of the fiber morphology is shown in figure 2, the scanning pattern of the fiber element distribution surface is shown in figure 3, and the diameter distribution of the fiber is 0.5-1.5 mu m.
Example 2:
as described in example 1, except that the calcium acetate in step (a) was replaced by calcium hydroxide, the molar ratio Zr: CH was added3Glacial acetic acid COOH =1: 3.
Example 3:
as described in example 1, except that in step (a) the calcium acetate was replaced by calcium oxide, the molar ratio Zr: CH was added3COOH =1: 3 iceAcetic acid.
Example 4:
as described in example 1, except that the barium acetate in step (a) was replaced by barium hydroxide, the molar ratio Zr: CH was added3Glacial acetic acid COOH =1: 3.
Example 5:
as described in example 1, except that in step (a) calcium acetate was replaced by barium oxide, the molar ratio Zr: CH was added3Glacial acetic acid COOH =1: 3.
Example 6:
as described in example 1, except that the barium acetate in step (a) was replaced by strontium hydroxide, the molar ratio Zr: CH was added3Glacial acetic acid COOH =1: 3.
Example 7:
as described in example 1, except that barium acetate in step (a) was replaced by strontium oxide, the molar ratio Zr: CH was added3Glacial acetic acid COOH =1: 3.
Example 8:
the procedure is as described in example 1, except that 1% by weight of polyethylene oxide is replaced by 6% by weight of polyvinyl alcohol in step (a).
Example 9:
the procedure is as described in example 1, except that 1% by weight of polyethylene oxide is replaced by 8% by weight of polyvinylpyrrolidone in step (a).
Claims (8)
1. The high-entropy zirconate inorganic fiber is characterized by being a single-phase solid solution, and the molecular formula of the high-entropy zirconate inorganic fiber is (CaSrBa) ZrO3The fiber diameter is 0.5-1.5 μm, and the crystal phase and the fiber form are kept stable under the high temperature condition of room temperature to 1400 ℃.
2. A process for the preparation of high entropy zirconate inorganic fibers according to claim 1, comprising the steps of:
(a) preparation of high-entropy zirconate precursor sol
The solid raw materials of basic zirconium carbonate, calcium source and strontium are mixedAdding a source and a barium source into water with a solid-water mass ratio of =1: 0.5-5 according to an element molar ratio of Zr, Ca, Sr and Ba = 3:1:1:1, and adding Zr, CH and the like under the condition of heating and stirring at 10-90 DEG C3Dissolving glacial acetic acid (COOH = 1) (1.5-6) to prepare high-entropy zirconate sol; adding high-molecular polymer with the mass fraction of 0.1-10% into the high-entropy zirconate sol, and fully dissolving to prepare the high-entropy zirconate precursor sol;
(b) preparation of high-entropy zirconate precursor fiber by electrostatic spinning method
Preparing the high-entropy zirconate precursor fiber from the high-entropy zirconate precursor sol obtained in the step (a) through electrostatic spinning, wherein the electrostatic spinning process condition is that the spinning distance is 4-30 cm, the spinning voltage is 8-50 kV, the sol propelling speed is 0.6-4.0 mL/h, the ambient temperature is 10-35 ℃, and the ambient humidity is 10-65%;
(c) preparation of high-entropy zirconate inorganic fiber
Heating the high-entropy zirconate precursor fiber prepared in the step (b) to 450-600 ℃ at a heating rate of 0.5-5 ℃/min under an atmosphere condition, and preserving the heat for 30-180 min; and then heating to 800-1200 ℃ at the heating rate of 1-10 ℃/min, and preserving the heat for 1-5 h to prepare the high-entropy zirconate inorganic fiber.
3. A process for the preparation of high entropy zirconate inorganic fibers of claim 2 wherein the calcium source in step (a) is one or a combination of calcium acetate, calcium hydroxide, calcium oxide.
4. A process for the preparation of high entropy zirconate inorganic fibers of claim 2 wherein the strontium source in step (a) is one of strontium acetate, strontium hydroxide, strontium oxide or combinations thereof.
5. A process for the preparation of high entropy zirconate inorganic fibers of claim 2 wherein the barium source of step (a) is one or a combination of barium acetate, barium hydroxide, barium oxide.
6. Preparation of high entropy zirconate inorganic fiber according to claim 2The method is characterized in that when the calcium source, the strontium source and the barium source are all acetate, the glacial acetic acid in the step (a) is added in a molar ratio of Zr to CH3COOH =1 (1.5-2.5); when one of the calcium source, the strontium source and the barium source is acetate, the glacial acetic acid added in the step (a) has the mol ratio of Zr to CH3COOH =1 (3-4); when two of the calcium source, the strontium source and the barium source are acetate, the molar ratio of the glacial acetic acid added in the step (a) is Zr to CH3COOH =1 (2-3); when none of the calcium source, the strontium source and the barium source is acetate, the glacial acetic acid added in the step (a) is Zr to CH in a molar ratio3COOH = 1: (3.5~5)。
7. A process for preparing high entropy zirconate inorganic fibers as claimed in claim 2, wherein the high molecular weight polymer in step (a) is one of or a combination of polyethylene oxide, polymethyl methacrylate, polyvinyl pyrrolidone, polyvinyl alcohol.
8. A process for the preparation of high entropy zirconate inorganic fibers of claim 2 wherein the atmosphere in step (c) is one or a combination of air, nitrogen, and water vapor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110376381.3A CN113089135B (en) | 2021-04-08 | 2021-04-08 | High-entropy zirconate inorganic fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110376381.3A CN113089135B (en) | 2021-04-08 | 2021-04-08 | High-entropy zirconate inorganic fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113089135A true CN113089135A (en) | 2021-07-09 |
| CN113089135B CN113089135B (en) | 2022-08-09 |
Family
ID=76675048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110376381.3A Active CN113089135B (en) | 2021-04-08 | 2021-04-08 | High-entropy zirconate inorganic fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113089135B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981487A (en) * | 2021-10-25 | 2022-01-28 | 成都大学 | High-entropy carbonate electrocatalyst and preparation method thereof |
| CN114751737A (en) * | 2021-08-19 | 2022-07-15 | 厦门稀土材料研究所 | Zirconic acid rare earth-based high-entropy ceramic nanofiber and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030368A (en) * | 2010-11-18 | 2011-04-27 | 西南科技大学 | Preparation method of pure-phase high-performance rare earth zirconate material |
| CN105624834A (en) * | 2016-01-30 | 2016-06-01 | 山东大学 | Barium zirconate fiber and method for preparing same |
| CN108505145A (en) * | 2018-04-11 | 2018-09-07 | 山东大学 | A kind of calcium zirconate fiber and preparation method thereof |
| CN110272278A (en) * | 2019-05-17 | 2019-09-24 | 东华大学 | Thermal barrier coating high entropy ceramic powder and preparation method thereof |
| CN110606740A (en) * | 2019-09-11 | 2019-12-24 | 中国科学院金属研究所 | High-entropy rare earth hafnate ceramic material and preparation method thereof |
| CN110668811A (en) * | 2019-11-18 | 2020-01-10 | 郑州大学 | High-entropy zirconate ceramic and preparation method thereof |
-
2021
- 2021-04-08 CN CN202110376381.3A patent/CN113089135B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030368A (en) * | 2010-11-18 | 2011-04-27 | 西南科技大学 | Preparation method of pure-phase high-performance rare earth zirconate material |
| CN105624834A (en) * | 2016-01-30 | 2016-06-01 | 山东大学 | Barium zirconate fiber and method for preparing same |
| CN108505145A (en) * | 2018-04-11 | 2018-09-07 | 山东大学 | A kind of calcium zirconate fiber and preparation method thereof |
| CN110272278A (en) * | 2019-05-17 | 2019-09-24 | 东华大学 | Thermal barrier coating high entropy ceramic powder and preparation method thereof |
| CN110606740A (en) * | 2019-09-11 | 2019-12-24 | 中国科学院金属研究所 | High-entropy rare earth hafnate ceramic material and preparation method thereof |
| CN110668811A (en) * | 2019-11-18 | 2020-01-10 | 郑州大学 | High-entropy zirconate ceramic and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751737A (en) * | 2021-08-19 | 2022-07-15 | 厦门稀土材料研究所 | Zirconic acid rare earth-based high-entropy ceramic nanofiber and preparation method and application thereof |
| CN114751737B (en) * | 2021-08-19 | 2024-06-18 | 厦门稀土材料研究所 | Rare earth zirconate-based high-entropy ceramic nanofiber and preparation method and application thereof |
| CN113981487A (en) * | 2021-10-25 | 2022-01-28 | 成都大学 | High-entropy carbonate electrocatalyst and preparation method thereof |
| CN113981487B (en) * | 2021-10-25 | 2022-04-29 | 成都大学 | High-entropy carbonate electrocatalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113089135B (en) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113089135B (en) | High-entropy zirconate inorganic fiber and preparation method thereof | |
| CN111233445B (en) | High-temperature high-strength flexible zirconia-silica fiber membrane and preparation method and application thereof | |
| CN103553596B (en) | Preparation method of zirconic acid lanthanum ceramic fiber | |
| CN114751737B (en) | Rare earth zirconate-based high-entropy ceramic nanofiber and preparation method and application thereof | |
| CN106929927B (en) | Preparation method of polyacetylacetonatozirconium precursor sol spinning solution and submicron zirconia crystal fiber | |
| CN113308764B (en) | Silicon-based ceramic micro-nanofiber heat insulation felt and preparation method thereof | |
| CN113089132B (en) | Zirconate fiber and preparation method thereof | |
| CN105002601A (en) | Preparation method of polycrystalline Al2O3-Y3Al5O12 complex-phase fibers or pure YAG fibers | |
| TW201035400A (en) | Process of manufacturing inorganic nanofibers | |
| CN112813537B (en) | Rare earth zirconate inorganic fiber and preparation method thereof | |
| CN113957567A (en) | TiO 22-SiO2Precursor sol spinning solution and preparation method of titanium-silicon composite oxide nano-fiber | |
| JP6238286B2 (en) | Zirconia continuous fiber and production method thereof | |
| CN103643402A (en) | Preparation method for lanthanum zirconate ceramic fiber blanket | |
| Deng et al. | High strength, low thermal conductivity and collapsible of Y2O3-stablized HfO2 crystalline fibrous membranes | |
| CN108505145B (en) | Calcium zirconate fiber and preparation method thereof | |
| CN115477546B (en) | Medium-entropy ceramic nanofiber aerogel and preparation method thereof | |
| CN109750388B (en) | Preparation method of defect fluorite phase gadolinium zirconate fiber | |
| CN114804894A (en) | Multi-element complex-phase micro-nano ceramic fiber and preparation method and application thereof | |
| CN102000577B (en) | Magnetic nanocomposite fiber and preparation method and application thereof | |
| CN112876244B (en) | Strontium zirconate inorganic fiber and preparation method thereof | |
| CN110117841B (en) | Method for preparing mullite nanofibers by electrospinning biphase precursors | |
| CN102351516B (en) | Method for preparing alumina-based continuous fibers by using SiO2 nano powder raw material | |
| RU2716621C1 (en) | Method of producing modified aluminium oxide fibres | |
| CN109402785A (en) | Hollow MgO-Al2O3The preparation method of Thermal Insulating Ceramic Fibers | |
| JP2023167827A (en) | Manufacturing method of zirconia continuous fiber precursor and manufacturing method of zirconia continuous fiber |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |