CN111233445A - High-temperature high-strength flexible zirconia-silica fiber membrane and preparation method and application thereof - Google Patents
High-temperature high-strength flexible zirconia-silica fiber membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a high-temperature high-strength flexible zirconia-silica fiber membrane and a preparation method and application thereof. ZrO prepared by the invention2‑SiO2The fiber membrane has the advantages of highly ordered fiber arrangement, uniform fiber diameter, compact structure and smaller grain size,the strength is higher, and the material also has flexible behaviors such as bending winding, folding stretching and the like, and has wide application prospect in the fields of structural reinforcement materials, high-temperature flexible refractory materials, fire-fighting heat insulation materials, flexible electronic devices, chemical corrosion resistant materials, aerospace and the like.
Description
Technical Field
The invention relates to a high-temperature high-strength flexible zirconia-silica fiber membrane and a preparation method thereof, in particular to a high-temperature high-strength flexible zirconia-silica fiber membrane taking a metal organic polymer with a linear spinnable structure as a precursor and a preparation method thereof, belonging to the field of inorganic nonmetallic ceramic fiber materials.
Background
Zirconia has shown irreplaceability in many applications due to its extremely high melting point (2710 ℃), low thermal conductivity, excellent chemical stability and mechanical properties. The zirconia refractory fiber material not only has excellent physical and chemical properties of zirconia, but also has excellent characteristics of large length-diameter ratio, good flexibility, high mechanical strength and the like, and has important functions in the fields of aerospace and national defense, building thermal protection and civil industry. The zirconia fiber is composed of polycrystalline particles, and crystal grains forming the fiber rapidly grow at high temperature, so that the flexibility of the fiber is lost, the strength is reduced, and the high-temperature service performance of the fiber is seriously influenced. Therefore, how to make zirconia fiber maintain high strength and flexibility under high temperature condition is a very challenging problem facing its application.
Chinese patent document CN 109576820A discloses a preparation method of high-strength and high-toughness zirconia nanofibers, however, the heat treatment temperature of the method is 700 ℃, the heat treatment temperature is low, and the method cannot ensure that the zirconia nanofibers still have high strength and high flexibility at the high temperature of 1300 ℃. Chinese patent document CN 103451851a discloses a method for preparing a flexible high-strength zirconia nanofiber membrane, which comprises adding metal oxide nanoparticles to inhibit the growth of crystal grains at a lower heat treatment temperature, and enhancing the flexibility and strength of the zirconia nanofiber membrane at 1000 ℃, while at 1300 ℃, the growth of zirconia crystal grains cannot be inhibited, and the fiber membrane also cannot have usable mechanical properties at 1300 ℃.
Therefore, in order to obtain the zirconia fiber with good mechanical properties at high temperature, the conflict between the flexibility and the strength of the zirconia fiber is essentially solved starting from the aspects of delaying crystallization and inhibiting grain growth. The invention is therefore proposed.
Disclosure of Invention
Aiming at the defects of the prior art and the process, the invention provides a high-temperature high-strength flexible zirconia fiber membrane and a preparation method thereof, in particular to a high-temperature high-strength flexible zirconia fiber membrane taking a metal organic polymer with a linear spinnable structure as a precursor and a preparation method thereof. According to the invention, amorphous silicon oxide is introduced, zirconium oxide is embedded into an amorphous silicon oxide matrix, the formed Zr/Si amorphous interface and the formed Zr-O-Si bond inhibit the crystallization of zirconium oxide grains, and the crystallization temperature is increased. At the high temperature of 1300 ℃, the formed amorphous silicon oxide nano layer has the sintering resistance function as a barrier layer, the growth of crystal grains is further delayed, the structural integrity and the size integrity of the fiber are kept, and the flexibility of the fiber film is ensured; meanwhile, the viscosity of the spinning solution and the spinning parameters are controlled to obtain the high-orientation nanofiber membrane, so that the strength of the nanofiber membrane is greatly improved, the brittleness of the zirconia fiber at high temperature is overcome, and the high-orientation nanofiber membrane has high strength.
The technical scheme of the invention is as follows:
the high-strength high-temperature flexible zirconia-silica fiber membrane comprises zirconia and amorphous silica, wherein the zirconia is embedded into an amorphous silica matrix to form a Zr/Si amorphous interface. The formed Zr-O-Si bond inhibits the crystallization of the zirconia crystal grains and increases the crystallization temperature.
According to the present invention, the zirconia-silica fiber film preferably forms an amorphous silica nanolayer at a high temperature of 1300 ℃ or higher. The amorphous silicon oxide nano layer can be used as a barrier layer and has the sintering resistance effect, the growth of crystal grains is further delayed, the structural integrity and the size integrity of the fiber are kept, and the flexibility of the fiber film is ensured.
According to the invention, preference is given toThe zirconia-silica fiber membrane contains ZrO2-SiO2Nano-fiber grains, the average grain size of the grains is 1-50 nm;
preferably, the mechanical strength of the zirconia-silica fiber membrane is 1 to 7 MPa.
According to the invention, the preparation method of the high-temperature high-strength flexible zirconia-silica fiber membrane comprises the following steps:
(1) dissolving a zirconium source in a solvent, adding or not adding a stabilizing agent, adding a spinning auxiliary agent, water and a silicon source, stirring and aging to obtain a spinning solution;
(2) performing electrostatic spinning on the spinning solution to obtain a precursor fiber membrane;
(3) and carrying out heat treatment on the precursor fiber film to obtain the high-temperature high-strength flexible zirconia-silica fiber film.
According to the present invention, preferred conditions in step (1) are as follows:
preferably, the zirconium source is zirconium Polyacetylacetonate (PAZ), and the stabilizer is yttrium nitrate;
preferably, the solvent is one or a mixture of more than two of absolute methanol, absolute ethanol, acetone and N, N-dimethylformamide;
preferably, the silicon source is methyl orthosilicate or silane, and further preferably, the silane is methyltrimethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane or gamma-chloropropyltriethoxysilane;
preferably, the spinning auxiliary agent is polyoxyethylene;
preferably, the spinning solution contains 5 to 60 percent of silicon by mole, and more preferably 30 to 50 percent of silicon by mole; the zirconium content is 50% -70%, and the mass ratio of water to the zirconium source is 1:2.08-1: 5.2; the mass ratio of the zirconium source to the solvent is 1:3-1: 5; the mass ratio of the stabilizer to the zirconium source is 0:1-0.16:1, and the mass ratio of the spinning auxiliary agent to the solvent is 1:300-1: 500;
preferably, the stirring and aging time is 60-900min, the stirring and aging process ensures that the silicon source is hydrolyzed completely, and slag balls are prevented from being generated in the spinning process.
Preferably, the viscosity of the spinning dope is 12 to 30 mPs.
According to the present invention, preferred conditions in step (2) are as follows:
preferably, the electrospinning conditions: relative humidity of 30-60%, preferably 40-50%; the temperature is 15-40 ℃, the further optimization is 20-30 ℃, the spinning voltage is 6-20KV, the receiving distance is 10-30cm, and the propelling speed is 0.8-2.5 ml/h; the receiving device is a metal roller, and the rotating speed of the roller is 40-1000r/min, and preferably 80-500 r/min.
According to the present invention, preferred conditions in step (3) are as follows:
the heat treatment is carried out in an air atmosphere and comprises the following steps: gradually heating from room temperature to 800-1300 deg.C, heating rate of 1-5 deg.C/min, and maintaining at 800-1300 deg.C for 0-300min, preferably 60-200 min;
preferably, the heat treatment procedure is: heating from room temperature to 600 ℃ at a heating rate of 1 ℃/min, then heating to 1200 ℃ at a heating rate of 2 ℃/min, and then heating to 1300 ℃ at a temperature of 5 ℃/min.
According to the invention, the preparation method of the high-temperature high-strength flexible zirconia-silica fiber membrane comprises the following steps:
(1) preparing a zirconium-silicon polymer precursor spinning solution: dissolving poly (zirconium acetylacetonate) (PAZ) in a solvent by taking PAZ as a zirconium source, and stirring for dissolving; adding yttrium nitrate, and stirring until the yttrium nitrate is dissolved; adding a spinning auxiliary agent, heating, stirring and dissolving; adding a silicon source with the silicon content of 5-60%, stirring and aging for 60-900min to obtain a spinning solution;
(2) spinning a precursor fiber film: under the conditions of 15-40 ℃, 30-60% of ambient humidity and 40-1000r/min of rotation speed of a roller receiving device, carrying out electrostatic spinning on the spinning solution to obtain a precursor fiber membrane; the prepared precursor fiber film has the characteristics of uniform fiber diameter, good fiber continuity and high degree of unidirectional fiber arrangement, and the unidirectional arrangement greatly improves the strength of the fiber film in the direction;
(3) carrying out heat treatment on the obtained precursor nanofiber membrane in air atmosphere to obtain flexible ZrO2/SiO2A nanofiber membrane.
According to the invention, the poly-acetylacetone zirconium (PAZ) can be prepared by referring to the prior art, and can be obtained by synthesizing a precursor-acetylacetone zirconium polymer by taking acetylacetone and zirconium oxychloride as main raw materials, referring to Chinese patent document CN 1459418A.
ZrO of the invention2/SiO2The nanofiber membrane has high unidirectional arrangement, fine grain size at high temperature, high strength and excellent high-temperature flexibility, and can be used as a structural reinforcing material, a high-temperature flexible refractory material, a fire-fighting heat-insulating material, a flexible electronic device, a chemical corrosion-resistant material, an aerospace field and the like.
According to the invention, the high-temperature high-strength flexible zirconia-silica fiber membrane is applied to structural reinforcement materials, high-temperature flexible refractory materials, fire-fighting heat insulation materials, flexible electronic devices and chemical corrosion resistant materials.
The invention has the technical characteristics and excellent effects that:
1. the high-temperature high-strength flexible zirconia-silica fiber membrane has high unidirectional arrangement, fine grain size at 1300 ℃, high mechanical strength and excellent high-temperature flexibility. The mechanical strength can reach 4.9MPa, and the flexible wire has flexible behaviors of folding, stretching, bending, winding and the like.
2. The preparation method is simple and controllable, and the orientation of the fiber membrane can be regulated and controlled by regulating the viscosity of the spinning solution, the spinning distance and the rotating speed of the roller.
3. The invention does not need complex heat treatment process and atmosphere protection, has simple preparation process and is easy for industrialized production.
Description of the drawings:
FIG. 1 is a photograph of a precursor fiber film obtained in step (2) of example 1 of the present invention;
FIG. 2 is a photograph showing a folded highly flexible fibrous membrane obtained by high temperature treatment at 1300 ℃ in example 1 of the present invention;
FIG. 3 is an SEM photograph of the ordered fiber membrane made in example 2;
FIG. 4 is a graph showing a grain size distribution of silicon oxide after heat treatment at 1300 ℃ in example 1;
fig. 5 is a TEM photograph of the microstructure of the zirconia-silica fiber film obtained in example 1.
The specific embodiment is as follows:
the present invention is further illustrated by, but not limited to, specific embodiments thereof with reference to the accompanying drawings.
The starting materials used in the examples are commercially available and were not further processed.
Example 1
A preparation method of a high-temperature high-strength flexible zirconia-silica fiber membrane comprises the following preparation steps:
(1) adding 200g of PAZ into 1000g of absolute ethyl alcohol, stirring until the PAZ is completely dissolved, adding 25g of yttrium nitrate, stirring until the PAZ is completely dissolved, adding 2g of polyethylene oxide, dropwise adding 60g of deionized water, heating to 45 ℃, stirring until the PAZ is completely dissolved, then adding 172g of ethyl orthosilicate, and stirring for 8 hours to obtain a precursor spinning solution.
(2) Performing electrostatic spinning on the precursor spinning solution in the step (1) under the conditions that the spinning parameters are 45% of humidity, 25 ℃ of temperature, 11KV of voltage, 1.5ml/h of propelling speed, 20cm of receiving distance and 80r/min of roller receiving speed to obtain a precursor fiber membrane; the picture of the object is shown in figure 1.
(3) Carrying out heat treatment on the precursor fiber membrane spun in the step (2) to obtain ZrO2/SiO2Nanofiber membranes, ZrO obtained2/SiO2The nanofiber membrane is highly ordered, good in flexibility and high in strength. The heat treatment procedure is as follows: heating from room temperature to 600 ℃ at a heating rate of 1 ℃/min, then heating to 1200 ℃ at a heating rate of 2 ℃/min, and then heating to 1300 ℃ at a temperature of 5 ℃/min.
ZrO obtained in this example2-SiO2The nanofiber had a small grain size with an average grain size of 27nm and a grain size distribution as shown in fig. 4. ZrO (ZrO)2-SiO2The nanofiber membrane has high strength of 4.9MPa, flexible behaviors such as folding, stretching and the like, and ZrO2-SiO2The nanofiber membrane can be folded into a boat, and the physical photograph is shown in fig. 2.
Example 2
As described in example 1, except that:
adding 200g of PAZ into 667g of absolute ethyl alcohol in the step (1), stirring until the PAZ is completely dissolved, adding 25g of yttrium nitrate, and stirring until the PAZ is completely dissolved; adding 2g of polyoxyethylene, dropwise adding 60g of deionized water, heating to 45 ℃, stirring until the polyoxyethylene is completely dissolved, then adding 172g of tetraethoxysilane, and stirring for 2 hours to obtain a precursor spinning solution.
The obtained precursor spinning solution has good spinnability, the precursor fiber is longer than that of the embodiment 1, the fiber diameter is more uniform, and ZrO2-SiO2The nanofiber membrane was highly oriented and the SEM photograph of the ordered fiber membrane is shown in fig. 3.
Example 3
As described in example 1, except that:
adding 200g of PAZ into 1000g of absolute ethyl alcohol in the step (1), stirring until the PAZ is completely dissolved, adding 2g of polyoxyethylene, dropwise adding 60g of deionized water, heating to 45 ℃, stirring until the PAZ is completely dissolved, then adding 172g of tetraethoxysilane, and stirring for 8 hours to obtain a precursor spinning solution;
without addition of yttrium nitrate, ZrO2No phase change, SiO2Is always in an amorphous state, ZrO2-SiO2The nanofiber membrane has the same high strength and excellent flexibility.
Example 4
As described in example 1, except that:
performing electrostatic spinning on the precursor spinning solution in the step (1) in the step (2) under the conditions that the spinning parameters are 45% of humidity, 25 ℃ of temperature, 11KV of voltage, 1.5ml/h of propelling speed, 20cm of receiving distance and 500r/min of roller receiving speed to obtain a precursor fiber membrane;
the obtained precursor fiber film has high orientation degree, and compared with the fiber film in the embodiment 1, the rotation speed is higher, the obtained precursor fiber has shorter length, and the obtained precursor fiber film is compact.
Example 5
As described in example 1, except that:
and (3) carrying out heat treatment on the precursor fiber membrane spun in the step (2), wherein the heat treatment process comprises the following steps: heating from room temperature to 600 ℃ at a heating rate of 1 ℃/min, heating to 1100 ℃ at a heating rate of 2 ℃/min from 600 ℃, and preserving heat for 120 min;
ZrO obtained2-SiO2The nanofiber membrane is highly ordered, has multiple flexible behaviors such as bending, winding, folding, stretching and the like, and has high strength.
Example 6
As described in example 1, except that:
(1) adding 200g of PAZ into 667g of absolute ethyl alcohol in the step (1), stirring until the PAZ is completely dissolved, adding 2g of polyethylene oxide, dropwise adding 60g of deionized water, heating to 45 ℃, stirring until the PAZ is completely dissolved, then adding 113g of methyltrimethoxysilane, and stirring for 8 hours to obtain a precursor spinning solution;
(2) performing electrostatic spinning on the precursor spinning solution in the step (1) under the conditions that the spinning parameters are 45% of humidity, 25 ℃ of temperature, 11KV of voltage, 1.5ml/h of propelling speed, 20cm of receiving distance and 80r/min of roller receiving speed to obtain a precursor fiber membrane;
(3) and (3) carrying out heat treatment on the precursor fiber membrane spun in the step (2), wherein the heat treatment process comprises the following steps: heating from room temperature to 600 ℃ at a heating rate of 1 ℃/min, then heating to 1200 ℃ at a heating rate of 2 ℃/min, and then heating to 1300 ℃ at a temperature of 5 ℃/min;
the obtained precursor spinning solution is more stable, the spinnability is good, the fiber is straight and uniform, and the obtained ZrO2-SiO2The nanofiber membrane has good flexibility and lower strength than that of example 1.
Comparative example 1
Example 1, step (1), 200g of PAZ was added to 1000g of absolute ethanol in step (1), stirred until completely dissolved, 25g of yttrium nitrate was added, and stirred until completely dissolved; adding 2g of polyoxyethylene, dropwise adding 60g of deionized water, heating to 45 ℃, stirring until the deionized water is completely dissolved, then adding 172g of tetraethoxysilane, and stirring for 2 hours to obtain a precursor spinning solution;
compared with the example 1, the aging time of the precursor spinning solution is changed, the hydrolysis degree of the tetraethoxysilane is not enough, the viscosity is 4 mPas, the viscosity is lower,the spinnability is reduced, a large amount of slag balls are generated in the electrostatic spinning process, precursor fibers are short, and the obtained ZrO2/SiO2The nanofiber membrane has poor flexibility and low strength.
Comparative example 2
As described in step (1) of example 1, 200g of PAZ was added to 1000g of absolute ethanol, stirred until completely dissolved, and then 25g of yttrium nitrate was added and stirred until completely dissolved; adding 2g of polyoxyethylene, dropwise adding 60g of deionized water, heating to 45 ℃, stirring until the deionized water is completely dissolved, then adding 104g of tetraethoxysilane, and stirring for 8 hours to obtain a precursor spinning solution;
compared with the example 1, the content of silicon is reduced, after the heat treatment at 1300 ℃, because the amorphous silicon oxide can not completely surround the zirconium oxide crystal grains, the growth of the crystal grains can not be inhibited at high temperature, and the obtained ZrO2-SiO2The nanofiber membrane decreases in flexibility and strength.
Comparative example 3
Performing electrostatic spinning on the precursor spinning solution in the step (1) under the conditions that the spinning parameters are 45% of humidity, 25 ℃ of temperature, 11KV of voltage, 1.5ml/h of propelling speed, 20cm of receiving distance and 200r/min of roller receiving speed to obtain a precursor fiber film as in the step (2) of the embodiment 1;
ZrO obtained in comparison with example 12-SiO2The nanofiber membrane is only partially ordered.
Comparative example 4
As described in step (1) of example 1, in step (1), 200g of PAZ was added to 1000g of absolute ethanol, stirred until completely dissolved, and then 25g of yttrium nitrate was added and stirred until completely dissolved; adding 2g of polyoxyethylene, dropwise adding 60g of deionized water, heating to 45 ℃, stirring until the deionized water is completely dissolved, then adding 113g of methyltrimethoxysilane, and stirring for 2h to obtain a precursor spinning solution;
compared with the embodiment 1, the silicon source is changed and the stirring time is reduced, the hydrolysis degree of the tetraethoxysilane is low, a large amount of liquid drops splash in the electrostatic spinning process, the obtained precursor fiber is short in length, the continuity of the fiber is not enough, the fiber diameter is not uniform, and the obtained ZrO2-SiO2The nanofiber membrane has lower strength and toughnessA difference;
comparative example 5
As described in step (1) of example 1, in step (1), 200g of PAZ was added to 667g of anhydrous ethanol, stirred until completely dissolved, then 25g of yttrium nitrate was added, stirred until completely dissolved; adding 2g of polyoxyethylene, dropwise adding 60g of deionized water, heating to 45 ℃, stirring until the deionized water is completely dissolved, then adding 172g of tetraethoxysilane, and stirring for 8 hours to obtain a precursor spinning solution;
compared with the example 1, the mass ratio of the solvent is reduced, the spinning solution is aged quickly, the viscosity is increased extremely quickly, the sol stability is poor, the spinnability is poor, and the obtained fiber has thick diameter and ZrO2-SiO2The nanofiber membrane has low strength.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the invention, and these modifications and improvements should be considered within the scope of the invention.
Claims (10)
1. The high-temperature high-strength flexible zirconia-silica fiber membrane is characterized in that the chemical composition of the fiber membrane comprises zirconia and amorphous silica, wherein the zirconia is embedded in an amorphous silica matrix to form a Zr/Si amorphous interface.
2. A high-temperature high-strength flexible zirconia-silica fiber membrane according to claim 1, wherein said zirconia-silica fiber membrane contains ZrO2-SiO2The average grain size of the nano-fiber grains is 1-50 nm.
3. The high-temperature high-strength flexible zirconia-silica fiber membrane according to claim 1, wherein the mechanical strength of the zirconia-silica fiber membrane is 1 to 7 MPa.
4. The method for preparing the high-temperature high-strength flexible zirconia-silica fiber membrane of claim 1, comprising the steps of:
(1) dissolving a zirconium source in a solvent, adding or not adding a stabilizing agent, adding a spinning auxiliary agent, water and a silicon source, stirring and aging to obtain a spinning solution;
(2) performing electrostatic spinning on the spinning solution to obtain a precursor fiber membrane;
(3) and carrying out heat treatment on the precursor fiber film to obtain the high-temperature high-strength flexible zirconia-silica fiber film.
5. The method for preparing a high-temperature high-strength flexible zirconia-silica fiber membrane according to claim 4, wherein the zirconium source in step (1) is zirconium Polyacetylacetonate (PAZ), and the stabilizer is yttrium nitrate;
preferably, the solvent is one or a mixture of more than two of absolute methanol, absolute ethanol, acetone and N, N-dimethylformamide;
preferably, the silicon source is methyl orthosilicate or silane, and further preferably, the silane is methyltrimethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane or gamma-chloropropyltriethoxysilane;
preferably, the spinning auxiliary agent is polyethylene oxide.
6. The preparation method of the high-temperature high-strength flexible zirconia-silica fiber membrane according to claim 4, wherein the spinning solution in the step (1) contains 5 to 60% by mole of silicon, preferably 30 to 50%; the zirconium content is 50% -70%, and the mass ratio of water to the zirconium source is 1:2.08-1: 5.2; the mass ratio of the zirconium source to the solvent is 1:3-1: 5; the mass ratio of the stabilizer to the zirconium source is 0:1-0.16:1, and the mass ratio of the spinning auxiliary agent to the solvent is 1:300-1: 500;
preferably, the viscosity of the spinning dope is 12 to 30 mPs.
7. The method for preparing a high-strength high-temperature flexible zirconia-silica fiber membrane according to claim 4, wherein the electrospinning conditions in the step (2) are as follows: relative humidity 30-60%, preferably 40-50%; the temperature is 15-40 ℃, the optimized temperature is 20-30 ℃, the spinning voltage is 6-20KV, the receiving distance is 10-30cm, and the propelling speed is 0.8-2.5 ml/h; the receiving device is a metal roller, and the rotating speed of the roller is 40-1000r/min, preferably 80-500 r/min.
8. The method for preparing a high-temperature high-strength flexible zirconia-silica fiber membrane according to claim 4, wherein the heat treatment in the step (3) is performed in an air atmosphere, and the heat treatment comprises: gradually heating from room temperature to 800-1300 deg.C, heating rate of 1-5 deg.C/min, and maintaining at 800-1300 deg.C for 0-300min, preferably 60-200 min.
9. The method for preparing a high-temperature high-strength flexible zirconia-silica fiber membrane according to claim 4, wherein the heat treatment procedure in the step (3) is as follows: heating from room temperature to 600 ℃ at a heating rate of 1 ℃/min, then heating to 1200 ℃ at a heating rate of 2 ℃/min, and then heating to 1300 ℃ at a temperature of 5 ℃/min.
10. Use of the high strength, high temperature flexible zirconia-silica fiber membrane of claim 1 in structural reinforcement, high temperature flexible refractory, fire protection insulation, flexible electronics, chemical resistant materials.
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| CN114561719A (en) * | 2022-01-19 | 2022-05-31 | 东华大学 | Cerium oxide/silicon oxide composite fiber material with fiber interweaving structure and preparation method and application thereof |
| CN114561720A (en) * | 2022-01-19 | 2022-05-31 | 东华大学 | High-infrared-emissivity flexible calcium chromate lanthanum/silicon oxide composite fiber material and preparation method and application thereof |
| CN114561719B (en) * | 2022-01-19 | 2024-04-26 | 东华大学 | Cerium oxide/silicon oxide composite fiber material with fiber interweaved structure and preparation method and application thereof |
| CN114561720B (en) * | 2022-01-19 | 2024-04-26 | 东华大学 | High-infrared-emissivity flexible calcium lanthanum chromate/silicon oxide composite fiber material and preparation method and application thereof |
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