Cerium oxide ytterbium composite material, preparation method thereof and application of cerium oxide ytterbium composite material in near-infrared barrier material
By preparing a core-shell structure of cerium oxide ytterbium composite material, the shortcomings of existing near-infrared blocking materials in terms of spectral control, thermal management, and environmental adaptability have been overcome, achieving highly efficient and energy-saving near-infrared blocking performance, which is suitable for outdoor thermal insulation materials such as building and automotive glass.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-22
- Publication Date
- 2026-04-10
AI Technical Summary
Existing near-infrared blocking materials have shortcomings in terms of spectral control accuracy, thermal management efficiency, environmental adaptability, and material system innovation, making it difficult to achieve highly efficient and energy-saving near-infrared blocking performance.
A core-shell structured composite material with cerium oxide as the core and ytterbium oxide as the shell is prepared by strictly controlling the particle size and pH value and combining it with a high-temperature calcination method to form a cerium oxide-ytterbium composite material with a specific particle size, which is used in spraying technology to achieve a large-area near-infrared blocking layer.
While ensuring visible light transmittance, it improves near-infrared blocking efficiency and solar radiation heat blocking efficiency, thereby enhancing the material's photothermal stability and service life. It is suitable for outdoor thermal insulation materials such as building and automotive glass.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of near-infrared blocking material preparation technology, specifically relating to a cerium oxide ytterbium composite material, its preparation method, and its application in near-infrared blocking materials. Background Technology
[0002] The core objective of near-infrared blocking technology is to selectively block or reflect near-infrared radiation in the solar spectrum while maintaining high visible light transmittance. Currently, materials used for near-infrared blocking have certain shortcomings in several dimensions, including material performance, stability, and cost. Firstly, in terms of spectral control precision, traditional materials struggle to achieve precise narrowband control, and parasitic absorption or reflection in non-target wavelengths is a common problem, leading to a trade-off between visible light transmittance and near-infrared blocking efficiency. Secondly, regarding thermal management efficiency, existing blocking materials are insufficient in blocking solar radiation in the 780–2500 nm wavelength range, and the process of converting absorbed near-infrared light energy into heat dissipation easily causes thermal aging, affecting the material's lifespan. Thirdly, in terms of environmental adaptability, organic blocking materials have poor photothermal stability and are prone to chemical degradation under continuous illumination, while inorganic semiconductor materials face the challenges of high brittleness and difficulty in flexible processing. Finally, in terms of material system innovation, while novel photonic crystals, plasma metamaterials, and other nanostructured materials have shown potential for spectral control, they are still limited by complex fabrication processes, high costs for large-area fabrication, and incompatibility with existing glass processes, hindering industrialization. These material-level shortcomings collectively restrict the development and application expansion of high-efficiency, energy-saving near-infrared blocking technology. Therefore, the present invention provides a cerium oxide ytterbium composite material with excellent near-infrared blocking performance, which achieves near-infrared blocking performance by being prepared as a functional coating. Summary of the Invention
[0003] The present invention aims to provide a method for preparing cerium oxide ytterbium composite material, the method thereof, and its application in near-infrared blocking materials.
[0004] The present invention first provides a cerium oxide-ytterbium composite material, wherein the morphology of the cerium oxide-ytterbium composite material is a core-shell structure with cerium oxide as the core and ytterbium oxide as the shell, wherein the D50 of the cerium oxide core is below 0.1 μm and the D90 is between 0.1 and 0.2 μm.
[0005] This invention also provides a method for preparing the above-mentioned cerium oxide ytterbium composite material, comprising the following specific steps: (1) Cerium oxide is dispersed in water and ground to obtain a cerium oxide suspension; the D50 of cerium oxide in the cerium oxide suspension is below 0.1 μm and the D90 is between 0.1 and 0.2 μm; (2) Slowly add ytterbium chloride solution to cerium oxide suspension. After the addition is complete, add alkaline solution to adjust the pH value to 8-13. Centrifuge to collect the precipitate, wash and ignite to obtain cerium oxide ytterbium composite material.
[0006] The molar ratio of cerium oxide to ytterbium chloride is 1:0.3~0.6.
[0007] The solid content of cerium oxide in the cerium oxide suspension is 10%.
[0008] The concentration of the ytterbium chloride solution is 0.05~0.2 mol / L; preferably 0.1~0.2 mol / L.
[0009] The alkaline solution is ammonia or sodium hydroxide solution with a concentration of 0.1~0.5 mol / L; preferably 0.2~0.4 mol / L.
[0010] The pH value is preferably 9 to 12.
[0011] The centrifugation is a high-speed centrifugation with a rotation speed of 12000~15000 r / min.
[0012] The burning is carried out in an air atmosphere, with a burning temperature of 700~1000℃, preferably 800~900℃, and a burning time of 4~6 hours.
[0013] Furthermore, the cerium oxide is cerium oxide synthesized with the assistance of polyvinylpyrrolidone.
[0014] Specifically, the preparation method of cerium oxide is as follows: 0.5%~4% (w / v) polyvinylpyrrolidone is added to a 0.1~0.5 mol / L solution of cerium nitrate or cerium chloride, and reacted with 0.1~0.5 mol / L sodium hydroxide or ammonia water, with the pH value controlled at 7~13; the filter cake after reaction is repeatedly washed to obtain Ce(OH)3; and calcined at 600~900℃ for 4~6 hours.
[0015] As one of the preferred methods for preparing the above-mentioned cerium oxide, the concentration of the polyvinylpyrrolidone is preferably 1% to 3% w / v.
[0016] As one of the preferred embodiments of the above-mentioned method for preparing cerium oxide, the concentration of cerium nitrate or cerium chloride is preferably 0.2~0.4 mol / L. As one of the preferred methods for preparing the above-mentioned cerium oxide, the pH value is preferably 8 to 12.
[0017] As one of the preferred methods for preparing the above-mentioned cerium oxide, the calcination temperature is preferably 600~800℃.
[0018] The present invention also provides the application of the above-mentioned cerium oxide ytterbium composite material in near-infrared blocking materials.
[0019] This invention prepares cerium oxide nuclei of a specific particle size, then performs heterogeneous nucleation and deposition of ytterbium under strictly controlled pH and molar ratio conditions, and finally obtains a novel composite material with excellent near-infrared blocking properties through high-temperature calcination. This composite material can simultaneously improve its near-infrared blocking efficiency and enhance its solar radiation heat blocking efficiency while maintaining excellent visible light transmittance, thereby improving the material's photothermal stability and extending its service life. The cerium oxide-ytterbium composite material prepared by this invention can be used in spray coating technology to achieve large-area preparation of near-infrared blocking layers, providing a new approach for the efficient and energy-saving development and application of near-infrared blocking technology. Attached Figure Description
[0020] Figure 1 The XRD pattern of the cerium oxide ytterbium composite material prepared in Example 1; Figure 2 This is a TEM image of the cerium oxide ytterbium composite material prepared in Example 1; Figure 3 This is a particle size distribution diagram of the cerium oxide suspension in Example 1; Figure 4 This is a particle size distribution diagram of the cerium oxide suspension in Comparative Example 5. Detailed Implementation
[0021] The present invention will be described in detail below with reference to the embodiments, but these should not be construed as limiting the scope of protection of the present invention.
[0022] Example 1
[0023] (1) Dissolve 2g of polyvinylpyrrolidone in 100mL of water, slowly pour it into 2.9L of 0.2mol / L cerium nitrate solution and stir for 10min. Add 0.1mol / L sodium hydroxide dropwise to the cerium nitrate solution until the pH reaches 10.0. Wash the filter cake with pure water 30 times under vacuum at 5L / cycle to obtain pure Ce(OH)3. After calcining at 750℃ for 5 hours in air atmosphere and cooling, cerium oxide is obtained.
[0024] (2) Cerium oxide was dispersed in water, and the solid content was controlled at about 10% before grinding to obtain a cerium oxide suspension with D50: 0.098 μm and D90: 0.157 μm. Figure 3 ).
[0025] (3) Take 300g of cerium oxide suspension with a solid content of 10%, and slowly add 498ml of 0.1mol / L ytterbium chloride to the cerium oxide suspension. After the addition is completed, add sodium hydroxide with a concentration of 0.4mol / L. Stop the addition when the pH value reaches 11.0. The resulting solution is put into a high-speed centrifuge and the speed is adjusted to 15000r / min for 3 minutes / time. After washing with water, calcine at 800℃ for 5 hours to obtain cerium oxide-ytterbium composite material with excellent near-infrared blocking performance.
[0026] Example 2
[0027] (1) Dissolve 3g of polyvinylpyrrolidone in 100mL of water, slowly pour it into 1.93L of 0.3mol / L cerium chloride solution and stir for 10min. Add 0.4mol / L sodium hydroxide solution dropwise to cerium nitrate solution until the pH reaches 10.5. Wash the filter cake with pure water 30 times under vacuum at 5L / time to obtain pure Ce(OH)3. After calcination at 700℃ for 6 hours and cooling, cerium oxide is obtained.
[0028] (2) Disperse cerium oxide in water, control the solid content at about 10%, grind it, control the D50 to about 0.1 μm, and obtain cerium oxide suspension.
[0029] (3) Take 300g of cerium oxide suspension with a solid content of 10%, and slowly add 97ml of 0.4mol / L ytterbium chloride to the cerium oxide suspension. After the addition is completed, add 0.4mol / L ammonia water. Stop the addition when the pH value reaches 10. The resulting solution is put into a high-speed centrifuge and the speed is adjusted to 13000r / min for 3 minutes / time. After washing with water, calcine at 850℃ for 6 hours to obtain cerium oxide-ytterbium composite material with excellent near-infrared blocking performance.
[0030] Example 3
[0031] (1) Dissolve 1g of polyvinylpyrrolidone in 100mL of water, slowly pour it into 5.8L of 0.1mol / L cerium nitrate solution and stir for 10min. Add 0.4mol / L ammonia solution dropwise to the cerium nitrate solution until the pH reaches 8.7. Wash the filter cake with pure water 30 times under vacuum at 5L / time to obtain pure Ce(OH)3. After calcination at 680℃ for 4 hours and cooling, cerium oxide is obtained.
[0032] (2) Disperse cerium oxide in water and grind it to control the solid content at about 10% and control the D50 to about 0.1 μm to obtain cerium oxide suspension.
[0033] (3) Take 300g of cerium oxide suspension with a solid content of 10%, slowly add 290ml of 0.2mol / L ytterbium chloride to the cerium oxide suspension, add 0.3mol / L ammonia water after the addition is finished, stop the addition when the pH value reaches 11.5, and put the resulting solution into a high-speed centrifuge and adjust the speed to 12000r / min for 3 minutes / time. After washing with water, calcine at 900℃ for 4 hours to obtain cerium oxide ytterbium composite material with excellent near-infrared blocking performance.
[0034] Comparative Example 1
[0035] (1) The preparation of cerium oxide is the same as in Example 1; (2) Take 498 mL of 0.1 mol / L ytterbium chloride, add 0.4 mol / L sodium hydroxide dropwise, stop adding when the pH value reaches 11.0, and put the resulting solution into a high-speed centrifuge with the speed adjusted to 10000 r / min for 3 minutes / time. After washing with water, calcine at 800℃ for 5 hours to obtain ytterbium oxide. (3) 30g of cerium oxide and 9.8g of ytterbium oxide are added to 200g of water and ground in a grinder. After the D50 reaches 0.8μm, it is taken out and placed in an oven at 120℃ to dry and obtain a uniform mixed powder.
[0036] Comparative Example 2
[0037] (1) Dissolve 2g of polyvinylpyrrolidone in 100mL of water, slowly pour it into 2.53L of ytterbium chloride solution with a concentration of 0.2mol / L, and stir for 10min. Add 0.1mol / L sodium hydroxide solution dropwise to cerium nitrate solution until the pH reaches 10.0. Wash the filter cake with pure water 30 times under vacuum at a concentration of 5L / time to obtain pure Yb(OH)3. After calcining at 800℃ for 5 hours and cooling, ytterbium oxide is obtained.
[0038] (2) Disperse ytterbium oxide in water and grind it to a solid content of about 10% to obtain a ytterbium oxide suspension with a D50 of 0.15 μm.
[0039] (3) Take 300g of ytterbium oxide suspension with a solid content of 10%, slowly add 380ml of 0.1mol / L cerium nitrate to the cerium oxide suspension, add 0.4mol / L sodium hydroxide after the addition is finished, stop the addition when the pH value reaches 11.0, and put the resulting solution into a high-speed centrifuge and adjust the speed to 12000r / min for 3 minutes / time. After washing with water, calcine at 750℃ for 5 hours to obtain a composite material with ytterbium oxide as the core and cerium oxide as the coating.
[0040] Comparative Example 3
[0041] 1.55 L of 0.3 mol / L cerium chloride solution and 0.33 L of 0.3 mol / L ytterbium chloride solution were stirred and mixed thoroughly. 2 g of polyvinylpyrrolidone was dissolved in water and poured into the mixed solution, then stirred. 0.2 mol / L ammonia solution was added dropwise to the mixed solution until the pH reached 10. The resulting filter cake was washed 30 times with pure water under vacuum at 5 L / cycle to obtain a pure Ce(OH)3·Yb(OH)3 mixed filter cake. The filter cake was then calcined at 800℃ for 6 hours to obtain a cerium oxide and ytterbium oxide composite material.
[0042] Comparative Example 4
[0043] The cerium oxide suspension is the same as in Example 1. Take 300g of cerium oxide suspension with a solid content of 10%, and slowly add 1.743L of 0.1mol / L ytterbium chloride dropwise to the cerium oxide suspension. After the addition is complete, add 0.4mol / L sodium hydroxide dropwise. Stop the addition when the pH value reaches 10.0. The resulting solution is centrifuged in a high-speed centrifuge at 15000r / min for 3 minutes each time. After washing with water, calcine at 800℃ for 6 hours to obtain a composite material with cerium oxide nucleation and ytterbium oxide coating on an excessively thick shell.
[0044] Comparative Example 5
[0045] (1) The preparation of cerium oxide is the same as in Example 1.
[0046] (2) Cerium oxide is dispersed in water and ground to a solid content of about 10% to obtain a cerium oxide suspension with D50: 0.218 μm and D90: 1.294 μm.
[0047] (3) Same as in Example 1, a composite material with a large-sized cerium oxide core and ytterbium oxide coating was obtained.
[0048] The composite materials prepared in the above examples and comparative examples were used to prepare coatings on ordinary white wave surfaces, and the visible light transmittance and near-infrared blocking rate were tested. The results are shown in Table 1 below.
[0049] Table 1 Performance tests of composite material coatings prepared in Examples 1-3 and Comparative Examples 1-5
[0050] As can be seen, the cerium oxide-ytterbium oxide composite material with a core-shell structure, prepared in the embodiments of the present invention, exhibits excellent visible light transmittance, high near-infrared blocking rate and total solar energy blocking rate, and good heat insulation effect, thereby improving the photothermal stability of the material. The physical mixing, reverse core-shell structure, or one-step in-situ composite methods in Comparative Examples 1-3 all have varying degrees of influence on the material's performance. Furthermore, the particle size of the core material and the coating amount of the shell material also have a certain impact on the material's transmittance and near-infrared blocking rate.
[0051] The core-shell structured cerium oxide ytterbium composite material prepared by this invention can be used in outdoor thermal insulation materials such as architectural glass and automotive glass, and has broad application prospects.
[0052] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A cerium oxide ytterbium composite material, characterized in that, The morphology of the cerium oxide-ytterbium composite material is a core-shell structure with cerium oxide as the core and ytterbium oxide as the shell, wherein the D50 of the cerium oxide core is below 0.1 μm and the D90 is between 0.1 and 0.2 μm.
2. The method for preparing the cerium oxide-ytterbium composite material according to claim 1, characterized in that, The specific steps include the following: (1) Cerium oxide is dispersed in water and ground to obtain a cerium oxide suspension; the D50 of cerium oxide in the cerium oxide suspension is below 0.1 μm and the D90 is between 0.1 and 0.2 μm; (2) Slowly add ytterbium chloride solution to cerium oxide suspension. After the addition is complete, add alkaline solution to adjust the pH value to 8-13. The precipitate was collected by centrifugation, washed, and calcined to obtain a cerium oxide-ytterbium composite material.
3. The method for preparing cerium oxide ytterbium composite material according to claim 2, characterized in that, The molar ratio of cerium oxide to ytterbium chloride is 1:0.3~0.
6.
4. The method for preparing cerium oxide ytterbium composite material according to claim 2, characterized in that, The solid content of cerium oxide in the cerium oxide suspension is 10%.
5. The method for preparing cerium oxide ytterbium composite material according to claim 2, characterized in that, The concentration of the ytterbium chloride solution is 0.05~0.2 mol / L.
6. The method for preparing cerium oxide ytterbium composite material according to claim 2, characterized in that, The alkaline solution is ammonia or sodium hydroxide solution with a concentration of 0.1~0.5 mol / L.
7. The method for preparing cerium oxide ytterbium composite material according to claim 2, characterized in that, The burning temperature is 700~1000℃, and the burning time is 4~6 hours.
8. The method for preparing cerium oxide ytterbium composite material according to claim 2, characterized in that, The cerium oxide is cerium oxide synthesized with the assistance of polyvinylpyrrolidone.
9. The method for preparing the cerium oxide-ytterbium composite material according to claim 8, characterized in that, The preparation method of the cerium oxide is as follows: 0.5%~4% (w / v) polyvinylpyrrolidone is added to a 0.1~0.5mol / L solution of cerium nitrate or cerium chloride, and reacted with 0.1~0.5mol / L sodium hydroxide or ammonia water, with the pH value controlled at 7~13; the filter cake after reaction is repeatedly washed to obtain Ce(OH)3; and calcined at 600~900℃ for 4~6 hours.
10. The application of the cerium oxide ytterbium composite material according to claim 1 as a near-infrared blocking material.