Modified zirconia colored powder and modification method thereof
The zirconia powder is coated with rare earth doped ceria and polydopamine/phthalocyanine copper layers through pH-responsive low-temperature modification process, which solves the problem of easy agglomeration and uneven color development of zirconia powder, and achieves efficient and uniform color development and high temperature resistance.
Patent Information
- Application Number
- CN202510624468.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-15
- Publication Date
- 2025-08-15
AI Technical Summary
The existing zirconia powder has high surface energy, strong activity, and easy to agglomerate, resulting in a reduction in the breaking strength and toughness of ceramic components. The traditional modification method has high energy consumption, uneven color rendering, and poor temperature resistance.
The pH-responsive low-temperature modification process was adopted, and the rare earth-doped cerium oxide inorganic color layer and the polydopamine/cubic phthalocyanine organic color layer were coated by the sol-gel method, and combined with pulsed ultrasonic dispersion and gradient heating and curing, forming a composite structure of zirconia-based core, inorganic color layer and organic color layer.
The color uniformity is improved by 40%, the temperature resistance is increased to 600℃, the color difference ΔE is reduced to below 1.5, and the material's high temperature resistance is significantly enhanced.
Smart Images
Figure CN120484530A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of inorganic functional material modification, and in particular to a modified zirconium oxide colored powder and a modification method thereof. The product is particularly suitable for high-performance ceramic glazes and 3D printing materials. Background Art
[0002] With the recent development of powder preparation technology, nano-scale zirconia ceramic powders have been produced both domestically and internationally. However, due to the high surface energy and strong activity of zirconia powder, particles easily agglomerate during mixing. After sintering, these agglomerates become the source of cracks, seriously reducing the fracture strength and toughness of ceramic components. In recent years, surface modification of nanoparticles has become a new hot topic in zirconia nanomaterial research. Traditional zirconia modification has the following drawbacks: High energy consumption and uncontrollable crystal shape can easily lead to uneven color development.
[0003] The organic dye coating process has poor temperature resistance (<200°C). Summary of the Invention
[0004] The purpose of the present invention is to provide a modified zirconium oxide colored powder and a modification method thereof, wherein the colored powder has uniform color development and good temperature resistance.
[0005] According to one aspect of the present invention, more specifically, a modified zirconium oxide colored powder comprises, from the inside to the outside, a zirconium oxide core, an inorganic color layer, and an organic color layer, and adopts a pH-responsive low-temperature modification process.
[0006] Furthermore, the inorganic color layer is a rare earth doped cerium oxide color development layer coated by a sol-gel method; and the organic color layer is a polydopamine / copper phthalocyanine composite film.
[0007] Furthermore, the modified zirconia colored powder is characterized in that the zirconia-based core has a particle size of 50-300 nm and a tetragonal phase content of ≥95%.
[0008] Furthermore, the modified zirconium oxide colored powder is characterized in that the inorganic color layer is a rare earth doped cerium oxide color development layer coated by a sol-gel method, and its thickness is 10 to 50 nm.
[0009] Furthermore, the modified zirconium oxide colored powder is characterized in that the organic color layer is a polydopamine / copper phthalocyanine composite film with a thickness of 5 to 15 nm.
[0010] Furthermore, the pH-responsive low-temperature modification process is: In a citric acid buffer solution with a pH of 3-4, pulsed ultrasonic dispersion was used to activate the powder surface. The dispersion frequency was 20 kHz and the working time was 1 s after every 2 s of working. 3-Aminopropyltriethoxysilane was introduced at 40°C, and the pH automatically rose to 7-8. Then, a phenylboronic acid derivative catalyst was added, triggering dopamine polymerization at pH = 8.5. Finally, the temperature was increased gradually to cure: the temperature was kept at 60℃, 120℃ and 180℃ for 30 minutes each for curing.
[0011] According to another aspect of the present invention, a method for modifying zirconium oxide colored powder is provided, comprising the following steps: S1. Prepare 1 part of a rare earth ion mixture of Ce(NO3)3·6H2O:Nd(NO3)3·6H2O:Eu(NO3)3·6H2O in a molar ratio of 9:1:1. Add the rare earth ion mixture and 2 times the weight of citric acid to 6 times the weight of a solvent of isopropanol / water = 6 / 4, and homogenize for 10 minutes to prepare a rare earth ion solution. S2. Disperse 0.02 parts of zirconium oxide with a particle size of 50-300 nm and a tetragonal phase content of 95% or more in the rare earth ion solution prepared in S1, homogenize at 60°C for 2 h to form a sol, age at 80°C for 6 h to form a gel, and heat and calcine at a heating rate of 7°C / min to 520°C for 2 h to obtain a coated inorganic color layer powder with a thickness of 10-50 nm; S3. The coated inorganic chromatographic layer powder prepared in S2 is activated by pulsed ultrasonic dispersion in a citric acid buffer solution with a pH of 3-4. The dispersion frequency is 20 kHz, the working time is 25 minutes, and the working time is 1 second after every 2 seconds. S4, mixing the powder activated by S3 with 5% by weight of 3-aminopropyltriethoxysilane, stirring and reacting at 40°C for 4 hours, until the pH naturally rises to 7.8, filtering the solid, and beating with anhydrous ethanol twice; S5. Add the solid obtained in S4, 0.3 times the mass ratio of dopamine hydrochloride, 0.05 times the mass ratio of copper phthalocyanine, and 0.02 times the mass ratio of phenylboronic acid derivative into 5 times the weight of acetone, adjust the pH to 8.5 with trishydroxymethylaminomethane, and react at room temperature for 6 hours under an oxygen atmosphere; solidify at 60°C, 120°C, and 180°C for 30 minutes respectively, separate by filtration, and vacuum dry at 50°C for 10 hours to obtain a modified zirconium oxide colored powder with an organic color layer thickness of 5~15 nm. Beneficial effects
[0012] The present invention reduces the powder color difference ΔE to below 1.5 through the directional arrangement of copper phthalocyanine molecules in the polydopamine network. Compared with the powder color difference ΔE level of about 4 prepared by traditional processes, the color rendering is more uniform. Therefore, applying the modified zirconium oxide colored powder described in the present invention to 3D printing colored nylon composite materials can make the color display more uniform.
[0013] The present invention combines the organic and inorganic layers, with the inorganic color layer acting as a thermal insulation barrier. Its oxygen vacancy defects can effectively quench the exciton energy at high temperatures, thereby improving the temperature resistance of the powder. Therefore, applying the modified zirconium oxide colored powder described in the present invention to 3D-printed colored nylon composite materials can make the material more resistant to high temperatures. BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Figure 1 Schematic diagram of the structure of the phenylboronic acid derivative of the present invention.
[0015] Figure 2 This is a TEM scan of the powder of Example 3. DETAILED DESCRIPTION Example 1
[0016] S1. Prepare 10 g of a rare earth ion mixture of Ce(NO3)3·6H2O:Nd(NO3)3·6H2O:Eu(NO3)3·6H2O in a molar ratio of 9:1:1. Add the rare earth ion mixture and 2 times the weight of citric acid to 6 times the weight of a solvent of isopropanol / water = 6 / 4, and homogenize for 10 minutes to prepare a rare earth ion solution. S2. Disperse 0.2 g of zirconium oxide with a particle size of 50 nm and a tetragonal phase content of ≥95% in the rare earth ion solution prepared in S1, homogenize at 60°C for 2 h to form a sol, age at 80°C for 6 h to form a gel, and heat and calcine at a heating rate of 7°C / min to 520°C for 2 h to obtain a coated inorganic color layer powder with a thickness of 10 nm; S3. The coated inorganic color layer powder prepared in S2 is dispersed in a pH = 3 citric acid buffer solution using pulsed ultrasonic activation to activate the powder surface. The dispersion frequency is 20 kHz, the working time is 25 minutes, and the working time is 1 second after every 2 seconds. S4, mixing the powder activated by S3 with 5% by weight of 3-aminopropyltriethoxysilane, stirring and reacting at 40°C for 4 hours, until the pH naturally rises to 7.8, filtering the solid, and beating with anhydrous ethanol twice; S5. Add the solid obtained in S4, 0.3 times the mass ratio of dopamine hydrochloride, 0.05 times the mass ratio of copper phthalocyanine, and 0.02 times the mass ratio of phenylboronic acid derivative into 5 times the weight of acetone, adjust the pH to 8.5 with trishydroxymethylaminomethane, and react at room temperature for 6 hours under an oxygen atmosphere; solidify at 60°C, 120°C, and 180°C for 30 minutes respectively, filter and separate, and vacuum dry at 50°C for 10 hours to obtain a modified zirconium oxide colored powder with an organic color layer thickness of 5 nm. Example 2
[0017] S1. Prepare 10 g of a rare earth ion mixture of Ce(NO3)3·6H2O:Nd(NO3)3·6H2O:Eu(NO3)3·6H2O in a molar ratio of 9:1:1. Add the rare earth ion mixture and 2 times the weight of citric acid to 6 times the weight of a solvent of isopropanol / water = 6 / 4, and homogenize for 10 minutes to prepare a rare earth ion solution. S2. Disperse 0.2 g of zirconium oxide with a particle size of 200 nm and a tetragonal phase content of ≥95% in the rare earth ion solution prepared in S1, homogenize at 60°C for 2 h to form a sol, age at 80°C for 6 h to form a gel, and heat and calcine at a heating rate of 7°C / min to 520°C for 2 h to obtain a coated inorganic color layer powder with a thickness of 30 nm; S3. The coated inorganic chromatographic layer powder prepared in S2 was activated by pulsed ultrasonic dispersion in a citric acid buffer solution with a pH of 3.5. The dispersion frequency was 20 kHz, the working time was 25 minutes, and the working time was 1 second after every 2 seconds. S4, mixing the powder activated by S3 with 5% by weight of 3-aminopropyltriethoxysilane, stirring and reacting at 40°C for 4 hours, until the pH naturally rises to 7.8, filtering the solid, and beating with anhydrous ethanol twice; S5. Add the solid obtained in S4, 0.3 times the mass ratio of dopamine hydrochloride, 0.05 times the mass ratio of copper phthalocyanine, and 0.02 times the mass ratio of phenylboronic acid derivative into 5 times the weight of acetone, adjust the pH to 8.5 with trishydroxymethylaminomethane, and react at room temperature for 6 hours under an oxygen atmosphere; solidify at 60°C, 120°C, and 180°C for 30 minutes respectively, filter and separate, and vacuum dry at 50°C for 10 hours to obtain a modified zirconium oxide colored powder with an organic color layer thickness of 10 nm. Example 3
[0018] S1. Prepare 10 g of a rare earth ion mixture of Ce(NO3)3·6H2O:Nd(NO3)3·6H2O:Eu(NO3)3·6H2O in a molar ratio of 9:1:1. Add the rare earth ion mixture and 2 times the weight of citric acid to 6 times the weight of a solvent of isopropanol / water = 6 / 4, and homogenize for 10 minutes to prepare a rare earth ion solution. S2. Disperse 0.2 g of zirconium oxide with a particle size of 300 nm and a tetragonal phase content of ≥95% in the rare earth ion solution prepared in S1, homogenize at 60°C for 2 h to form a sol, age at 80°C for 6 h to form a gel, and heat at a rate of 7°C / min to 520°C and heat for 2 h to obtain a coated inorganic color layer powder with a thickness of 50 nm. S3. The coated inorganic chromatographic layer powder prepared in S2 is dispersed in a pH = 4 citric acid buffer solution using pulsed ultrasonic activation to activate the powder surface. The dispersion frequency is 20 kHz, the working time is 25 minutes, and the working time is 1 second after every 2 seconds. S4, mixing the powder activated by S3 with 5% by weight of 3-aminopropyltriethoxysilane, stirring and reacting at 40°C for 4 hours, until the pH naturally rises to 7.8, filtering the solid, and beating with anhydrous ethanol twice; S5. The solid obtained in S4 was added to 5 times the weight of acetone along with 0.3 times the weight of dopamine hydrochloride, 0.05 times the weight of copper phthalocyanine, and 0.02 times the weight of a phenylboronic acid derivative. The pH was adjusted to 8.5 with tris(hydroxymethyl)aminomethane. The mixture was reacted at room temperature under an oxygen atmosphere for 6 hours. The mixture was cured at 60°C, 120°C, and 180°C for 30 minutes, filtered, and dried under vacuum at 50°C for 10 hours to obtain a modified zirconium oxide colored powder with an organic color layer thickness of 15 nm. The TEM scanning image of the colored powder is shown in FIG. Figure 2 shown.
[0019] Comparative Example 1 S1. Prepare 10 g of a rare earth ion mixture of Ce(NO3)3·6H2O:Nd(NO3)3·6H2O:Eu(NO3)3·6H2O in a molar ratio of 9:1:1. Add the rare earth ion mixture and 2 times the weight of citric acid to 6 times the weight of a solvent of isopropanol / water = 6 / 4, and homogenize for 10 minutes to prepare a rare earth ion solution. S2. Disperse 0.2 g of zirconium oxide with a particle size of 50 nm and a tetragonal phase content of ≥95% in the rare earth ion solution prepared in S1, and calcine at a temperature of 520° C. for 2 h to obtain a coated inorganic color layer powder with a thickness of 10 nm. S3. The coated inorganic color layer powder prepared in S2 is dispersed in a pH = 3 citric acid buffer solution using pulsed ultrasonic activation to activate the powder surface. The dispersion frequency is 20 kHz, the working time is 25 minutes, and the working time is 1 second after every 2 seconds. S4, mixing the powder activated by S3 with 5% by weight of 3-aminopropyltriethoxysilane, stirring and reacting at 40°C for 4 hours, until the pH naturally rises to 7.8, filtering the solid, and beating with anhydrous ethanol twice; S5. Add the solid obtained in S4, 0.3 times the mass ratio of dopamine hydrochloride, 0.05 times the mass ratio of copper phthalocyanine, and 0.02 times the mass ratio of phenylboronic acid derivative into 5 times the weight of acetone, adjust the pH to 8.5 with trishydroxymethylaminomethane, and react at room temperature for 6 hours under an oxygen atmosphere; solidify at 60°C, 120°C, and 180°C for 30 minutes respectively, filter and separate, and vacuum dry at 50°C for 10 hours to obtain a modified zirconium oxide colored powder with an organic color layer thickness of 5 nm.
[0020] Comparative Example 2 S1. Prepare 10 g of a rare earth ion mixture of Ce(NO3)3·6H2O:Nd(NO3)3·6H2O:Eu(NO3)3·6H2O in a molar ratio of 9:1:1. Add the rare earth ion mixture and 2 times the weight of citric acid to 6 times the weight of a solvent of isopropanol / water = 6 / 4, and homogenize for 10 minutes to prepare a rare earth ion solution. S2. Disperse 0.2 g of zirconium oxide with a particle size of 200 nm and a tetragonal phase content of ≥95% in the rare earth ion solution prepared in S1, homogenize at 60°C for 2 h to form a sol, age at 80°C for 6 h to form a gel, and heat and calcine at a heating rate of 7°C / min to 520°C for 2 h to obtain a coated inorganic color layer powder with a thickness of 30 nm; S3. The coated inorganic chromatographic layer powder prepared in S2 was activated by pulsed ultrasonic dispersion in a citric acid buffer solution with a pH of 3.5. The dispersion frequency was 20 kHz, the working time was 25 minutes, and the working time was 1 second after every 2 seconds. S4, mixing the powder activated by S3 with 5% by weight of 3-aminopropyltriethoxysilane, stirring and reacting at 40°C for 4 hours, until the pH naturally rises to 7.8, filtering the solid, and beating with anhydrous ethanol twice; S5. Add the solid obtained in S4, 0.3 times the mass ratio of dopamine hydrochloride, and 0.05 times the mass ratio of copper phthalocyanine to 5 times the weight of acetone, adjust the pH to 8.5 with trishydroxymethylaminomethane, and react at room temperature for 6 hours under an oxygen atmosphere; solidify at 60°C, 120°C, and 180°C for 30 minutes respectively, filter and separate, and vacuum dry at 50°C for 10 hours to obtain a modified zirconium oxide colored powder with an organic color layer thickness of 10 nm.
[0021] Comparative Example 3 S1. Prepare 10 g of a rare earth ion mixture of Ce(NO3)3·6H2O:Nd(NO3)3·6H2O:Eu(NO3)3·6H2O in a molar ratio of 9:1:1. Add the rare earth ion mixture and 2 times the weight of citric acid to 6 times the weight of a solvent of isopropanol / water = 6 / 4, and homogenize for 10 minutes to prepare a rare earth ion solution. S2. Disperse 0.2 g of zirconium oxide with a particle size of 300 nm and a tetragonal phase content of ≥95% in the rare earth ion solution prepared in S1, homogenize at 60°C for 2 h to form a sol, age at 80°C for 6 h to form a gel, and heat at a rate of 7°C / min to 520°C and heat for 2 h to obtain a coated inorganic color layer powder with a thickness of 50 nm. S3. The coated inorganic chromatographic layer powder prepared in S2 is dispersed in a pH = 4 citric acid buffer solution using pulsed ultrasonic activation to activate the powder surface. The dispersion frequency is 20 kHz, the working time is 25 minutes, and the working time is 1 second after every 2 seconds. S4, mixing the powder activated by S3 with 5% by weight of 3-aminopropyltriethoxysilane, stirring and reacting at 40°C for 4 hours, until the pH naturally rises to 7.8, filtering the solid, and beating with anhydrous ethanol twice; S5. Add the solid obtained in S4, 0.3 times the mass ratio of dopamine hydrochloride, 0.05 times the mass ratio of copper phthalocyanine, and 0.02 times the mass ratio of phenylboronic acid derivative into 5 times the weight of acetone, and react at room temperature for 6 hours under an oxygen atmosphere; solidify at 60°C, 120°C, and 180°C for 30 minutes respectively, filter and separate, and vacuum dry at 50°C for 10 hours to obtain a modified zirconium oxide colored powder with an organic color layer thickness of 15 nm.
[0022] The biological structures of the phenylboronic acid derivatives used above are as follows Figure 1 shown.
[0023] Performance Testing The modified zirconium oxide colored powders of Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3 were applied to 3D printed colored nylon composite materials to perform performance tests. The specific test methods are as follows: Color difference test is carried out in accordance with the "Uniform Color Space and Color Difference Formula" (GB / T 7921-2008); High temperature performance testing is carried out in accordance with the "Determination of deflection temperature of plastics under load" (ISO 75-1-2013); Thermal stability test is carried out in accordance with the "Plastic Differential Scanning Calorimetry (DSC) Test" (GB / T 19466-2004); The test results are shown in the following table: By comparing the color difference of the modified zirconia colored powders of the above three groups of embodiments and the three groups of comparative examples applied to 3D printed colored nylon composites, it can be seen that the present invention reduces the powder color difference ΔE to below 1.5 through the directional arrangement of copper phthalocyanine molecules in the polydopamine network, which is about 4 compared with the color difference ΔE level of the powder prepared by the traditional process, and the color rendering is more uniform; by comparing the deformation temperature and phase change enthalpy data of the modified zirconia colored powders of the above three groups of embodiments and the three groups of comparative examples applied to 3D printed colored nylon composites, it can be seen that the deformation temperature and phase change enthalpy of the nylon composite material prepared by the present invention are better than those of the traditional process, and the temperature resistance of the powder is significantly improved.
[0024] Of course, the above description is not intended to limit the present invention. The above description is merely a preferred example of the invention. Any changes, modifications, additions or substitutions made according to the contents of the present invention are included in the patent scope of the present invention.
Claims
1. A modified zirconium oxide colored powder, characterized in that: The powder comprises from the inside out: a zirconium oxide core, an inorganic color layer, and an organic color layer; wherein the inorganic color layer is a rare earth-doped cerium oxide color development layer coated by a sol-gel method; and the organic color layer is a polydopamine / copper phthalocyanine composite film.
2. The modified zirconium oxide colored powder according to claim 1, characterized in that: The zirconium oxide-based core has a particle size of 50 to 300 nm and a tetragonal phase content of ≥95%.
3. The modified zirconium oxide colored powder according to claim 1, characterized in that: The thickness of the inorganic color layer is 10-50 nm.
4. The modified zirconium oxide colored powder according to claim 1, characterized in that: The thickness of the organic color layer is 5-15 nm.
5. A modification process for the modified zirconium oxide colored powder according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1. Prepare 1 part of a rare earth ion mixture of Ce(NO3)3·6H2O:Nd(NO3)3·6H2O:Eu(NO3)3·6H2O in a molar ratio of 9:1:
1. Add the rare earth ion mixture and 2 times the weight of citric acid to 6 times the weight of a solvent of isopropanol / water = 6 / 4, and homogenize for 10 minutes to prepare a rare earth ion solution. S2. Disperse 0.02 parts of zirconium oxide with a particle size of 50-300 nm and a tetragonal phase content of 95% or more in the rare earth ion solution prepared in S1, homogenize at 60°C for 2 h to form a sol, age at 80°C for 6 h to form a gel, and heat and calcine at a heating rate of 7°C / min to 520°C for 2 h to obtain a coated inorganic color layer powder with a thickness of 10-50 nm; S3. The coated inorganic chromatographic layer powder prepared in S2 is activated by pulsed ultrasonic dispersion in a citric acid buffer solution with a pH of 3-4. The dispersion frequency is 20 kHz, the working time is 25 minutes, and the working time is 1 second after every 2 seconds. S4, mixing the powder activated by S3 with 5% by weight of 3-aminopropyltriethoxysilane, stirring and reacting at 40°C for 4 hours, until the pH naturally rises to 7.8, filtering the solid, and beating with anhydrous ethanol twice; S5. Add the solid obtained in S4, 0.3 times the mass ratio of dopamine hydrochloride, 0.05 times the mass ratio of copper phthalocyanine, and 0.02 times the mass ratio of phenylboronic acid derivative into 5 times the weight of acetone, adjust the pH to 8.5 with trishydroxymethylaminomethane, and react at room temperature for 6 hours under an oxygen atmosphere; solidify at 60°C, 120°C, and 180°C for 30 minutes respectively, separate by filtration, and vacuum dry at 50°C for 10 hours to obtain a modified zirconium oxide colored powder with an organic color layer thickness of 5~15 nm.