Preparation method of multi-color ion-doped zirconia ceramic with photochromic property and product of multi-color ion-doped zirconia ceramic
By using a method for preparing zirconium oxide ceramics doped with rare earth and transition metal ions, the problems of easy decomposition and structural instability of photochromic materials at high temperatures have been solved, achieving multicolor photochromic properties, which are suitable for information storage and anti-counterfeiting labeling.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JINGDEZHEN CERAMIC UNIV
- Filing Date
- 2026-01-12
- Publication Date
- 2026-04-28
AI Technical Summary
Existing photochromic materials are easily decomposed at high temperatures, their structure is easily damaged, their chemical stability is poor, and their color changes are limited, making it difficult to achieve multicolor effects.
Multicolor photochromic zirconia ceramics were prepared by using rare earth and transition metal ion doped zirconia ceramics through pressure forming, firing, infiltration and sintering steps to form a tetragonal zirconia crystal structure with excellent optical properties.
It is not easily decomposed at high temperatures, has a stable structure, possesses multicolor photochromic properties, and has a fast response speed, making it suitable for fields such as information storage and anti-counterfeiting labels.
Smart Images
Figure CN121930007A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of ceramic materials technology, and in particular to a method for preparing multi-colored ion-doped zirconium oxide ceramics with photochromic properties and the product thereof. Background Technology
[0002] Photochromic materials are materials whose color changes reversibly in response to external light stimulation. Due to their pronounced color changes and reversible optical responses, photochromism, especially the superior thermal stability, chemical resistance, fatigue resistance, and mechanical strength of inorganic photochromic luminescent materials, has been widely developed. Unfortunately, most materials exhibit extensive visible absorption from the light centers, resulting in relatively simple and monochromatic photochromic colors, typically ranging from pale white to gray. Although some progress has been made in designing multicolor photochromic materials, selecting a suitable matrix crystal structure or stabilizing defect distribution remains a significant challenge. Furthermore, traditional organic and inorganic photochromic materials are prone to decomposition at high temperatures, leading to irreversible structural damage and poor stability.
[0003] Zirconia ceramics, as a novel ceramic material, possess many excellent physicochemical properties. They exhibit superior photoelectric properties, high coefficients of thermal expansion and refractive indices, low thermal conductivity and coefficients of friction, excellent chemical stability, and resistance to corrosion and erosion. These characteristics have made zirconia materials a hot topic in scientific research and production applications. Developing a multicolor photochromic ceramic material based on zirconia luminescent ceramics—one that is not easily decomposed at high temperatures, has a durable structure, good chemical stability, and excellent optical properties—will be beneficial for the technological application and development of photochromic materials. Summary of the Invention
[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing multicolor ion-doped zirconia ceramics with photochromic properties. This method involves modification with rare earth and transition metal ions to obtain multicolor photochromic luminescent ceramic materials that are not easily decomposed at high temperatures, have a stable structure, good chemical stability, and excellent optical properties. Another objective of this invention is to provide products prepared using the above method.
[0005] The objective of this invention is achieved through the following technical solution:
[0006] The present invention provides a method for preparing multicolor ion-doped zirconium oxide ceramics with photochromic properties, comprising the following steps:
[0007] (1) 2-6 mol% yttrium oxide stabilized zirconium oxide powder was pressure molded to obtain a green blank;
[0008] (2) The green blank is fired in air at a temperature of 900-1100°C for 1-2 hours to obtain a zirconia green body;
[0009] (3) The zirconia blank is impregnated in a coloring ion solution for 10–60 min, and then dried to obtain an ion-doped zirconia blank; the coloring ion solution is one or a combination of Eu(NO3)3, Er(NO3)3, Pr(NO3)3, Nd(NO3)3, Ce(NO3)3, Ni(NO3)2, Co(NO3)2, Fe(NO3)3, and Al(NO3)3 solutions; the concentration of the coloring ion solution is 0.5–3.0 mol / L;
[0010] (4) The ion-doped zirconia blank is sintered in air at a temperature of 1450-1550°C for 1-10 h, and then cooled to room temperature in the furnace to obtain dense, multicolored ion-doped zirconia ceramic with photochromic properties.
[0011] Furthermore, in step (1) of the present invention, the pressure for pressure forming is 10-25 MPa and the time is 10-30 s.
[0012] The product prepared by the above-mentioned method for preparing multicolor ion-doped zirconia ceramics with photochromic properties has a main crystal phase of tetragonal zirconia and exhibits photoluminescence after irradiation with light at a wavelength of 365 nm for 0.5 seconds.
[0013] The present invention has the following beneficial effects:
[0014] (1) This invention proposes a method for preparing multi-colored ion-doped zirconia ceramics with photochromic properties. Multi-colored zirconia ceramics with photochromic properties are obtained by doping with rare earth and transition metal ions. The photochromic zirconia material of this invention exhibits excellent photochromic luminescence properties under ultraviolet excitation, and the zirconia ceramics display rich colors when sintered at high temperatures of 1450–1550℃, thus effectively solving the technical problems of easy decomposition, structural damage, and poor chemical stability in existing technologies at high temperatures.
[0015] (2) The multicolor photochromic zirconia ceramic of this invention can achieve rapid color-changing emission after being irradiated by a 365 nm ultraviolet lamp, and has the characteristics of fast response speed and high contrast. It has superior performance in applications such as information storage and anti-counterfeiting labels. Based on the excellent stability of zirconia ceramic, its multicolor photochromic properties can be maintained for a long time.
[0016] (3) The multicolor photochromic zirconia ceramic of the present invention has potential application value in smart terminal devices, such as photochromic luminescent ceramic backplates. This material has obvious color change and luminescence characteristics, and can be used to make anti-counterfeiting marks to improve the security and recognizability of products. In terms of information storage and encryption, this material can be used to make high-density optical storage media devices. Attached Figure Description
[0017] The present invention will now be described in further detail with reference to the embodiments and accompanying drawings:
[0018] Figure 1 These are XRD patterns of ion-doped zirconium oxide ceramics with multicolor and photochromic properties prepared in Examples 1, 2, 3, 4, and 5 of this invention.
[0019] Figure 2 These are optical images of ion-doped zirconia ceramics with multicolor and photochromic properties prepared according to Examples 1, 2, 3, 4, and 5 of the present invention (a: before light irradiation; b: after light irradiation; from left to right are Examples 1, 2, 3, 4, and 5). Detailed Implementation
[0020] Example 1:
[0021] This embodiment describes a method for preparing multicolor ion-doped zirconium oxide ceramics with photochromic properties, the steps of which are as follows:
[0022] (1) 3 mol% yttrium oxide stabilized zirconium oxide powder with a purity > 99.9% was pressure molded at a pressure of 10 MPa for 10 s to obtain a green blank;
[0023] (2) The above-mentioned green blank was fired at 900°C in air atmosphere for 1 h to obtain a zirconia blank;
[0024] (3) The above zirconia blank was impregnated in a coloring ion solution of Eu(NO3)3 (purity > 99.9%) with a concentration of 2.0 mol / L for 10 min, and then dried at 80℃ for 12 h to obtain ion-doped zirconia blank;
[0025] (4) The above-mentioned ion-doped zirconia blank was sintered in air at a temperature of 2℃ / min to 1450℃ and held for 3 h. Then it was cooled to room temperature in the furnace to obtain a dense pink zirconia ceramic with a tetragonal zirconia phase as the main crystal phase and green luminescence properties.
[0026] Example 2:
[0027] This embodiment describes a method for preparing multicolor ion-doped zirconium oxide ceramics with photochromic properties, the steps of which are as follows:
[0028] (1) 3 mol% yttrium oxide stabilized zirconium oxide powder with a purity > 99.9% was pressure molded at a pressure of 15 MPa for 10 s to obtain a green blank;
[0029] (2) The above-mentioned green blank was fired at 900°C in air atmosphere for 1 h to obtain a zirconia blank;
[0030] (3) The above-mentioned zirconia blank was impregnated in a coloring ion solution formed by mixing Eu(NO3)3 (purity > 99.9%) solution and Er(NO3)3 (purity > 99.9%) solution. The concentration of Eu(NO3)3 in the coloring ion solution was 2.0 mol / L and the concentration of Er(NO3)3 was 1.0 mol / L. The impregnation time was 10 min. Then it was dried at 80℃ for 12 h to obtain ion-doped zirconia blank.
[0031] (4) The above-mentioned ion-doped zirconia blank was sintered in air at a temperature of 2℃ / min to 1450℃ and held for 3 h. Then it was cooled to room temperature in the furnace to obtain dense pink zirconia ceramic with a tetragonal zirconia phase as the main crystal phase and a warm yellow luminescence.
[0032] Example 3:
[0033] This embodiment describes a method for preparing multicolor ion-doped zirconium oxide ceramics with photochromic properties, the steps of which are as follows:
[0034] (1) 3 mol% yttrium oxide stabilized zirconium oxide powder with a purity > 99.9% was pressure molded at a pressure of 20 MPa for 20 s to obtain a green blank;
[0035] (2) The above-mentioned green blank was fired at 1000°C in air atmosphere for 1 h to obtain a zirconia blank;
[0036] (3) The above-mentioned zirconia blank was impregnated in a coloring ion solution formed by mixing Eu(NO3)3 (purity > 99.9%) solution and Nd(NO3)3 (purity > 99.9%) solution. The concentration of Eu(NO3)3 in the coloring ion solution was 2.0 mol / L and the concentration of Nd(NO3)3 was 1.0 mol / L. The impregnation time was 20 min. Then, it was dried at 80℃ for 12 h to obtain ion-doped zirconia blank.
[0037] (4) The above-mentioned ion-doped zirconia blank was sintered in air at a temperature of 2℃ / min to 1450℃ and held for 3 h. Then it was cooled to room temperature in the furnace to obtain a dense purple zirconia ceramic with a tetragonal zirconia phase as the main crystal phase and red luminescence properties.
[0038] Example 4:
[0039] This embodiment describes a method for preparing multicolor ion-doped zirconium oxide ceramics with photochromic properties, the steps of which are as follows:
[0040] (1) 3 mol% yttrium oxide stabilized zirconium oxide powder with a purity > 99.9% was pressure molded at a pressure of 25 MPa for 20 s to obtain a green blank;
[0041] (2) The above-mentioned green blank was fired at 1000°C in air atmosphere for 2 hours to obtain a zirconia blank;
[0042] (3) The above-mentioned zirconia blank was impregnated in a coloring ion solution formed by mixing Eu(NO3)3 (purity > 99.9%) solution and Pr(NO3)3 (purity > 99.9%) solution. The concentration of Eu(NO3)3 in the coloring ion solution was 2.0 mol / L and the concentration of Pr(NO3)3 was 1.0 mol / L. The impregnation time was 20 min. Then, it was dried at 80℃ for 12 h to obtain ion-doped zirconia blank.
[0043] (4) The above-mentioned ion-doped zirconia blank was sintered in air at a temperature of 2℃ / min to 1500℃ and held for 3 h. Then it was cooled to room temperature in the furnace to obtain a dense yellow zirconia ceramic with a tetragonal zirconia phase as the main crystal phase and red luminescence properties.
[0044] Example 5:
[0045] This embodiment describes a method for preparing multicolor ion-doped zirconium oxide ceramics with photochromic properties, the steps of which are as follows:
[0046] (1) 3 mol% yttrium oxide stabilized zirconium oxide powder with a purity > 99.9% was pressure molded at a pressure of 25 MPa for 30 s to obtain a green blank;
[0047] (2) The above-mentioned green blank was fired at 1100°C in air atmosphere for 1 h to obtain a zirconia blank;
[0048] (3) The above-mentioned zirconia blank was impregnated in a coloring ion solution formed by mixing Eu(NO3)3 (purity > 99.9%) solution, Al(NO3)3 (purity > 99.9%) solution, and Ni(NO3)2 (purity > 99.9%) solution. The concentration of Eu(NO3)3 in the coloring ion solution was 2.0 mol / L, the concentration of Al(NO3)3 was 1.0 mol / L, and the concentration of Ni(NO3)2 was 0.5 mol / L. The impregnation time was 30 min, and then it was dried at 80℃ for 12 h to obtain ion-doped zirconia blank;
[0049] (4) The above-mentioned ion-doped zirconia blank was sintered in air at a temperature of 2℃ / min to 1550℃ and held for 3 h. Then it was cooled to room temperature in the furnace to obtain a dense green zirconia ceramic with a tetragonal zirconia phase as the main crystal phase and orange-red luminescence properties.
[0050] Performance testing:
[0051] one, X X-ray diffraction experiment:
[0052] The multicolor and photochromic zirconia ceramic materials (samples) prepared in Examples 1, 2, 3, 4, and 5 were subjected to... X XRD diffraction experiments were conducted to obtain the XRD diffraction patterns corresponding to each embodiment.
[0053] Figure 1 The multicolor and photochromic zirconia ceramic materials prepared in Examples 1, 2, 3, 4, and 5 have diffraction angles of 10–80°. X X-ray diffraction patterns; the XRD patterns of all samples have the same characteristics as... t The ZrO2 phase (JCPDS -070-4426) exhibits very well-matched sharp diffraction peaks, and there are no diffraction peaks corresponding to the doped compounds. Characteristic peaks of the tetragonal phase appear at approximately 30°, 35°, and 75°. t (111) t (002), t (200) t (004) and t (400) indicates that these samples are all stable. t -ZrO2 single phase. Compared with the standard card composition, the introduction of rare earth and transition metal ions in the prepared 3YSZ ceramics caused a slight shift of the (101) peak to a smaller diffraction angle, resulting in... t The unit cell volume of ZrO2 expands slightly. This indicates that rare earth and transition metal ions are effectively incorporated into the crystal lattice, and the introduction of dopant ions has virtually no effect on the phase composition of the prepared zirconia ceramic.
[0054] II. Experiments involving multiple colors and photochromic phenomena:
[0055] Figure 2 Photoluminescence image of a multicolor and photochromic zirconia ceramic material (sample) prepared in an embodiment of the present invention. Figure 2 (a) shows photographs of the zirconia ceramic samples prepared in Examples 1, 2, 3, 4, and 5, doped with rare earth and transition metal ions. Figure 2 (b) is a photograph of the zirconia ceramic samples prepared in Examples 1, 2, 3, 4 and 5 after being irradiated with light at a wavelength of 365 nm for 0.5 seconds in the dark at room temperature.
[0056] from Figure 2 Figure (a) shows that the sample surface doped with ions is pink (Example 1), light pink (Example 2), purple (Example 3), yellow (Example 4), and green (Example 5). Figure (b) shows that after being irradiated with light at a wavelength of 365 nm for 0.5 seconds, the sample surface emits light in the colors of green (Example 1), warm yellow (Example 2), red (Example 3), dark red (Example 4), and orange-red (Example 5). This indicates that the sample exhibits rapid photoluminescence under irradiation with light at a wavelength of 365 nm and shows a relatively obvious color change on the sample surface. The sample has strong multicolor properties and photochromic luminescence.
Claims
1. A method for preparing multicolor ion-doped zirconium oxide ceramic with photochromic properties, characterized in that... Includes the following steps: (1) 2-6 mol% yttrium oxide stabilized zirconium oxide powder was pressure molded to obtain a green blank; (2) The green blank is fired in air at a temperature of 900-1100°C for 1-2 hours to obtain a zirconia green body; (3) The zirconia blank is impregnated in a coloring ion solution for 10–60 min, and then dried to obtain an ion-doped zirconia blank; the coloring ion solution is one or a combination of Eu(NO3)3, Er(NO3)3, Pr(NO3)3, Nd(NO3)3, Ce(NO3)3, Ni(NO3)2, Co(NO3)2, Fe(NO3)3, and Al(NO3)3 solutions; the concentration of the coloring ion solution is 0.5–3.0 mol / L; (4) The ion-doped zirconia blank is sintered in air at a temperature of 1450-1550°C for 1-10 h, and then cooled to room temperature in the furnace to obtain dense, multicolored ion-doped zirconia ceramic with photochromic properties.
2. The method for preparing multicolor ion-doped zirconium oxide ceramics with photochromic properties according to claim 1, characterized in that: In step (1), the pressure for pressure forming is 10-25 MPa and the time is 10-30 s.
3. A product prepared by the method for preparing multicolor ion-doped zirconium oxide ceramic with photochromic properties as described in claim 1 or 2.
4. The product according to claim 3, characterized in that: The main crystal phase of the multicolor and photochromic ion-doped zirconia ceramic is the tetragonal zirconia phase; it exhibits photoluminescence after being irradiated with light at a wavelength of 365 nm for 0.5 seconds.