Preparation method of stable photochromic red luminescent europium ion doped zirconia ceramic and product of stable photochromic red luminescent europium ion doped zirconia ceramic

Abstract

The invention discloses a preparation method of stable photochromic red luminescent europium ion doped zirconium oxide ceramic and a product thereof, 2-6 mol% yttrium oxide stabilized zirconium oxide (2-6YSZ) is used as a raw material, an Eu (NO3) 3 solution is used as a coloring ion solution, and Eu < 3 + > ions are doped to obtain the stable photochromic red luminescent europium ion doped zirconium oxide ceramic. And the stable photochromic red luminescent zirconia ceramic with a stable single-phase structure is successfully prepared through a high-temperature sintering process. The zirconia ceramic not only can generate a relatively fast photoluminescence phenomenon and has obvious color conversion, but also has relatively strong photoinduced red luminescence performance. The product obtained by the invention has wide application prospects, and can be applied to intelligent terminal equipment, such as polychromatic photochromic luminescent ceramic backboards, information storage, encryption, ultraviolet detection, temperature monitoring and the like.

Description

Technical Field

[0001] This invention relates to the field of ceramic materials technology, and in particular to a method for preparing stable photochromic red luminescent europium ion-doped zirconium oxide ceramic and its product. 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 make zirconia materials a hot topic in scientific research and production applications. Developing a multicolor photochromic ceramic material based on zirconia 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 existing technologies and provide a stable method for preparing photochromic red-emitting europium ion-doped zirconia ceramics. 3+ Ion doping modification is used to obtain multicolor ceramic materials with photochromic luminescence that are not easily decomposed at high temperatures, have a stable structure, good chemical stability, and excellent optical properties. Another object of this invention is to provide products prepared using the above-described method.

[0005] The objective of this invention is achieved through the following technical solution:

[0006] This invention provides a method for preparing stable photochromic red-emitting europium ion-doped zirconium oxide ceramic, 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 Eu(NO3)3 coloring ion solution with a concentration of 0.5 to 3.0 mol / L for 10 to 60 min, and then dried to obtain an ion-doped zirconia blank;

[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 europium ion-doped photochromic red luminescent zirconia ceramic.

[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 stable photochromic red luminescent europium ion-doped zirconia ceramic has a main crystalline phase of tetragonal zirconia as the main crystalline phase; the surface of the photochromic luminescent zirconia ceramic is white, and it turns red after being irradiated 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 stable method for preparing photochromic red-emitting europium ion-doped zirconium oxide ceramics, using Eu... 3+ Ion doping yields photochromic zirconia ceramics. The photochromic zirconia material of this invention exhibits excellent photochromic luminescence properties under ultraviolet excitation, and the sintering temperature of the zirconia ceramic is between 1450 and 1550°C, thus effectively solving the technical problems of easy decomposition at high temperatures, easy structural damage, and poor chemical stability in existing technologies.

[0015] (2) The stable photochromic red-emitting europium-doped zirconia ceramic of this invention can achieve rapid color-changing emission after irradiation with 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 stable photochromic red luminescent europium ion-doped zirconium oxide 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 stable photochromic red-luminescent europium ion-doped zirconium oxide ceramics prepared according to Embodiments 1, 2, 3, and 4 of the present invention.

[0019] Figure 2 This is an optical image of a stable photochromic red luminescent europium ion-doped zirconium oxide ceramic prepared according to Embodiment 1 of the present invention (a: before light irradiation; b: after light irradiation). Detailed Implementation

[0020] Example 1:

[0021] This embodiment describes a method for preparing stable photochromic red-emitting europium ion-doped zirconium oxide ceramic, 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 0.5 mol / L Eu(NO3)3 (purity > 99.9%) coloring ion solution 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 dense europium ion-doped photochromic red luminescent zirconia ceramic with tetragonal zirconia as the main crystal phase.

[0026] Example 2:

[0027] This embodiment describes a method for preparing stable photochromic red-emitting europium ion-doped zirconium oxide ceramic, 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 20 s to obtain a green blank;

[0029] (2) The above-mentioned green blank was fired at 1000°C in air atmosphere for 1 h to obtain a zirconia blank;

[0030] (3) The above zirconia blank was impregnated in a 1.0 mol / L Eu(NO3)3 (purity > 99.9%) coloring ion solution for 30 min, and then 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 1500℃ and held for 3 h. Then it was cooled to room temperature in the furnace to obtain dense europium ion-doped photochromic red luminescent zirconia ceramic with the tetragonal zirconia phase as the main crystal phase.

[0032] Example 3:

[0033] This embodiment describes a method for preparing stable photochromic red-emitting europium ion-doped zirconium oxide ceramic, 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 30 s to obtain a green blank;

[0035] (2) The above-mentioned green blank was fired at 1000°C in air atmosphere for 2 hours to obtain a zirconia blank;

[0036] (3) The above zirconia blank was impregnated in a 1.5 mol / L Eu(NO3)3 (purity > 99.9%) coloring ion solution for 10 min, and then 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 1500℃ and held for 3 h. Then it was cooled to room temperature in the furnace to obtain dense europium ion-doped photochromic red luminescent zirconia ceramic with the tetragonal zirconia phase as the main crystal phase.

[0038] Example 4:

[0039] This embodiment describes a method for preparing stable photochromic red-emitting europium ion-doped zirconium oxide ceramic, 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 30 s to obtain a green blank;

[0041] (2) The above-mentioned green blank was fired at 1100°C in air atmosphere for 1 h to obtain a zirconia blank;

[0042] (3) The above zirconia blank was impregnated in a 2.0 mol / L Eu(NO3)3 (purity > 99.9%) coloring ion solution for 60 min, and then 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 1550℃ and held for 3 h. Then it was cooled to room temperature in the furnace to obtain dense europium ion-doped photochromic red luminescent zirconia ceramic with the tetragonal zirconia phase as the main crystal phase.

[0044] Performance testing:

[0045] one, X X-ray diffraction experiment:

[0046] The photochromic red luminescent europium ion-doped zirconium oxide ceramic materials (samples) prepared in Examples 1, 2, 3, and 4 were subjected to... X XRD diffraction experiments were conducted to obtain the XRD diffraction patterns corresponding to each embodiment.

[0047] Figure 1 The photochromic red luminescent europium ion-doped zirconia ceramic materials prepared in Examples 1, 2, 3, and 4 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 Eu 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 Eu ions in the prepared 3YSZ ceramics caused a slight shift of the (101) peak to a smaller diffraction angle due to the smaller Zr content. 4+ (r = 0.720 Å, CN = 6) was affected by a larger Eu 3+(r = 0.89 Å, CN = 6) was replaced, resulting in t -ZrO2 showed a slight expansion in unit cell volume. This indicates that Eu 3+ The ions are effectively incorporated into the crystal lattice, and the introduction of Eu ions has virtually no effect on the phase composition of the prepared 3YSZ ceramic.

[0048] II. Photochromic phenomenon experiment:

[0049] Figure 2 This is a photochromic emission photograph of the photochromic red-emitting europium ion-doped zirconium oxide ceramic material (sample) prepared in Example 1 of this invention. Figure 2 Image (a) is a photograph of the zirconia ceramic sample prepared in Example 1. Figure 2 (b) is a photograph of the zirconia ceramic sample prepared in Example 1 after being irradiated with light at a wavelength of 365 nm for 0.5 seconds in the dark at room temperature.

[0050] from Figure 2 In (a), it can be seen that the surface of the Eu-doped photochromic luminescent zirconia ceramic is white. Figure 2 As can be seen in (b), the sample surface turns red after being irradiated with 365 nm wavelength light for 0.5 seconds, indicating that the sample exhibits rapid and strong photoluminescence under 365 nm wavelength light irradiation.

Claims

1. A method for preparing stable photochromic red-luminescent europium ion-doped zirconium oxide ceramic, 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 Eu(NO3)3 coloring ion solution with a concentration of 0.5 to 3.0 mol / L for 10 to 60 min, and then dried to obtain an ion-doped zirconia blank; (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 europium ion-doped photochromic red luminescent zirconia ceramic.

2. The method for preparing stable photochromic red-luminescent europium ion-doped zirconium oxide ceramic 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. The product prepared by the method of preparing stable photochromic red luminescent europium ion-doped zirconium oxide ceramic as described in claim 1 or 2.

4. The product according to claim 3, characterized in that: The main crystalline phase of the photochromic luminescent zirconia ceramic is the tetragonal phase of zirconia; the surface of the photochromic luminescent zirconia ceramic is white, and it turns red after being irradiated with light at a wavelength of 365nm for 0.5 seconds.

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