Rare earth ion doped functional nanocrystalline glass and its manufacturing method

Abstract

The present invention 3+ Rare earth ion doped Lu4Zr3O 12 This paper discloses a functional nanocrystalline glass and a method for manufacturing the same. The glass components include, in mole percent, SiO2: 57-59, Al2O3: 12-16, ZnO: 14-18, Li2O: 6-8, ZrO2: 3-5, Lu2O3: 2-3, and Er2O3: 0.05-0.2, and the sum of the glass components is 100. The present invention uses a combination design and heat treatment process control to add Er to the glass. 3+ Rare earth ion doped Lu4Zr3O 12 The present invention achieves the controllable fabrication of functional nanocrystals of glass, which have potential applications in low-temperature optical thermometry.

Description

[Technical Field]

[0001] The present invention relates to the field of glass, in particular to Er 3+ Rare earth ion doped Lu4Zr3O 12 The present invention relates to a functional nanocrystalline glass and a method for producing the same. [Background technology]

[0002] Oxides composed of RE2O3-MO2 (RE=La-Lu; M=Ti, Zr, Hf) have many unique properties. Oxides of this type may have defect fluorite, pyrochlore, or δ-phase rhombohedral structures, the specific structure depending on the chemical composition of the oxide and the order-disorder transitions they exhibit, such as pyrochlore to defect fluorite, rhombohedral δ-phase to defect fluorite, and β-phase (hexagonal) to defect fluorite, all of which are strongly dependent on temperature and annealing time. The chemical formula of oxides in these systems is generally [AB]2O 8-x For example, A2B2O7 pyrochlore, A4B3O 12 The δ phase and the β phase of A2BO5, where A and B are trivalent and tetravalent cations, respectively. These oxides often have favorable physical and chemical properties, particularly low thermal conductivity and high solubility of rare earth ions. These properties make these oxides promising for applications such as thermal barrier coatings, nuclear waste solidification materials, hosts for luminescent rare earth ions, and pigments.

[0003] In recent years, δ-phase RE4Zr3O 12 The optical properties of crystals have been widely studied. For example, Y4Zr3O 12 :Gd 3+ UV emission of Y4Zr3O 12 :EU 3+ Many of these materials are synthesized by the sol-gel method, high-temperature sintering, sintering, co-precipitation, mechanical activation, solution combustion, etc. However, in glasses, the δ phase RE4Zr3O 12 Therefore, the δ-phase RE4Zr3O 12Therefore, there is a need to provide new materials and methods for depositing Summary of the Invention [Problem to be solved by the invention]

[0004] The object of the present invention is to 3+ Rare earth ion doped Lu4Zr3O 12 The present invention provides a functional nanocrystalline glass and a method for producing the same, which has a simple manufacturing process, allows control of the size of the nanocrystals, and is low cost.

[0005] The solutions adopted by the present invention to solve the above technical problems are as follows: Er 3+ Rare earth ion doped Lu4Zr3O 12 A functional nanocrystalline glass, the glass comprising a glass matrix and Lu4Zr3O in the glass matrix. 12 and Er 3+ It contains nanocrystals made of rare earth ions.

[0006] Preferably, the glass components include, in mole percent, SiO2: 57-59, Al2O3: 12-16, ZnO: 14-18, Li2O: 6-8, ZrO2: 3-5, Lu2O3: 2-3, and Er2O3: 0.05-0.2, and the total of the glass components is 100.

[0007] Preferably, the nanocrystals have a size of 5-10 nm.

[0008] Preferably, the glass further comprises 0.1-0.3 mol % Sb2O3.

[0009] Lu4Zr3O 12 The method for producing functional nanocrystalline glass includes: All raw materials are weighed according to the composition, mixed uniformly, and placed in a crucible. The mixture is melted at 1600-1650°C for 1-3 hours, then poured into a mold and quenched. The quenched glass is annealed at 600-650°C for 2-4 hours and cooled to room temperature to obtain precast glass. The precast glass is heat-treated at 700-800°C for 5-7 hours to obtain the Lu4Zr3O 12 Obtaining a functional nanocrystalline glass.

[0010] Lu4Zr3O 12 Functional nanocrystalline glasses can be used as low-temperature optical thermometric materials.

[0011] Preferably, the low temperature range is from -263°C to 25°C.

[0012] Compared with the prior art, the present invention has the following advantages: The present invention is based on the design and optimization of glass composition, and employs the melting and quenching heat treatment method to extract Er from glass. 3+ Doped Lu4Zr3O 12 The present invention produces Lu4Zr3O, which has a simple manufacturing process and can flexibly adjust and control the composition and size of the nanocrystals. 12 By combining nanocrystals with glass, the excellent stability of the glass substrate can be effectively utilized to form Lu4Zr3O 12 This improves the stability of the nanocrystals and prevents agglomeration. Furthermore, such nanocrystal-glass composites have potential applications in low-temperature optical thermometry. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 shows XRD of Lu4Zr3O12 functional nanocrystalline glass obtained under heat treatment at different temperatures of precast glass AP of Example 1. [Figure 2] Transmission electron microscope images of the functional nanocrystalline glass obtained at 760 °C in Figure 1, where (a) is a bright-field image, (b) is a magnified image, and (c) is an HR-TEM image. [Figure 3]Figure 1 shows the EDS spectrum of the functional nanocrystalline glass obtained at 760 °C in Figure 1. (a) Two-view image of the sample, (b) Lu, (c) Zr, (d) Er, (e) Si, (f) Zn, (g) Al, and (h) O distributions are shown. [Figure 4] (a) shows the normalized emission spectrum of the functional nanocrystalline glass obtained at 760°C in Figure 1, (b) shows the emission intensity ratio between the 2H11 / 2 → 4I15 / 2 and 4S3 / 2 → 4I15 / 2 transition emissions, and (c) shows the curves of relative sensitivity (SR) and absolute sensitivity (SA). DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention will be described in detail below with reference to the drawings and examples, but the contents of the present invention are not limited to the following examples.

[0015] Example 1 In this embodiment, Er 3+ Rare earth ion doped Lu4Zr3O 12 A functional nanocrystalline glass is provided, which comprises a glass matrix, Lu4Zr3O 12 and Er 3+ The glass contains nanocrystals of rare earth ions. The glass components are, in mole percent, 58 mole percent SiO2, 13 mole percent Al2O3, 15 mole percent ZnO, 7 mole percent Li2O, 4 mole percent ZrO2, 2.9 mole percent Lu2O3, and 0.1 mole percent Er2O3. The glass further contains 0.2 mole percent Sb2O3.

[0016] The raw materials were weighed according to the composition, mixed uniformly, and placed in a crucible. The materials were melted at 1630°C for 2 hours, then poured into a brass mold and quenched. The quenched glass was quickly transferred to a tempering furnace and annealed at 630°C for 3 hours. The power was turned off and the furnace was cooled to room temperature to obtain precast glass (hereinafter referred to as AP). The AP glass was then heat-treated at 700°C, 720°C, 740°C, and 760°C for 6 hours to obtain the Lu4Zr3O 12 Functional nanocrystalline glasses were obtained.

[0017] As shown in Figure 1, a broad diffraction halo (Figure 1) is observed for the AP sample, indicating that the AP sample is primarily amorphous and lacks detectable nanocrystalline phases. When heat-treated at 700 °C, a weak diffraction peak appears around 30°. As the heat-treatment temperature increases, this peak gradually becomes stronger, and simultaneously, other diffraction peaks with larger diffraction angles also appear (Figure 1). These diffraction peaks are due to the presence of Lu4Zr3O 12 The diffraction peaks are consistent with those of the crystal (PDF#77-738, space group R

[16] ), and the heat-treated glass contains Lu4Zr3O 12 This indicates that nanocrystalline crystals are precipitated.

[0018] As shown in Figure 2, after heat treatment, numerous dark spots (10-25 nm) were observed in the sample, and these dark spots were distributed almost uniformly within the sample (Figure 2a). The enlarged image shown in Figure 2b reveals that these dark spots are composed of multiple small nanocrystals (5-10 nm) with clear lattice fringes, indicating the aggregation of small nanocrystals. The HR-TEM image (Figure 2c) shows that the spacing between the crystal planes of these small nanocrystals is approximately 2.97 μm, indicating the formation of Lu4Zr3O 12 The distance between the crystal planes of the crystals (=2.9763 μm, PDF#77-738) is consistent with the distance between the crystal planes of the crystals (=2.9763 μm, PDF#77-738). The XRD pattern and HR-TEM images show that the glass was converted into Lu4Zr3O after heat treatment. 12 It has been proven that nanocrystals were precipitated. After further heat treatment, the glass was converted to Lu4Zr3O 12 To prove the precipitation of nanocrystals, EDS mapping was performed on the sample treated at 760°C for 6 hours, and the results are shown in Figure 3. The elemental distribution in the area shown in Figure 3a reveals that Lu (Figure 3b) and Zr (Figure 3c) are concentrated in these nanocrystals, and the analysis results from XRD and TEM are consistent. Although the concentration of Er2O3 in the glass is relatively low and the contrast in Figure 3d is also relatively weak, the distribution of Er (Figure 3d) is almost consistent with the distribution of Lu and Zr, indicating that Er 3+ The ion is Lu4Zr3O 12The other elements, such as Si (Fig. 3e), Zn (Fig. 3f), Al (Fig. 3g), and O (Fig. 3h), are distributed almost uniformly in the sample. 3+ The ion is Lu4Zr3O 12 The nanocrystals are doped with Er 3+ It can change the local environment and optical properties of the ions. Er 3+ Doped Lu4Zr3O 12 To evaluate the potential application of nanocrystalline microcrystalline glasses in low-temperature optical thermometry, we measured the emission spectrum of a sample heat-treated at 760°C for 6 hours, and then measured its temperature-dependent change (Fig. 4). Figure 4a shows the normalized emission spectrum recorded at 10-296K (Fig. 4a shows the following temperatures from bottom to top around 525nm: 10K, 20K, 40K, 60K, 80K, 100K, 120K, 140K, 160K, 180K, 200K, 225K, 250K, 275K, and 296K). Absolute temperature sensitivity S A increases with increasing temperature, reaching a maximum value at 465 K, and the relative temperature sensitivity S R decreased with increasing temperature (Fig. 4c). A is 0.3%K -1 , S R is 1.03%K -1 From the above results, Er 3+ Doped Lu4Zr3O 12 Microcrystalline glasses containing nanocrystals have been found to have potential applications in low-temperature optical thermometry.

[0019] <Example 2> This example is substantially the same as Example 1, except that the glass components, in mole percent, include 57 mole percent SiO2, 16 mole percent Al2O3, 18 mole percent ZnO, 6 mole percent Li2O, 3 mole percent ZrO2, 2 mole percent Lu2O3, 0.2 mole percent Er2O3, and further include 0.1 mole percent Sb2O3. The AP glass was heat-treated at 760°C for 6 hours. S at 300K A is 0.25%K -1 , S R is 1.13%K-1 It was.

[0020] Example 3 This example is substantially the same as Example 1, except that the glass components, in mole percent, include 59 mole percent SiO2, 12 mole percent Al2O3, 14 mole percent ZnO, 8 mole percent Li2O, 5 mole percent ZrO2, 3 mole percent Lu2O3, 0.05 mole percent Er2O3, and further include 0.3 mole percent Sb2O3. The AP glass was heat-treated at 760°C for 6 hours. S at 300K A is 0.28%K -1 , S R is 1.20%K -1 It was. Although the preferred specific embodiments of the present invention have been described in detail above, those skilled in the art can make many modifications and changes based on the concept of the present invention without any creative work. Therefore, technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments based on the concept of the present invention and the prior art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A rare earth ion-doped functional nanocrystalline glass, the glass comprising a glass matrix and a rare earth ion-doped nanocrystalline glass. ４ Zr ３ O １２ and Er ３＋ nanocrystals comprising rare earth ions; The glass component is, in mol %, SiO ２ : 57-59, Al ２ O ３ : 12-16, ZnO: 14-18, Li ２ O: 6 to 8, ZrO ２ : 3-5, Lu ２ O ３ : 2-3, Er ２ O ３ : 0.05 to 0.2, and the sum of the glass components is 100.

2. 2. The rare earth ion-doped functional nanocrystalline glass according to claim 1, wherein the size of the nanocrystals is 5-10 nm.

3. The glass further comprises 0.1-0.3 mol % Sb ２ O ３ The rare earth ion-doped functional nanocrystalline glass according to claim 2, characterized in that it comprises:

4. A method for producing the rare earth ion-doped functional nanocrystalline glass according to any one of claims 1 to 3, comprising the steps of: weighing all raw materials according to the composition, uniformly mixing them, placing them in a crucible, melting them at 1600 to 1650°C for 1 to 3 hours, pouring them into a mold and quenching them; annealing the quenched glass at 600 to 650°C for 2 to 4 hours, and cooling it to room temperature to obtain a precast glass; and heat-treating the precast glass at 700 to 800°C for 5 to 7 hours to obtain the Lu ion-doped functional nanocrystalline glass. ４ Zr ３ O １２ and a step of obtaining a functional nanocrystalline glass.

5. 10. Use of the rare earth ion-doped functional nanocrystalline glass according to claim 1 as a low-temperature optical thermometric material.

6. 6. The use according to claim 5, wherein the low temperature range is from -263°C to 25°C.

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