Rare earth ion doped functional nanocrystalline glass and preparation method thereof

Abstract

The invention discloses Lu4Zr3O12 functional nanocrystalline glass doped with Er < 3 + > rare earth ions and a preparation method of the Lu4Zr3O12 functional nanocrystalline glass. The glass comprises the following components (in molar percentage): 57 to 59 percent of SiO2 and 12 to 16 percent of Al2O3; the glass comprises the following components in percentage by weight: 14 to 18 percent of ZnO, 6 to 8 percent of Li2O, 3 to 5 percent of ZrO2, 2 to 3 percent of Lu2O3 and 0.05 to 0.2 percent of Er2O3, wherein the sum of the components of the glass is 100 percent. Through composition design and heat treatment process regulation and control, controllable preparation of the Lu4Zr3O12 functional nanocrystalline doped with Er < 3 + > rare earth ions in the glass is realized, and the functional nanocrystalline glass has potential application value in the aspect of low-temperature optical temperature measurement.

Description

Technical Field

[0001] The present invention relates to the field of glass, and in particular to an Er 3+ Rare earth ion doped Lu4Zr3O 12 Functional nanocrystalline glass and preparation method thereof. Background Art

[0002] Oxides composed of RE2O3-MO2 (RE = La-Lu; M = Ti, Zr, Hf) have many special properties. Such oxides may have defective fluorite structure, pyrochlore structure or delta phase rhombohedral structure, depending on the chemical composition of these oxides and the order-disorder transitions they exhibit, such as pyrochlore to defective fluorite, rhombohedral delta phase to defective fluorite, beta phase (hexagonal) to defective fluorite, which are strongly dependent on temperature and annealing time. The chemical formula of the oxides in these systems can generally be expressed as [AB]2O 8-x , such as A2B2O7 pyrochlore, A4B3O 12 δ-phase and A2BO5β-phase, where A and B are trivalent and tetravalent cations, respectively. In most cases, these oxides have good physical and chemical properties, especially low thermal conductivity and high solubility of rare earth ions. These special properties make these oxides promising for use in thermal insulation coatings, nuclear waste solidification, hosts for luminescent rare earth ions, and pigments.

[0003] In recent years, the δ phase RE4Zr3O 12 The optical properties of crystals have been extensively studied, such as Y4Zr3O 12 :Gd 3+ UV luminescence, Y4Zr3O 12 :Eu 3+ Most of these materials are synthesized by sol-gel and high temperature sintering, sintering, coprecipitation or mechanical activation and solution combustion. However, it is impossible to directly synthesize δ-phase RE4Zr3O in glass. 12 Therefore, it is necessary to provide a kind of RE4Zr3O that can precipitate δ phase in glass. 12 new materials and methods. Summary of the invention

[0004] The object of the present invention is to provide a 3+ Rare earth ion doped Lu4Zr3O 12 Functional nanocrystalline glass and its preparation method. Its preparation process is simple, the size of nanocrystalline is controllable, and the cost is low.

[0005] The solution adopted by the present invention to solve the above technical problems is:

[0006] A kind of 3+Rare earth ion doped Lu4Zr3O 12 Functional nanocrystalline glass The glass comprises a glass matrix and a glass matrix composed of Lu4Zr3O 12 And Er 3+ Nanocrystals composed of rare earth ions.

[0007] Preferably, the glass components include, in molar percentage, SiO2: 57-59, Al2O3: 12-16; ZnO: 14-18, Li2O: 6-8, ZrO2: 3-5, Lu2O3: 2-3, Er2O3: 0.05-0.2, and the sum of the above glass components is 100.

[0008] Preferably, the size of the nanocrystals is 5-10 nm.

[0009] Preferably, the glass further comprises 0.1-0.3 mol % Sb2O3.

[0010] The Lu4Zr3O 12 The preparation method of functional nanocrystalline glass comprises the following steps: weighing all raw materials according to the above composition and mixing them evenly, placing them in a crucible, melting them at 1600-1650°C for 1-3 hours, and then pouring them into a mold for quenching; rapidly annealing the quenched glass at 600-650°C for 2-4 hours, cooling it to room temperature, and obtaining prefabricated glass; heat treating the prefabricated glass at 700-800°C for 5-7 hours, and obtaining the Lu4Zr3O 12 Functional nanocrystalline glass.

[0011] The Lu4Zr3O 12 Application of functional nanocrystalline glass in low-temperature optical temperature measurement materials.

[0012] Preferably, the low temperature range is -263°C to 25°C.

[0013] Compared with the prior art, the present invention has the following beneficial effects:

[0014] The present invention is based on glass composition design and optimization, and adopts melt quenching-heat treatment method to prepare Er in glass. 3+ :Lu4Zr3O 12 The preparation process is simple, and the composition and size of nanocrystals can be flexibly adjusted; the present invention converts Lu4Zr3O 12 Nanocrystals and glass composites can effectively utilize the excellent stability of the glass matrix to improve Lu4Zr3O 12 The stability of nanocrystals can be improved by preventing them from agglomerating. At the same time, such nanocrystals can be composited with glass, which has potential application value in low-temperature optical temperature measurement. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 The Lu4Zr3O obtained by heat treatment of the prefabricated glass AP in Example 1 at different temperatures 12 XRD pattern of functional nanocrystalline glass.

[0016] Figure 2 for Figure 1 Transmission electron microscopy images of the functional nanocrystalline glass obtained at a temperature of 760°C, where (a) is a bright field image, (b) is a magnified image, and (c) is a HR-TEM image.

[0017] Figure 3 for Figure 1 EDS spectrum results of functional nanocrystalline glass obtained at 760°C. (a) Dual-field image of the sample and the distribution of (b) Lu, (c) Zr, (d) Er, (e) Si, (f) Zn, (g) Al, and (h) O.

[0018] Figure 4 (a) Figure 1 Normalized emission spectrum of the functional nanocrystalline glass obtained at 760°C. (b) 2 H 11 / 2 → 4 I 15 / 2 and 4 S 3 / 2 → 4 I 15 / 2 The emission intensity ratio between transition emissions. (c) Relative sensitivity (S R ) and absolute sensitivity S A curve. DETAILED DESCRIPTION

[0019] The present invention is further described below in conjunction with the accompanying drawings and embodiments, but the content of the present invention is not limited to the following embodiments.

[0020] Example 1

[0021] This embodiment provides a 3+ Rare earth ion doped Lu4Zr3O 12 Functional nanocrystalline glass, the glass comprising a glass matrix and a glass matrix composed of Lu4Zr3O 12 And Er 3+ Nanocrystals composed of rare earth ions. The glass components include 58SiO2-13Al2O3-15ZnO-7Li2O-4ZrO2-2.9Lu2O3-0.1Er2O3 in terms of molar percentage, and the glass also includes 0.2 molar percentage of Sb2O3.

[0022] The raw materials were weighed and mixed uniformly according to the above composition, placed in a crucible, melted at 1630°C for 2 hours, and then poured into a brass mold for quenching; the quenched glass was quickly transferred to a tempering furnace, annealed at 630°C for 3 hours, and cooled to room temperature with the furnace by turning off the power to obtain a prefabricated glass (hereinafter referred to as AP); the AP glass was heat treated at 700°C, 720°C, 740°C and 760°C for 6 hours to obtain the Lu4Zr3O 12 Functional nanocrystalline glass.

[0023] like Figure 1 As shown, for the AP sample, only a broad diffraction halo is observed ( Figure 1 ), indicating that the AP sample is mainly amorphous and there is no detectable nanocrystalline phase. When heat treated at 700℃, a weak diffraction peak appears at 30°. As the heat treatment temperature increases, the peak gradually strengthens, and other diffraction peaks with larger diffraction angles appear ( Figure 1 ). It was found that these diffraction peaks are similar to those of Lu4Zr3O 12 The diffraction peaks of the crystals (PDF#77-738, space group R

[16] ) are consistent, indicating the presence of Lu4Zr3O in the heat-treated glass. 12 Precipitation of crystalline nanocrystals.

[0024] Depend on Figure 2 It can be seen that after heat treatment, many dark spots (10-25 nm) were observed in the sample, and these dark spots were almost uniformly distributed in the sample ( Figure 2 a) In Figure 2 In the enlarged image shown in b, it is found that these black spots are composed of several small nanocrystals (5-10nm) with clear lattice fringes, indicating the aggregation of small nanocrystals. HR-TEM image ( Figure 2 c) shows that the interplanar spacing of these small nanocrystals is ∼2.97 μm, which is similar to that of Lu4Zr3O 12 The interplanar spacing of the crystals (=2.9763 μm, PDF#77-738) is consistent. XRD patterns and HR-TEM images confirm that Lu4Zr3O is precipitated in the glass after heat treatment. 12 In order to further confirm the Lu4Zr3O 12 The precipitation of nanocrystals was carried out by EDS mapping of the sample treated at 760℃ for 6h, as shown in Figure 3 shown. Figure 3 The element distribution in the region shown in a shows that Lu( Figure 3 b) and Zr( Figure 3 c) concentrated in these nanocrystals, which is consistent with the results of XRD and TEM analysis. Although the concentration of Er2O3 in the glass is low, Figure 3 The contrast in d is also relatively weak, but the distribution of Er ( Figure 3 d) is still largely consistent with the distribution of Lu and Zr, indicating that Er 3+ Ions doped into Lu4Zr3O 12 Nanocrystals. Other elements, such as Si ( Figure 3 e), Zn( Figure 3 f), Al( Figure 3 g) and O( Figure 3 h), is almost evenly distributed in the sample. During the heat treatment, Er 3+ Ions enter Lu4Zr3O 12 Nanocrystals, changing Er 3+ The local environment and optical properties of ions. 3+ :Lu4Zr3O 12 Nanocrystal-doped glass-ceramics have great potential for application in low-temperature optical temperature measurement. The emission spectra of samples heat treated at 760℃ for 6h were tested as a function of temperature (e.g. Figure 4 shown). Figure 4 a is the normalized emission spectrum recorded at 10-296 K. Absolute temperature sensitivity S A It increases with the increase of temperature and reaches the maximum value at 465K. The relative temperature sensitivity S R Decreases with increasing temperature ( Figure 4 c). S at 300K A 0.3% K -1 , S R 1.03% K -1 The results show that Er 3+ :Lu4Zr3O 12 Nanocrystalline glass-ceramics have potential application value in low-temperature optical temperature measurement.

[0025] Example 2

[0026] This embodiment is substantially the same as the embodiment 1, except that the glass components of this embodiment include 57SiO2-16Al2O3-18ZnO-6Li2O-3ZrO2-2Lu2O3-0.2Er2O3 in terms of molar percentage, and the glass further includes 0.1 molar percentage of Sb2O3, and the AP glass is heat treated at 760°C for 6 hours. A 0.25% K -1 , S R 1.13% K -1 .

[0027] Example 3

[0028] This embodiment is substantially the same as the embodiment 1, except that the glass components of this embodiment include 59SiO2-12Al2O3-14ZnO-8Li2O-5ZrO2-3Lu2O3-0.05Er2O3 in terms of molar percentage, and the glass further includes 0.3 molar percentage of Sb2O 3， The AP glass was heat treated at 760°C for 6 hours. A 0.28% K -1 , S R 1.20% K -1 .

[0029] The preferred specific embodiments of the present invention are described in detail above. It should be understood that a person skilled in the art can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solution that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A rare earth ion doped functional nanocrystalline glass, characterized in that: The glass comprises a glass matrix and a glass matrix composed of Lu4Zr3O 12 And Er 3+ Nanocrystals composed of rare earth ions.

2. The rare earth ion doped functional nanocrystalline glass according to claim 1, characterized in that: The glass components include, by molar percentage, SiO2: 57-59, Al2O3: 12-16, ZnO: 14-18, Li2O: 6-8, ZrO2: 3-5, Lu2O3: 2-3, Er2O3: 0.05-0.2, and the sum of the above glass components is 100.

3. The rare earth ion doped functional nanocrystalline glass according to claim 1, characterized in that: The size of the nanocrystals is 5-10 nm.

4. The rare earth ion doped functional nanocrystalline glass according to claim 2, characterized in that: The glass further comprises 0.1-0.3 mol % of Sb2O3.

5. A method for preparing rare earth ion-doped functional nanocrystalline glass according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: weighing all raw materials according to the above composition and mixing them uniformly, placing them in a crucible, melting them at 1600-1650°C for 1-3 hours, and then pouring them into a mold for quenching; rapidly annealing the quenched glass at 600-650°C for 2-4 hours, cooling it to room temperature, and obtaining prefabricated glass; heat treating the prefabricated glass at 700-800°C for 5-7 hours, and obtaining the Lu4Zr3O 12 Functional nanocrystalline glass.

6. Application of the rare earth ion doped functional nanocrystalline glass as claimed in claim 1 in low-temperature optical temperature measurement materials.

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

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