A rare earth ion doped functional nanocrystal glass and a preparation method thereof

Abstract

The present invention discloses an Er 3+ Rare earth ion doped Lu4Zr3O 12 Functional nanocrystalline glass and its preparation method. The glass components (in molar percentage) are: 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. The present invention achieves Er2O3 in glass through composition design and heat treatment process control. 3+ Rare earth ion doped Lu4Zr3O 12 Controllable preparation of functional nanocrystals, and this functional nanocrystal glass has potential application value in low-temperature optical temperature measurement.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of glass, in particular to an Er 3+ rare earth ion doped Lu4Zr3O 12 functional nanocrystal glass and preparation method thereof. BACKGROUND

[0002] Oxides consisting of RE2O3-MO2 (RE = La-Lu; M = Ti, Zr, Hf) have many special properties. Such oxides can have a defect-fluorite structure, a pyrochlore structure or a delta-rhombohedral structure, depending on the chemical composition of these oxides and the order-disorder transition exhibited, such as pyrochlore to defect-fluorite, rhombohedral delta phase to defect-fluorite, beta phase (hexagonal) to defect-fluorite, which are strongly dependent on temperature and annealing time. The chemical formula of the oxides in these systems can be generally represented as [AB]2O 8-x , such as A2B2O7 pyrochlore, A4B3O 12 delta phase and A2BO5 beta phase, where A and B are trivalent and tetravalent cations, respectively. In most cases, such oxides have good physical and chemical properties, especially low thermal conductivity and high solubility of rare earth ions. These special properties make such oxides promising for use in the fields of thermal barrier coatings, nuclear waste immobilization, hosts for luminescent rare earth ions and pigments, etc.

[0003] In recent years, the delta phase RE4Zr3O 12 crystals have been widely studied for their optical properties, such as UV luminescence of Y4Zr3O 12 : Gd 3+ , red latent fingerprint luminescence of Y4Zr3O 12 : Eu 3+ , etc. Most of these materials are synthesized by sol-gel and high-temperature sintering, sintering, eutectoid or mechanical activation, and solution combustion method, etc. However, the delta phase RE4Zr3O 12 cannot be directly synthesized in glass. Therefore, it is necessary to provide a new material and method capable of precipitating the delta phase RE4Zr3O 12 in glass. SUMMARY

[0004] The present application aims to provide an Er 3+ rare earth ion doped Lu4Zr3O 12 functional nanocrystal glass and preparation method thereof. The preparation process is simple, the nanocrystal size is controllable, and the cost is low.

[0005] The present application employs the following scheme to solve the above technical problems:

[0006] An Er 3+Rare earth ion doped Lu4Zr3O 12 Functional nanocrystalline glass includes 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 % of 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 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 to obtain prefabricated glass; heat treating the prefabricated glass at 700-800°C for 5-7 hours to obtain 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 controlled. 12 Nanocrystals and glass composites can effectively utilize the excellent stability of the glass matrix to improve Lu4Zr3O 12 The stability of nanocrystals is improved and their agglomeration is prevented. At the same time, such nanocrystals are compounded with glass and have 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 of 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 spectra of the 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 functional nanocrystalline glass obtained at 760℃. (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 with reference to the accompanying drawings and embodiments, but the present invention is not limited to the following embodiments.

[0020] Example 1

[0021] This embodiment provides an Er 3+ Rare earth ion doped Lu4Zr3O 12 Functional nanocrystalline glass, the glass includes 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] After the above raw materials are weighed according to the above composition and uniformly mixed, they are placed in a crucible, melted at 1630°C for 2h, and then poured into a brass mold for quenching; the quenched glass is quickly transferred to a tempering furnace, annealed at 630°C for 3h, and cooled to room temperature by turning off the power, to obtain a preform glass (hereinafter referred to as AP); the AP glass is heat-treated at 700°C, 720°C, 740°C and 760°C for 6h to obtain the Lu4Zr3O 12 functional nanocrystal glass.

[0023] As Figure 1 shown, for the AP sample, only a broad halo of diffraction is observed, indicating that the AP sample is mainly amorphous and no detectable nanocrystals exist. When heat-treated at 700°C, a weak diffraction peak appears at 30°, and with the increase of heat-treatment temperature, the peak gradually strengthens, and other diffraction peaks with larger diffraction angles also appear. Figure 1 It is found that these diffraction peaks are consistent with the diffraction peaks of Lu4Zr3O 12 crystals (PDF #77-738, space group R

[16] ), indicating the precipitation of Lu4Zr3O 12 crystal nanocrystals in the heat-treated glass.

[0024] As Figure 2 can be seen, after heat-treatment, many dark spots (10-25nm) are observed in the sample, and these dark spots are almost uniformly distributed in the sample Figure 2 a). In the enlarged image shown in Figure 2 b, it is found that these dark spots are composed of several small nanocrystals (5-10nm) with clear lattice fringes, indicating the aggregation of small nanocrystals. The HR-TEM image Figure 2 c) shows that the interplanar spacing of these small nanocrystals is ~2.97μm, which is consistent with the interplanar spacing of Lu4Zr3O 12 crystals (=2.9763μm, PDF #77-738). Both the XRD pattern and the HR-TEM image confirm the precipitation of Lu4Zr3O 12 nanocrystals in the glass after heat-treatment. In order to further confirm the precipitation of Lu4Zr3O 12 nanocrystals in the glass after heat-treatment, EDS mapping is performed on the sample treated at 760°C for 6h, as shown in Figure 3 . Figure 3 The element distribution in the area shown in Figure 3 a indicates that Lu Figure 3 b) and Zr Figure 3 c) are concentrated in these nanocrystals, which is consistent with the results of XRD and TEM analysis. Although the concentration of Er2O3 in the glass is relatively low, the contrast in Figure 3 d is also relatively weak, but the distribution of Er is consistent with the results of XRD and TEM analysis.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 4 h), is almost evenly distributed in the sample. During the heat treatment, Er 3+ ions enter Lu4Zr3O 12 Nanocrystals, changed Er 3+ The local environment and optical properties of ions. 3+ :Lu4Zr3O 12 The application potential of nanocrystal-doped glass-ceramics in low-temperature optical temperature measurement was studied. The emission spectrum of samples heat-treated at 760℃ for 6h was 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 increasing temperature and reaches its maximum value at 465K. The relative temperature sensitivity S R Decreases with increasing temperature ( ​ c). S at 300K A 0.3% K -1 , S R 1.03% K -1 The results showed that Er 3+ :Lu4Zr3O 12 Nanocrystalline glass-ceramics has potential application value in low-temperature optical temperature measurement.

[0025] Example 2

[0026] This embodiment is substantially the same as embodiment 1, except that the glass composition of this embodiment comprises, in terms of molar percentage, 57SiO2-16Al2O3-18ZnO-6Li2O-3ZrO2-2Lu2O3-0.2Er2O3, and the glass further comprises 0.1 molar percentage of Sb2O3. 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 example is substantially the same as Example 1, except that the glass composition of this example includes, in mole percent, 59 SiO2- 12 Al2O3- 14 ZnO - 8 Li2O - 5 ZrO2- 3 Lu2O3- 0.05 Er2O3, the glass further including an addition of 0.3 mole percent Sb2O3 3， The AP glass was heat treated at 760°C for 6 hours. The S A was 0.28% K -1 , S R was 1.20% K -1 .

[0029] The preferred embodiments of the application have been described above in detail. It should be understood that modifications and variations to the concepts herein disclosed can be made by those of ordinary skill in the art without departing from the scope of the application. Accordingly, such modifications and variations are intended to fall within the scope of the application as defined by the appended 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, 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.

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

3. The rare earth ion-doped functional nanocrystalline glass according to claim 1, characterized in that: The glass further comprises 0.1-0.3 mol % of Sb2O3.

4. 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 to obtain the Lu4Zr3O 12 Functional nanocrystalline glass.

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

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

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