Rare earth ion doped LiF glass-ceramic and preparation method thereof

Abstract

The present invention discloses a rare earth ion-doped LiF glass-ceramic and a preparation method thereof. The rare earth ion-doped LiF glass-ceramic is composed of the following components, measured by molar percentage: 50%-55% SiO2, 20%-25% B2O3, 20%-25% LiF, 0.5%-1% KBr, 0.01%-0.1% CeO2, 0.01%-0.1% Ag2O, and 0.1%-0.3% Sb2O3. The preparation method comprises the following steps: firstly preparing a rare earth-doped precursor glass by a high-temperature melt quenching method, then using a He-Cd laser with a wavelength of 325nm as an ultraviolet light source for laser irradiation, and finally selecting a suitable temperature for thermal development to obtain a transparent rare earth ion-doped LiF glass-ceramic with excellent physical and chemical properties and a locally controllable precipitated LiF crystal phase.

Description

Technical Field

[0001] The present invention relates to rare earth ion doped glass-ceramics, in particular to rare earth ion doped LiF glass-ceramics and a preparation method thereof. Background Art

[0002] Transparent glass-ceramics are a novel composite material consisting of both crystalline and glassy phases, obtained by holographically exposing a precursor glass and controlling nucleation and crystallization. Because the precipitated crystals are much smaller than visible light, they exhibit high transparency. The chemical composition of the glassy phase, the composition of the crystalline phase, and their morphology, quantity, and distribution all contribute to the properties of glass-ceramics.

[0003] Glass-ceramics combines the advantages of excellent fiber-forming properties of glass materials and excellent quantum efficiency of crystal materials. In addition, it has excellent comprehensive properties such as high mechanical strength, adjustable thermal expansion, good thermal shock resistance, chemical corrosion resistance and good thermal stability. By controlling the precipitated crystal phase and size, glass-ceramics can still maintain high transparency, and has become a research hotspot for rare earth ion-doped matrix materials.

[0004] Due to its unique structure, LiF crystals have a light transmission band of 0.1-7μm, making them suitable for use as infrared and ultraviolet windows or for X-ray spectrometry. Rare earth ion-doped LiF glass-ceramics, due to their wide optical band gap and potential thermoluminescence effect, enable detectors to measure high-energy radiation over a wide range, making them widely used in various detectors. Summary of the Invention

[0005] The present invention aims to provide a rare earth ion-doped LiF glass-ceramics and a preparation method thereof. The glass-ceramics have the advantages of high transparency, good thermal stability and mechanical properties, and controllable localization of the precipitated LiF crystal phase.

[0006] To achieve the above object, the present invention provides a rare earth ion-doped LiF glass-ceramics, which, in terms of molar percentage, comprises the following components:

[0007] 50%-55% SiO2,

[0008] 20%-25% B2O3,

[0009] 20%-25% LiF,

[0010] 0.5%-1% KBr,

[0011] 0.01%-0.1% CeO2,

[0012] 0.01%-0.1% Ag2O,

[0013] 0.1%-0.3% Sb2O3.

[0014] Further, in terms of mole percentage, it is composed of the following components:

[0015] 50%-54% SiO2,

[0016] 24%-25% B2O3,

[0017] 20%-24%LiF,

[0018] 0.5%-0.84% ​​KBr,

[0019] 0.03%-0.1% CeO2,

[0020] 0.01%-0.09% Ag2O,

[0021] 0.1%-0.25% Sb2O3.

[0022] Further, in terms of mole percentage, it is composed of the following components:

[0023] 53%-54% SiO2,

[0024] 24.3%-25% B2O3,

[0025] 21.83%-24%LiF,

[0026] 0.6%-0.84% ​​KBr,

[0027] 0.03%-0.05% CeO2,

[0028] 0.08%-0.09% Ag2O,

[0029] 0.15%-0.25% Sb2O3.

[0030] A method for preparing rare earth ion-doped LiF glass-ceramics comprises the following steps:

[0031] (1) Weighing various raw materials and thoroughly mixing them, wherein the raw materials are calculated based on the molar percentage of the rare earth ion-doped LiF glass-ceramics;

[0032] (2) melting the mixture obtained in step (1) at 1350-1450° C. and keeping the temperature for 0.5-2 hours to obtain a glass melt;

[0033] (3) pouring the glass melt obtained in step (2) into a mold and performing annealing treatment to obtain a precursor glass;

[0034] (4) irradiating the precursor glass obtained in step (3) with a He-Cd laser having a wavelength of 325 nm;

[0035] (5) The glass irradiated in step (4) is placed in a muffle furnace, and the glass is heat-treated at 500-550° C. for 2-4 hours, and then cooled to room temperature to obtain transparent rare earth ion-doped LiF microcrystalline glass.

[0036] The advantage of this invention lies in the controlled precipitation of LiF microcrystals in glass by adjusting the glass composition and optimizing the heat treatment process. This type of rare earth ion-doped LiF glass-ceramics combines the advantages of both glass and rare earth-doped LiF crystals. Furthermore, the glass has a short production cycle, a simple method, low cost, and is easy to mass produce. The preparation process can achieve large sizes and high doping levels. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 is the X-ray diffraction (XRD) pattern of the sample of Example 1 before heat treatment, showing an amorphous state;

[0038] Figure 2 This is the XRD curve of the sample in Example 1 after heat treatment at 500°C for 2 hours, and the precipitated crystal phase is LiF;

[0039] Figure 3 is the X-ray diffraction (XRD) pattern of the sample of Example 2 before heat treatment, showing an amorphous state;

[0040] Figure 4 This is the XRD curve of the sample in Example 2 after heat treatment at 550° C. for 4 hours, and the precipitated crystal phase is LiF. DETAILED DESCRIPTION

[0041] The invention is further described in detail below with reference to specific embodiments.

[0042] Example 1

[0043] Table 1 shows the molar percentage of each component of the rare earth ion-doped microcrystalline glass of Example 1.

[0044] raw material <![CDATA[SiO2]]> <![CDATA[B2O3]]> LiF KBr <![CDATA[CeO2]]> <![CDATA[Ag2O]]> <![CDATA[Sb2O3]]> Component (mol%) 50 25 24 0.6 0.05 0.05 0.3

[0045] Table 1 Raw materials of rare earth ion-doped glass-ceramics.

[0046] The specific preparation process is as follows: According to the molar percentage of each component in Table 1, accurately weigh analytically pure SiO2, B2O3, LiF, KBr, CeO2, Ag2O, and Sb2O3, mix them thoroughly and pour them into a crucible, keep them warm in an electric furnace at 1350°C for 0.5 hours, quickly pour the molten glass melt into the mold, and quickly transfer the glass to an annealing furnace after it is formed. After annealing at 400°C for 2 hours, cool it down with the furnace, and irradiate the annealed glass sample with a He-Cd laser of 325nm wavelength. The irradiated glass sample is then heat-treated at 500°C for 2 hours to obtain transparent microcrystalline glass. Figure 2 As shown, X-ray powder diffraction test and comparison with PDF card show that the crystal phase is LiF.

[0047] Example 2

[0048] Table 2 shows the molar percentage of each component of the rare earth ion-doped microcrystalline glass of Example 2.

[0049] raw material <![CDATA[SiO2]]> <![CDATA[B2O3]]> LiF KBr <![CDATA[CeO2]]> <![CDATA[Ag2O]]> <![CDATA[Sb2O3]]> Component (mol%) 55 24.3 20 0.5 0.01 0.09 0.1

[0050] Table 2 Raw materials of rare earth ion doped glass-ceramics.

[0051] The specific preparation process is as follows: According to the molar percentage of each component in Table 2, accurately weigh analytically pure SiO2, B2O3, LiF, KBr, CeO2, Ag2O, and Sb2O3, mix them thoroughly and pour them into a crucible, keep them warm in an electric furnace at 1450°C for 2 hours, quickly pour the molten glass melt into the mold, and quickly transfer the glass to an annealing furnace after it is formed. After annealing at 400°C for 2 hours, cool it down with the furnace, and irradiate the annealed glass sample with a He-Cd laser of 325nm wavelength; then heat treat the irradiated glass sample at 550°C for 4 hours to obtain transparent microcrystalline glass. Figure 4 As shown, X-ray powder diffraction test and comparison with PDF card show that the crystal phase is LiF.

[0052] Example 3

[0053] Table 3 shows the molar percentage of each component of the rare earth ion-doped microcrystalline glass of Example 3.

[0054] raw material <![CDATA[SiO2]]> <![CDATA[B2O3]]> LiF KBr <![CDATA[CeO2]]> <![CDATA[Ag2O]]> <![CDATA[Sb2O3]]> Component (mol%) 53.07 20.6 25 1 0.03 0.1 0.2

[0055] Table 3 Raw materials of rare earth ion doped glass-ceramics.

[0056] The specific preparation process is as follows: Analytically pure SiO2, B2O3, LiF, KBr, CeO2, Ag2O, and Sb2O3 were accurately weighed according to the molar percentages of the components listed in Table 3. After thorough mixing, the mixture was poured into a crucible and held in an electric furnace at 1400°C for one hour. The molten glass was quickly poured into a mold. Once formed, the glass was quickly transferred to an annealing furnace and annealed at 400°C for two hours, followed by cooling with the furnace. The annealed glass sample was irradiated with a 325nm He-Cd laser and then heat-treated at 510°C for three hours to obtain a transparent glass-ceramic. X-ray powder diffraction analysis and comparison with a PDF card revealed the crystalline phase to be LiF.

[0057] Example 4

[0058] Table 4 shows the molar percentage of each component of the rare earth ion-doped microcrystalline glass of Example 4.

[0059] raw material <![CDATA[SiO2]]> <![CDATA[B2O3]]> LiF KBr <![CDATA[CeO2]]> <![CDATA[Ag2O]]> <![CDATA[Sb2O3]]> Component (mol%) 54 20 24.9 0.84 0.1 0.01 0.15

[0060] Table 4 Raw materials of rare earth ion doped glass-ceramics.

[0061] The specific preparation process is as follows: Analytically pure SiO2, B2O3, LiF, KBr, CeO2, Ag2O, and Sb2O3 were accurately weighed according to the molar percentages of the components listed in Table 4. After thorough mixing, the mixture was poured into a crucible and held in an electric furnace at 1410°C for 0.7 hours. The molten glass was then quickly poured into a mold. Once formed, the glass was quickly transferred to an annealing furnace and annealed at 400°C for 2 hours, followed by cooling with the furnace. The annealed glass sample was irradiated with a 325nm He-Cd laser and then heat-treated at 530°C for 3.5 hours to obtain a transparent glass-ceramic. X-ray powder diffraction analysis and comparison with a PDF card revealed the crystalline phase to be LiF.

[0062] Example 5

[0063] Table 5 shows the molar percentage of each component of the rare earth ion-doped microcrystalline glass of Example 5.

[0064] raw material <![CDATA[SiO2]]> <![CDATA[B2O3]]> LiF KBr <![CDATA[CeO2]]> <![CDATA[Ag2O]]> <![CDATA[Sb2O3 <!-- 3 -->]]> Component (mol%) 53 24 21.83 0.8 0.04 0.08 0.25

[0065] Table 5 Raw materials of rare earth ion doped glass-ceramics.

[0066] The specific preparation process is as follows: Analytically pure SiO2, B2O3, LiF, KBr, CeO2, Ag2O, and Sb2O3 were accurately weighed according to the molar percentages of the components listed in Table 5. After thorough mixing, the mixture was poured into a crucible and held in an electric furnace at 1380°C for 0.6 hours. The molten glass was then quickly poured into a mold. Once formed, the glass was quickly transferred to an annealing furnace and annealed at 400°C for 2 hours, followed by cooling with the furnace. The annealed glass sample was irradiated with a He-Cd laser at a wavelength of 325 nm and then heat-treated at 540°C for 2 hours to obtain a transparent glass-ceramic. X-ray powder diffraction analysis and comparison with a PDF card revealed the crystalline phase to be LiF.

[0067] The above embodiments are used to illustrate the present invention rather than to limit the present invention. Any modifications and changes made to the present invention within the spirit of the present invention and the protection scope of the claims shall fall within the protection scope of the present invention.

Claims

1. A rare earth ion-doped LiF glass-ceramics, characterized by: Measured by mole percentage, it is composed of the following components: 50%-55% SiO2, 20%-25% B2O3, 20%-25%LiF, 0.5%-1% KBr, 0.01%-0.1%CeO2, 0.01%-0.1%Ag2O, 0.1%-0.3% Sb2O3.

2. The rare earth ion-doped LiF glass-ceramics according to claim 1, wherein: Measured by mole percentage, it is composed of the following components: 50%-54% SiO2, 24%-25% B2O3, 20%-24%LiF, 0.5%-0.84% ​​KBr, 0.03%-0.1%CeO2, 0.01%-0.09%Ag2O, 0.1%-0.25% Sb2O3.

3. The rare earth ion-doped LiF glass-ceramics according to claim 2, wherein: Measured by mole percentage, it is composed of the following components: 53%-54% SiO2, 24.3%-25% B2O3, 21.83%-24%LiF, 0.6%-0.84% ​​KBr, 0.03%-0.05%CeO2, 0.08%-0.09%Ag2O, 0.15%-0.25% Sb2O3.

4. A method for preparing rare earth ion-doped LiF glass-ceramics according to any one of claims 1 to 3, comprising the following steps: (1) Weighing various raw materials and thoroughly mixing them, wherein the raw materials are calculated based on the molar percentage of the rare earth ion-doped LiF glass-ceramics; (2) melting the mixture obtained in step (1) at 1350-1450°C and keeping the temperature for 0.5-2 hours to obtain a glass melt; (3) pouring the glass melt obtained in step (2) into a mold and performing annealing treatment to obtain precursor glass; (4) irradiating the precursor glass obtained in step (3) with a He-Cd laser having a wavelength of 325 nm; (5) The glass irradiated in step (4) is placed in a muffle furnace and heat-treated at 500-550°C for 2-4 hours, and then cooled to room temperature to obtain transparent rare earth ion-doped LiF microcrystalline glass.

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