Germanate microcrystalline glass for separating out LiLuF4 nanocrystals and preparation method of germanate microcrystalline glass

Abstract

The invention discloses germanate microcrystalline glass for separating out LiLuF4 nanocrystals and a preparation method of the germanate microcrystalline glass. The microcrystalline glass comprises the following components in percentage by mole: 40 to 50 percent of GeO2, 10 to 15 percent of LiF, 10 to 15 percent of LuF3, 10 to 20 percent of H3BO3, 5 to 10 percent of YF3 and 10 to 15 percent of La2O3. The preparation method comprises the following steps: weighing a certain mass of high-purity raw materials according to the molar percentage, uniformly mixing, melting in a lifting furnace at 1350-1450 DEG C, and keeping the temperature for 15-45 minutes; pouring the glass melt into a mold, putting the mold into a muffle furnace, carrying out annealing and heat preservation at 400-500 DEG C for 3-5 hours, naturally cooling to room temperature, and taking out to obtain base glass; and carrying out heat treatment on the prepared base glass in the crystallization temperature range for 1-6 hours, and then naturally cooling to room temperature to obtain the microcrystalline glass in which LiLuF4 nanocrystals are separated out.

Description

Technical Field

[0001] The invention relates to the field of rare earth doped microcrystalline glass, and in particular to a germanate microcrystalline glass containing LiLuF4 nanocrystals and a preparation method thereof. Background Art

[0002] With the rapid development of optoelectronic information technology, transparent optical materials represented by rare earth ion-doped luminescent glass have been widely used in laser light sources, display, luminescence, medicine and other fields. In order to obtain luminescent materials with excellent luminescence performance and good environmental adaptability, it is required that the matrix material used for doping luminescence has not only low phonon energy, but also good thermal, chemical stability and mechanical properties.

[0003] Glass-ceramics is a material between glass and crystal, combining the advantages of both. For oxyfluoride glass-ceramics, fluoride nanocrystals with low phonon energy are evenly distributed in the oxide glass network, and rare earth ions are preferentially enriched in the fluoride crystal phase, which determines that oxyfluoride glass-ceramics has the advantages of both oxide glass and fluoride crystals. It has both low phonon energy and high chemical and mechanical stability.

[0004] Since the size of the precipitated fluoride nanocrystals is generally tens of nanometers, which is much smaller than the wavelength of visible light, they have a high transmittance to visible light. Therefore, fluoride oxide glass-ceramics has gradually attracted attention and research interest in recent years. Summary of the invention

[0005] In order to solve the above technical problems existing in the prior art, the present invention discloses a germanate glass-ceramic that precipitates LiLuF4 nanocrystals and a preparation method thereof, specifically, by designing glass components, obtaining a basic glass by a melt quenching method, and then heat treating the basic glass, thereby precipitating LiLuF4 nanocrystals in the glass. The specific technical scheme is as follows:

[0006] A germanate glass-ceramic with LiLuF4 nanocrystals precipitated, the glass having a molar percentage composition of:

[0007]

[0008] A method for preparing germanate glass-ceramics for precipitating LiLuF4 nanocrystals comprises the following steps:

[0009] (1) Ingredients: GeO2, LiF, LuF3, H3BO3, YF3 and La2O3 are used as glass composition raw materials, and the corresponding mass of the raw materials is weighed according to the molar percentage of the above glass composition, and ground and mixed in a mortar;

[0010] (2) Melting: Pour the ground and mixed glass raw materials into a crucible and place it in a silicon carbon rod electric furnace for melting; (3) Molding: Pour the glass melt into a mold preheated at 400-500°C for molding;

[0011] (4) Annealing: The formed glass is placed in a muffle furnace for annealing at a temperature of 400 to 500 degrees Celsius for 3 to 5 hours, and then the power supply of the muffle furnace is turned off and the glass is cooled to room temperature.

[0012] (5) Heat treatment: Heat treatment is performed within the crystallization temperature range (600-650°C) for several hours;

[0013] (6) Polishing: The heat-treated glass is cut, ground, and polished to produce germanate glass-ceramics with LiLuF4 nanocrystals precipitated.

[0014] Furthermore, in step (2), the melting temperature is 1350 to 1450 degrees Celsius, and the melting time is 15 to 45 minutes.

[0015] Furthermore, in step (5), the crystallization temperature is 600-650°C.

[0016] The germanate glass-ceramics with precipitated LiLuF4 nanocrystals of the present invention has a simple and efficient preparation method and has potential application prospects in the fields of optical communication, three-dimensional display and solid-state lighting. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention.

[0018] Figure 1 This is the XRD diagram of the base glass and the microcrystalline glass in Example 1. DETAILED DESCRIPTION

[0019] The present invention will be further described below in conjunction with the accompanying drawings.

[0020] Example 1

[0021] According to the composition: 45GeO2-12LiF-10LuF3-15H3BO3-6YF3-12La2O3 (mol%), weigh the GeO2, LiF, LuF3, H3BO3, YF3, La2O3 powder raw materials with a total mass of 20 grams, put them into an agate mortar and grind them thoroughly and mix them evenly. Pour the mixed glass raw materials into a crucible, cover it with a mullite lid, place it in a 1400℃ silicon carbon rod electric furnace to melt for 45 minutes, then quickly pour the glass melt into a mold preheated at 500℃, after the glass is formed, transfer it to a 500℃ muffle furnace for annealing for 5 hours, and naturally cool it to room temperature to obtain the basic glass. The obtained basic glass is heated to 610℃ in a muffle furnace at a heating rate of 10℃ / min and kept warm for 3h to obtain germanosilicate microcrystalline glass containing LiLuF4 nanocrystals. The obtained microcrystalline glass is cut, ground and polished to make 10mm*10mm*1.5mm microcrystalline glass.

[0022] like Figure 1 Shown are the XRD patterns of base glass and glass-ceramics.

[0023] Example 2

[0024] According to the composition: 40GeO2-15LiF-10LuF3-15H3BO3-5YF3-15La2O3 (mol%), weigh the GeO2, LiF, LuF3, H3BO3, YF3, La2O3 powder raw materials with a total mass of 20 grams, put them into an agate mortar and grind them thoroughly and mix them evenly. Pour the mixed glass raw materials into a crucible, cover it with a mullite lid, place it in a 1350℃ silicon carbon rod electric furnace to melt for 25 minutes, then quickly pour the glass melt into a mold preheated at 400℃, after the glass is formed, transfer it to a 500℃ muffle furnace for annealing for 5 hours, and naturally cool it to room temperature to obtain the basic glass. The obtained basic glass is heated to 600℃ in a muffle furnace at a heating rate of 10℃ / min and kept warm for 4h to obtain germanosilicate microcrystalline glass containing LiLuF4 nanocrystals. The obtained microcrystalline glass is cut, ground and polished to make 10mm*10mm*1.5mm microcrystalline glass.

[0025] Example 3

[0026] According to the composition: 50GeO2-10LiF-12LuF3-11H3BO3-5YF3-12La2O3 (mol%), weigh the GeO2, LiF, LuF3, H3BO3, YF3, La2O3 powder raw materials with a total mass of 20 grams, put them into an agate mortar and grind them thoroughly and mix them evenly. Pour the mixed glass raw materials into a crucible, cover it with a mullite lid, place it in a 1450℃ silicon carbon rod electric furnace to melt for 30 minutes, then quickly pour the glass melt into a mold preheated at 500℃, after the glass is formed, transfer it to a 500℃ muffle furnace for annealing for 5 hours, and naturally cool it to room temperature to obtain the basic glass. The obtained basic glass is heated to 620℃ in a muffle furnace at a heating rate of 10℃ / min and kept warm for 3h to obtain germanosilicate microcrystalline glass containing LiLuF4 nanocrystals. The obtained microcrystalline glass is cut, ground and polished to make 10mm*10mm*1.5mm microcrystalline glass.

[0027] The above embodiments are used to illustrate the present invention rather than to limit the present invention. Any modification and change 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 germanate glass-ceramic with LiLuF4 nanocrystals, characterized in that: The molar percentage composition of the glass is: Raw material molar percentage (mol%) GeO240~50% LiF 10~15% LuF310~15% H3BO310~20% YF35~10% La2O310~15%.

2. A method for preparing germanate glass-ceramics from which LiLuF4 nanocrystals are precipitated as claimed in claim 1, characterized in that The steps include: (1) Ingredients: GeO2, LiF, LuF3, H3BO3, YF3 and La2O3 are used as glass composition raw materials, and the corresponding mass of the raw materials is weighed according to the molar percentage of the above glass composition, and ground and mixed in a mortar; (2) Melting: Pour the ground and mixed glass raw materials into a crucible and melt them in a silicon carbon rod electric furnace; (3) Molding: Pour the molten glass into a mold preheated to 400-500°C for molding; (4) Annealing: The formed glass is placed in a muffle furnace for annealing at a temperature of 400-500 degrees Celsius for 3-5 hours. The power of the muffle furnace is then turned off and the glass is cooled to room temperature. (5) Heat treatment: Heat treatment is performed within the crystallization temperature range (600-650°C) for several hours; (6) Polishing: The heat-treated glass is cut, ground, and polished to produce germanate glass-ceramics with LiLuF4 nanocrystals precipitated.

3. The preparation method according to claim 2, characterized in that: In step (2), the melting temperature is 1350-1450 degrees Celsius, and the melting time is 15-45 minutes.

4. The preparation method according to claim 2, characterized in that: The crystallization temperature in step (5) is 600-650°C.

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