Germanate microcrystalline glass for separating out Li3AlF6 nanocrystals and preparation method of germanate microcrystalline glass

Abstract

The invention discloses germanate microcrystalline glass for separating out Li3AlF6 nanocrystals and a preparation method of the germanate microcrystalline glass. The microcrystalline glass comprises the following components in percentage by mole: 40 to 45 percent of GeO2, 10 to 15 percent of LiF, 10 to 15 percent of LuF3, 10 to 20 percent of Al2O3, 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 1400-1500 DEG C, and preserving heat 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 2-8 hours, and then naturally cooling to room temperature to obtain the microcrystalline glass in which Li3AlF6 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 Li3AlF6 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, in recent years, fluoride oxide microcrystalline glass has gradually attracted attention and research interests, and has potential application prospects in the fields of optical communications, three-dimensional displays and solid-state lighting. 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 Li3AlF6 nanocrystals and a preparation method thereof, specifically, by designing glass components, obtaining a base glass by a melt quenching method, and then heat treating the base glass, thereby precipitating Li3AlF6 nanocrystals in the glass. The specific technical scheme is as follows: A germanate glass-ceramic with Li3AlF6 nanocrystals precipitated, the glass having a molar percentage composition of: Raw material molar percentage (mol%) GeO2 40~45% LiF 10~15% LuF310~15% Al2O3 10~20% YF3 5~10% La2O3 10~15%.

[0006] A method for preparing germanate glass-ceramics for precipitating Li3AlF6 nanocrystals comprises the following steps: (1) Ingredients: GeO2, LiF, LuF3, Al2O3, 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. The melting temperature is 1400-1500°C and the melting time is 25-30 minutes. (3) Molding: Pour the molten glass into a mold preheated to 400-500°C for molding; (4) Annealing: Place the formed glass in a muffle furnace for annealing at a temperature of 400-500°C for 3-5 hours, then turn off the power of the muffle furnace and cool it to room temperature. (5) Heat treatment: Heat treatment is performed within the crystallization temperature range for several hours; (6) Polishing: The heat-treated glass is cut, ground, and polished to produce germanate glass-ceramics with Li3AlF6 nanocrystals precipitated.

[0007] Furthermore, the crystallization temperature in step (5) is 650-750°C.

[0008] Furthermore, in step (2), the melting temperature is 1450° C. and the melting time is preferably 30 minutes.

[0009] Furthermore, the preheating temperature in step (3) is 450°C Furthermore, in step (4), the annealing temperature is 450° C. and the annealing time is 4 hours.

[0010] The germanate glass-ceramics with precipitated Li3AlF6 nanocrystals of the present invention can be used to prepare a volume Bragg grating (VBG) based on photothermorefractive (PTR) glass, and is applied to optical fields such as laser system design, three-dimensional display and imaging, and optical communication. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] 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.

[0012] Figure 1 : XRD diagram of base glass and glass-ceramics in Example 1 DETAILED DESCRIPTION

[0013] The present invention will be further described below in conjunction with the accompanying drawings. Example

[0014] According to the composition: 45GeO2-13LiF-12LuF3-15Al2O3-5YF3-10La2O3 (mol%), weigh the required GeO2, LiF, LuF3, Al2O3, 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, and place it in a silicon carbon rod electric furnace at 1450℃ for 30 minutes, then quickly pour the glass melt into a mold preheated at 500℃, and after the glass is formed, transfer it to a muffle furnace at 450℃ for annealing for 5 hours, and naturally cool it to room temperature to obtain the basic glass. The obtained basic glass is heated to 700℃ in a muffle furnace at a heating rate of 10℃ / min and kept warm for 4h to obtain germanosilicate microcrystalline glass containing Li3AlF6 nanocrystals. The obtained microcrystalline glass is cut, ground and polished to make 10mm*10mm*1.5mm microcrystalline glass. Example

[0015] According to the composition: 45GeO2-15LiF-10LuF3-10Al2O3-5YF3-15La2O3 (mol%), weigh the required GeO2, KF, K2CO3, H3BO3, YF3, and 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, and place it in a 1500℃ silicon carbon rod electric furnace for melting for 25 minutes, then quickly pour the glass melt into a mold preheated at 400℃, and after the glass is formed, transfer it to a 500℃ muffle furnace for annealing for 3 hours, and naturally cool it to room temperature to obtain the basic glass. The obtained basic glass is heated to 710℃ in a muffle furnace at a heating rate of 10℃ / min and kept warm for 3h to obtain germanosilicate microcrystalline glass containing Li3AlF6 nanocrystals. The obtained microcrystalline glass is cut, ground and polished to make 10mm*10mm*1.5mm microcrystalline glass. Example

[0016] According to the composition: 40GeO2-15LiF-13LuF3-15Al2O3-7YF3-10La2O3 (mol%), weigh 20 grams of the required GeO2, LiF, LuF3, Al2O3, YF3, and La2O3 powder raw materials, 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, and place it in a 1400℃ silicon carbon rod electric furnace for melting for 30 minutes, then quickly pour the glass melt into a mold preheated at 450℃, and after the glass is formed, transfer it to a 400℃ muffle furnace for annealing for 4 hours, and naturally cool it to room temperature to obtain the basic glass. The obtained basic glass is heated to 690℃ in a muffle furnace at a heating rate of 10℃ / min and kept warm for 5h to obtain germanosilicate microcrystalline glass containing Li3AlF6 nanocrystals. The obtained microcrystalline glass is cut, ground and polished to make 10mm*10mm*1.5mm microcrystalline glass.

[0017] 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 Li3AlF6 nanocrystals, characterized in that: The molar percentage composition of the glass is: Raw material molar percentage (mol%) GeO2 40~45% LiF 10~15% LuF310~15% Al2O3 10~20% YF3 5~10% La2O3 10~15%.

2. A method for preparing germanate glass-ceramics from which Li3AlF6 nanocrystals are precipitated as claimed in claim 1, characterized in that The steps include: (1) Ingredients: GeO2, LiF, LuF3, Al2O3, 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. The melting temperature is 1400-1500°C and the melting time is 25-30 minutes. (3) Molding: Pour the molten glass into a mold preheated to 400-500°C for molding; (4) Annealing: Place the formed glass in a muffle furnace for annealing at a temperature of 400-500°C for 3-5 hours, then turn off the power of the muffle furnace and cool it to room temperature. (5) Heat treatment: Heat treatment is performed within the crystallization temperature range for several hours; (6) Polishing: The heat-treated glass is cut, ground, and polished to produce germanate glass-ceramics with Li3AlF6 nanocrystals precipitated.

3. The preparation method according to claim 2, characterized in that: The crystallization temperature in step (5) is 650-750°C.

4. The preparation method according to claim 2, characterized in that: In step (2), the melting temperature is 1450° C. and the melting time is preferably 30 minutes.

5. The preparation method according to claim 2, characterized in that: The preheating temperature in step (3) is 450°C.

6. The preparation method according to claim 2, characterized in that: In step (4), the annealing temperature is 450° C. and the annealing time is 4 hours.

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