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

Abstract

The invention discloses germanate microcrystalline glass for separating out KF 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 KF, 5 to 10 percent of K2CO3, 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 1500-1600 DEG C, and keeping the temperature for 30-60 minutes; pouring the glass melt into a mold, putting the mold into an annealing furnace, carrying out annealing heat preservation at the temperature below the glass transition temperature 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 germanate microcrystalline glass in which the KF 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 KF 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 provides a germanate microcrystalline glass with precipitated KF 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 KF nanocrystals in the glass. The specific technical scheme is as follows: A germanate glass-ceramic with precipitated KF nanocrystals, the glass having a molar percentage composition of: Raw material molar percentage (mol%) GeO2 40~50% KF 10~15% K2CO3 10~15% H3BO3 10~20% YF3 5~10% La2O3 10~15%.

[0006] A method for preparing germanate glass-ceramics from which KF nanocrystals are precipitated comprises the following steps: (1) Ingredients: GeO2, KF, K2CO3, 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. The melting temperature is 1400-1600 degrees Celsius and the melting time is 30-60 minutes. (3) Molding: Pour the molten glass into a mold preheated to 500-600 degrees Celsius for molding; (4) Annealing: The formed glass is placed in a muffle furnace for annealing at a temperature of 500-600 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 for several hours; (6) Polishing: The heat-treated glass is cut, ground, and polished to produce germanate glass-ceramics with KF nanocrystals precipitated.

[0007] Furthermore, the crystallization temperature in step (5) is 700-800 degrees.

[0008] Furthermore, in step (2), the melting temperature is 1550 degrees Celsius, and the melting time is preferably 45 minutes.

[0009] Furthermore, in step (4), the annealing temperature is 550 degrees Celsius and the annealing time is 4 hours.

[0010] The germanate glass-ceramics from which KF nanocrystals are precipitated has excellent mechanical strength and thermal stability, and can be used to prepare volume Bragg gratings (VBGs) based on photothermorefractive (PTR) glass, and further applied to laser system design, three-dimensional display and imaging, and optical communication. The method can controllably precipitate KF nanocrystals in germanate glass. 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 1 is the XRD diagram of the base glass and the microcrystalline glass in Example 1 of the present invention. DETAILED DESCRIPTION

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

[0014] According to the composition: 40GeO2-15KF-10K2CO3-15H3BO3-5YF3-15La2O3 (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 45 minutes, then quickly pour the glass melt into a mold preheated at 550℃, and after the glass is formed, transfer it to a 500℃ 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 720℃ in a muffle furnace at a heating rate of 10℃ / min and kept warm for 5h to obtain germanosilicate microcrystalline glass containing KF nanocrystals. The obtained microcrystalline glass is cut, ground and polished to make 10mm*10mm*1.5mm microcrystalline glass. Example

[0015] According to the composition: 45GeO2-12KF-13K2CO3-10H3BO3-5YF3-15La2O3 (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 silicon carbon rod electric furnace at 1550℃ for 30 minutes, then quickly pour the glass melt into a mold preheated at 600℃, and after the glass is formed, transfer it to a muffle furnace at 550℃ for annealing for 4 hours, and naturally cool it to room temperature to obtain the basic glass. The obtained basic glass is heated to 730℃ in a muffle furnace at a heating rate of 10℃ / min and kept warm for 5h to obtain germanosilicate microcrystalline glass containing KF nanocrystals. The obtained microcrystalline glass is cut, ground and polished to make 10mm*10mm*1.5mm microcrystalline glass. Example

[0016] According to the composition: 45GeO2-12KF-10K2CO3-15H3BO3-6YF3-12La2O3 (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 silicon carbon rod electric furnace at 1480℃ for 45 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 600℃ for annealing for 4 hours, and naturally cool it to room temperature to obtain the basic glass. The obtained basic glass is heated to 720℃ in a muffle furnace at a heating rate of 10℃ / min and kept warm for 5h to obtain germanosilicate microcrystalline glass containing KF 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 precipitated KF nanocrystals, characterized in that: The molar percentage composition of the glass is: Raw material molar percentage (mol%) GeO2 40~50% KF 10~15% K2CO3 10~15% H3BO3 10~20% YF3 5~10% La2O3 10~15%.

2. A method for preparing germanate glass-ceramics with precipitated KF nanocrystals as claimed in claim 1, characterized in that The steps include: (1) Ingredients: GeO2, KF, K2CO3, 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. The melting temperature is 1400-1600 degrees Celsius and the melting time is 30-60 minutes. (3) Molding: Pour the molten glass into a mold preheated to 500-600 degrees Celsius for molding; (4) Annealing: The formed glass is placed in a muffle furnace for annealing at a temperature of 500-600 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 for several hours; (6) Polishing: The heat-treated glass is cut, ground, and polished to produce germanate glass-ceramics with KF nanocrystals precipitated.

3. The preparation method according to claim 2, characterized in that: The crystallization temperature in step (5) is 700-800 degrees.

4. The preparation method according to claim 2, characterized in that: In step (2), the melting temperature is 1550 degrees Celsius, and the melting time is preferably 45 minutes.

5. The preparation method according to claim 2, characterized in that: In step (4), the annealing temperature is 550 degrees Celsius and the annealing time is 4 hours.

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