CN109437572B - Precipitated BaTbF5Nanocrystalline germanosilicate microcrystalline glass and preparation method thereof - Google Patents

Abstract

The invention discloses a method for separating out BaTbF₅Nanocrystalline germanosilicate glass ceramics and a preparation method thereof. The microcrystalline glass comprises the following components in percentage by mole: GeO₂:20~40%、SiO₂:20~30%、Al₂O₃:5~10%、AlF₃:0~5%、Na₂CO₃:10~15%、TbF₃:3~10%、BaCO₃0 to 5% and BaF₂15 to 20 percent. The preparation method comprises the following steps: weighing a certain mass of raw materials according to the mol percentage in the range, fully grinding and uniformly mixing, and preparing the base glass by adopting a melting quenching method. Testing the thermal properties of the base glass by differential thermal analysis, heat treating the base glass in the crystallization temperature range for several hours to obtain a glass containing BaTbF₅Nanocrystalline germanosilicate glass-ceramics. The microcrystalline glass prepared by the invention has simple preparation method and higher transparency.

Description

Precipitated BaTbF5Nanocrystalline germanosilicate microcrystalline glass and preparation method thereof

Technical Field

The invention relates to the technical field of rare earth luminescent materials, in particular to a precipitated BaTbF₅Nanocrystalline germanosilicate glass ceramics and a preparation method thereof.

Background

The fluoride oxide microcrystalline glass is prepared by carrying out heat treatment on glass prepared from oxide and fluoride mixture at a certain temperature and time, and fluoride nano microcrystalline glass is controllably precipitated in the glass, and the glass matrix mainly comprises oxide. The fluoride oxide microcrystalline glass is a novel composite material with the advantages of both fluoride and oxide, and has better mechanical property, thermal stability and the like because the substrate is mainly oxide, and particularly, the physical and chemical properties of the glass are more stable because the glass is added with raw materials such as alumina and the like which enable the structure of the glass to be more compact. The oxyfluoride microcrystalline glass has the other advantage that an environment with low phonon energy can be provided for rare earth ions, the rare earth ions in the glass can be preferentially enriched in fluoride nano-crystalline grains with lower phonon energy, and the low phonon energy environment greatly reduces the non-radiative relaxation effect of the rare earth ions, so that the luminous efficiency of the glass is improved. Of course, the size of the fluoride nanocrystal is smaller than the wavelength of incident light, so that the oxyfluoride microcrystalline glass still maintains the characteristic of high transmittance of the original glass. It is these characteristics that the oxyfluoride microcrystalline glass has more excellent optical properties than glass and ceramics, the traditional glass and ceramics can not meet the requirements of modern industry and daily life, and the oxyfluoride microcrystalline glass also plays an important role in fields such as optical fiber amplifier, industrial detection, laser and display.

Due to Tb³⁺The energy level transition of (a) has two forms: one is that⁵D₄→⁷F_J(J = 0-6) transition between energy levels, and the fluorescence spectrum shows blue and violet light emission; the other is⁵D₃→⁷F_J(J = 0-6) transitions between energy levels, representing strong green emission. Therefore, Tb3+ is often used as a rare earth element for green light emission, and has wide application in white light LEDs and green fluorescent powder. In addition, Tb is excited by XRD rays³⁺The doped material also emits bright green light and its fluorescence emission matches the spectral sensitivity of the CCD, so Tb³⁺Are also commonly used as luminescent centers for scintillator materials. Tb³⁺Doped glass ceramics have Tb because of their lower phonon energy³⁺The luminescent efficiency is high, so the material is expected to become a novel green light emitting material and a microcrystalline glass scintillator material.

Disclosure of Invention

The invention aims to solve the technical problem of providing a BaTbF-containing material₅A novel fluorine oxygen germanium silicate microcrystalline glass of nano crystal and a preparation method thereof. The preparation process of the microcrystalline glass is simple, and the microcrystalline glass has high transparency. The specific technical scheme is as follows:

the germanium silicate microcrystalline glass for precipitating BaTbF5 nano crystals is prepared from the following raw materials in percentage by mole: GeO₂: 20~40%，SiO₂: 20~30%，Al₂O₃: 5~10%，AlF₃: 0~5%，Na₂O: 10~15%，TbF₃: 3~10%，BaCO₃: 0~5%，BaF₂: 15~20%。

Another object of the present invention is to provide a composition containing BaTbF₅The preparation method of the novel oxyfluoride germanosilicate microcrystal of the nanocrystalline specifically comprises the following steps:

1) preparing materials: with GeO₂，SiO₂，Al₂O₃，AlF₃，Na₂CO₃，TbF₃，BaCO₃And BaF₂Selecting the mol percentage of the glass composition as a glass composition raw material, weighing the raw material with corresponding mass, and grinding and mixing the raw material in a mortar uniformly;

2) melting: pouring the glass raw materials which are ground and mixed uniformly into a crucible, and putting the crucible into a silicon carbide rod electric furnace for melting, wherein the melting temperature is 1400-1550 ℃, and the melting time is 30-60 minutes;

3) molding: pouring the glass melt into a mold preheated to 450-550 ℃;

4) annealing: putting the formed glass into a muffle furnace for annealing at the temperature of 450-550 DEG C^oAnd C, annealing for 2-4 hours. Then, a power supply of the muffle furnace is closed and cooled to room temperature along with the furnace;

5) and (3) heat treatment: putting the annealed initial glass into a muffle furnace, and performing crystallization at a crystallization temperature range (600-750)^oC) Heat treatment for several hours;

6) polishing: and cutting, grinding and polishing the heat-treated glass to prepare the microcrystalline glass with the thickness of 10mm by 1.5 mm.

Drawings

Fig. 1 is an XRD pattern of the glass ceramics provided in example 2 of the present invention.

Detailed Description

The invention will be further explained with reference to the drawings.

Example 1:

according to the composition: 40GeO₂-15SiO₂-7Al₂O₃-3AlF₃-12Na₂CO₃-4TbF₃-19BaF₂(mol%) weighing the totalGeO required for a mass of 20 g₂、SiO₂、Al₂O₃、AlF₃、Na₂CO₃、TbF₃、BaF₂And (3) putting the powder raw materials into an agate mortar, fully grinding and uniformly mixing. Pouring the uniformly mixed glass raw materials into a crucible, covering a mullite cover, and placing at 1460^oMelting for 40 minutes in a C silicon carbide rod electric furnace, and then quickly pouring the glass melt into a preheating furnace of 450 DEG C^oC in the mold, after the glass is formed, the glass is turned into 550^oAnd C, annealing for 2 hours in a muffle furnace, and naturally cooling to room temperature to obtain the base glass. The base glass obtained is placed in a muffle furnace at 10^oThe temperature rise rate of C/min is increased to 600^oC, preserving the heat for 2 hours to obtain the product containing BaTbF₅Nanocrystalline germanosilicate glass-ceramics. And cutting, grinding and polishing the obtained glass ceramics to prepare the glass ceramics with the thickness of 10mm by 1.5 mm.

Example 2:

according to the composition: 35GeO₂-20SiO₂-7Al₂O₃-15Na₂CO₃-4TbF₃-5BaCO₃-14BaF₂(mol%) the GeO required was weighed so that the total mass was 20 g₂、SiO₂、Al₂O₃、Na₂CO₃、TbF₃、BaCO₃、BaF₂And (3) putting the powder raw materials into an agate mortar, fully grinding and uniformly mixing. Pouring the uniformly mixed glass raw materials into a crucible, covering a mullite cover, and placing 1480^oMelting for 50 minutes in a C silicon carbide rod electric furnace, and then quickly pouring the glass melt into a preheating 480^oC in the mold, after the glass is formed, the glass is turned into 550^oAnd C, annealing for 2 hours in a muffle furnace, and naturally cooling to room temperature to obtain the base glass. The base glass obtained is placed in a muffle furnace at 10^oThe temperature rise rate of C/min is increased to 610^oC, preserving the heat for 2 hours to obtain the product containing BaTbF₅Nanocrystalline germanosilicate glass-ceramics. The obtained glass ceramics are cut, ground and polished to be made into 10mm 1.5 mm.

In this embodiment, a composition containing BaTbF₅XRD of nanocrystalline germanosilicate glass ceramics is shown in figure 1。

Example 3:

according to the composition: 30GeO₂-25SiO₂-10Al₂O₃-10Na₂CO₃-5TbF₃-5BaCO₃-15BaF₂(mol%) the GeO required was weighed so that the total mass was 20 g₂、SiO₂、Al₂O₃、Na₂CO₃、TbF₃、BaCO₃、BaF₂And (3) putting the powder raw materials into an agate mortar, fully grinding and uniformly mixing. Pouring the uniformly mixed glass raw materials into a crucible, covering a mullite cover, and placing the crucible at 1500 DEG C^oMelting in a silicon carbide rod electric furnace for 60 minutes, then quickly pouring the glass melt into a mold preheated to 500 ℃, and transferring into 550 after glass is formed^oAnd C, annealing for 3 hours in a muffle furnace, and naturally cooling to room temperature to obtain the base glass. The base glass obtained is placed in a muffle furnace at 10^oThe temperature rise rate of C/min is increased to 640^oC, preserving the heat for 2 hours to obtain the product containing BaTbF₅Nanocrystalline germanosilicate glass-ceramics. And cutting, grinding and polishing the obtained glass ceramics to prepare the glass ceramics with the thickness of 10mm by 1.5 mm.

Example 4:

according to the composition: 25GeO₂-28SiO₂-5Al₂O₃-5AlF₃-13Na₂CO₃-7TbF₃-2BaCO₃-15BaF₂(mol%) the GeO required was weighed so that the total mass was 20 g₂、SiO₂、Al₂O₃、AlF3、Na₂CO₃、TbF₃、BaCO₃、BaF₂And (3) putting the powder raw materials into an agate mortar, fully grinding and uniformly mixing. Pouring the uniformly mixed glass raw materials into a crucible, covering the crucible with a mullite cover, and placing the crucible on an 1520^oMelting for 60 minutes in a C silicon carbide rod electric furnace, and then rapidly pouring the glass melt into a preheating furnace 500^oC in the mold, after the glass is formed, the glass is turned into 550^oAnd C, annealing for 3 hours in a muffle furnace, and naturally cooling to room temperature to obtain the base glass. The base glass obtained is placed in a muffle furnace at 10^oThe temperature rise rate of C/min is increased to 660^oC and heat preservation2h to obtain a product containing BaTbF₅Nanocrystalline germanosilicate glass-ceramics. And cutting, grinding and polishing the obtained glass ceramics to prepare the glass ceramics with the thickness of 10mm by 1.5 mm.

The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the appended claims.

Claims (2)

1. Precipitated BaTbF₅The nanocrystalline germanosilicate glass ceramics are characterized by comprising the following raw materials in percentage by mol:

the component mol%

GeO₂ 20~40%

SiO₂ 20~30%

Al₂O₃ 5~10%

AlF₃ 0~5%

Na₂CO₃ 10~15%

TbF₃ 3~10%

BaCO₃ 0~5%

BaF₂ 15~20%。

2. Precipitated BaTbF according to claim 1₅The preparation method of the nanocrystalline germanosilicate glass ceramics is characterized by comprising the following steps:

1) preparing materials: with GeO₂，SiO₂，Al₂O₃，AlF₃，Na₂CO₃，TbF₃，BaCO₃And BaF₂Weighing raw materials with corresponding mass according to the selected mol percentage of the glass composition, grinding and mixing the raw materials in a mortarMixing uniformly;

2) melting: pouring the glass raw material which is ground and mixed uniformly into a crucible, and putting the crucible into a silicon carbide rod electric furnace for melting, wherein the melting temperature is 1450-1550 DEG C^oC, melting time is 30-60 minutes;

3) molding: pouring the glass melt into a preheating furnace with the temperature of 450-550 DEG C^oC in the mold;

4) annealing: putting the formed glass into a muffle furnace for annealing at the temperature of 450-550 DEG C^oC, annealing for 2-4 hours, and then closing a power supply of the muffle furnace to cool to room temperature along with the furnace;

5) and (3) heat treatment: at a crystallization temperature of 600 to 700 deg.C^oC, carrying out heat treatment for several hours in the range of C;

6) polishing: and cutting, grinding and polishing the heat-treated glass to prepare the microcrystalline glass with the thickness of 10mm by 1.5 mm.

Images