CN114455842B - Precipitation of Bi 2 GeO 5 Nanocrystalline high-density bismuth germanate microcrystalline glass and preparation method thereof - Google Patents
Precipitation of Bi 2 GeO 5 Nanocrystalline high-density bismuth germanate microcrystalline glass and preparation method thereof Download PDFInfo
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- CN114455842B CN114455842B CN202210058244.XA CN202210058244A CN114455842B CN 114455842 B CN114455842 B CN 114455842B CN 202210058244 A CN202210058244 A CN 202210058244A CN 114455842 B CN114455842 B CN 114455842B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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Abstract
The invention discloses a method for separating out Bi 2 GeO 5 Nanocrystalline high-density bismuth germanate microcrystalline glass and a preparation method thereof. The microcrystalline glass comprises the following raw materials in percentage by mole: geO (GeO) 2 :60~40%、Bi 2 O 3 :45~25%、Ga 2 O 3 :15~0%、Na 2 CO 3 :15~10%、Al 2 O 3 15-0%. The preparation method of the microcrystalline glass comprises the following steps: the raw materials with certain mass are weighed according to the mole percentage, fully ground and uniformly mixed, and the precursor glass is prepared by adopting a melt quenching method. Analyzing the thermal properties of glass by differential heat, and performing heat treatment in a crystallization temperature range for several hours to obtain Bi-containing glass 2 GeO 5 Nanocrystalline high-density bismuth germanate microcrystalline glass with density up to 6.2g/cm 3 . The microcrystalline glass prepared by the method is simple in preparation method and still has high transparency.
Description
Technical Field
The invention relates to the technical field of rare earth luminescent materials, in particular to a method for separating out Bi 2 GeO 5 Nanocrystalline high-density bismuth germanate microcrystalline glass and a preparation method thereof.
Background
Glass ceramics are ceramic-like materials obtained by heat treatment crystallization of glass. The microcrystalline glass is different from common glass and ceramics, and consists of most glass matrixes and a small amount of precipitated tiny grains, and the size of the grains is generally required to be smaller than 1 mu m, so that most microcrystalline glass is still transparent and keeps higher transmittance after being watched from outside. For rare earth doped microcrystalline glass, rare earth ions are preferentially selected and enriched in a crystalline phase with a low phonon energy environment, so that the luminous performance of the glass is greatly enhanced, and a new thought is provided for improving the light yield of the glass. The oxide glass ceramic system is the glass ceramic system which is studied at the earliest time, has a plurality of excellent characteristics such as good mechanical processing performance, chemical stability, thermal stability and the like, and is widely applied.
The bismuth germanate glass has higher density, excellent anti-radiation performance and potential application value in the field of high-energy physics. In addition, the bismuthate glass has low phonon energy, high near infrared band transmittance, good chemical stability, easy processing and potential application value in the optical field, and is an ideal rare earth ion doped luminescent material. The microcrystalline phase is precipitated in bismuth germanate glass, and the bismuth germanate glass is expected to be a near infrared luminescent material with excellent performance.
Disclosure of Invention
In order to solve the technical problems existing in the prior art, the invention aims to provide a method for separating out Bi 2 GeO 5 Nanocrystalline high-density bismuth germanate microcrystalline glass and a preparation method thereof.
Precipitation of Bi 2 GeO 5 The nanocrystalline bismuth germanate microcrystalline glass is prepared from the following raw materials in percentage by mole: geO (GeO) 2 : 60~40%、Bi 2 O 3 : 45~25%、Ga 2 O 3 : 15~0%、Na 2 CO 3 : 15~10%、Al 2 O 3 : 15~0%。
Another object of the present invention is to provide a method for separating Bi out 2 GeO 5 The preparation method of the nanocrystalline high-density bismuth germanate microcrystal specifically comprises the following steps:
1) And (3) batching: the method comprises the steps of weighing raw materials with corresponding mass according to mole percentages of the glass composition by using Ge-containing compounds and/or salts, bi-containing compounds and/or salts, na-containing compounds and/or salts and Ga-containing compounds and salts, and grinding and mixing uniformly in a mortar;
2) Melting: pouring the uniformly ground and mixed glass raw materials into a crucible, and putting the crucible into a silicon carbide rod electric furnace for melting, wherein the melting temperature is 1000-1100 ℃, and the melting time is 30-50 minutes;
3) And (3) forming: pouring the glass melt into a cast iron mold preheated to 450-550 ℃;
4) Annealing: the formed glass is put into a muffle furnace for annealing at the annealing temperature of 350-420 DEG C o And C, annealing for 2-4 hours. Then closing a muffle furnace power supply, and cooling to room temperature along with the furnace;
5) And (3) heat treatment: placing the annealed initial glass into a muffle furnace, and crystallizing at a certain temperatureWithin the range (500-700) o C) Heat treatment for several hours;
5) Polishing: cutting, grinding and polishing the glass after heat treatment to obtain the microcrystalline glass.
Precipitation of Bi according to the present invention 2 GeO 5 The nanocrystalline high-density bismuth germanate microcrystalline glass has high density, simple preparation process and high transparency.
Drawings
Fig. 1 is an XRD of bismuth germanate glass ceramics provided in example 1 of the present invention.
Description of the embodiments
The invention is further described below with reference to the accompanying drawings.
The glass compositions of 4 specific examples of the high-density bismuth germanate glass ceramics of the present invention are shown in Table 1:
table 1: specific 4 examples glass formulations
Example 1:
the composition is as follows: 40GeO 2 -40Bi 2 O 3 -12Na 2 CO 3 -8 Al 2 O 3 (mol%) GeO was weighed out to give a total mass of 20 g 2 、Bi 2 O 3 、Na 2 CO 3 、Ga 2 O 3 The powder raw materials are put into an agate mortar to be fully ground and uniformly mixed. Pouring the uniformly mixed glass raw materials into a crucible, covering a mullite cover, and placing the crucible into 1100 o C, melting in a silicon carbide rod electric furnace for 35 minutes, and then rapidly pouring glass melt into a preheating 380 o C, after the glass is formed, turning into 410 o Annealing in a muffle furnace for 2 hours, and naturally cooling to room temperature to obtain the initial glass. The initial glass obtained was heated in a muffle furnace at a temperature of 10 o The temperature rise rate of C/min is increased to 560 o C and preserving heat for 3 hours to obtain the Bi-containing alloy 2 GeO 5 Nanocrystalline high-density bismuth germanate microcrystalline glass. Cutting, grinding and polishing the obtained glass ceramics to obtain the glass ceramics.
In this example, the precipitate Bi 2 GeO 5 XRD of the nanocrystalline bismuth germanate microcrystalline glass is shown in figure 1.
Example 2:
the composition is as follows: 45GeO 2 -35Bi 2 O 3 -10Na 2 CO 3 -10Ga 2 O 3 (mol%) GeO was weighed out to give a total mass of 20 g 2 、Bi 2 O 3 、Na 2 CO 3 、Ga 2 O 3 The powder raw materials are put into an agate mortar to be fully ground and uniformly mixed. Pouring the uniformly mixed glass raw materials into a crucible, covering a mullite cover, and placing the crucible into 1100 o C, melting in a silicon carbide rod electric furnace for 35 minutes, and then rapidly pouring glass melt into a preheating 390 o C, in the cast iron mould, turning into 400 after the glass is formed o Annealing in a muffle furnace for 3 hours, and naturally cooling to room temperature to obtain the initial glass. The initial glass obtained was heated in a muffle furnace at a temperature of 10 o The temperature rise rate of C/min rises to 570 o C, and preserving heat for 2 hours to obtain the Bi-containing alloy 2 GeO 5 Nanocrystalline high-density bismuth germanate microcrystalline glass. Cutting, grinding and polishing the obtained glass ceramics to obtain the glass ceramics.
Example 3:
the composition is as follows: 40GeO 2 -35Bi 2 O 3 -15Na 2 CO 3 -10Ga 2 O 3 (mol%) GeO was weighed out to give a total mass of 20 g 2 、Bi 2 O 3 、Na 2 CO 3 、Ga 2 O 3 The powder raw materials are put into an agate mortar to be fully ground and uniformly mixed. Pouring the uniformly mixed glass raw materials into a crucible, covering a mullite cover, and placing 1050 o C, melting in a silicon carbide rod electric furnace for 40 minutes, then rapidly pouring glass melt into a cast iron mold preheated to 380 ℃, and turning into 400 after glass is formed o Annealing in a muffle furnace for 3 hours, and naturally cooling to room temperature to obtain the initial glass. The initial glass obtained was heated in a muffle furnace at a temperature of 10 o The temperature rise rate of C/min is increased to 560 o C and preserving heat for 5h to obtain the Bi-containing alloy 2 GeO 5 Nanocrystalline high-density bismuth germanate microcrystalline glass. Cutting, grinding and polishing the obtained glass ceramics to obtain the glass ceramics.
Example 4:
the composition is as follows: 50GeO 2 -30Bi 2 O 3 -10Na 2 CO 3 -10Al 2 O 3 (mol%) GeO was weighed out to give a total mass of 20 g 2 、Bi 2 O 3 、Na 2 CO 3 、Ga 2 O 3 The powder raw materials are put into an agate mortar to be fully ground and uniformly mixed. Pouring the uniformly mixed glass raw materials into a crucible, covering a mullite cover, and setting the glass raw materials at 1000 o C, melting in a silicon carbide rod electric furnace for 40 minutes, and then rapidly pouring glass melt into a preheating 380 o C, after the glass is formed, turning into 390 o Annealing in a muffle furnace for 3 hours, and naturally cooling to room temperature to obtain the initial glass. The initial glass obtained was heated in a muffle furnace at a temperature of 10 o The temperature rise rate of C/min rises to 570 o C, and preserving heat for 2 hours to obtain the Bi-containing alloy 2 GeO 5 Nanocrystalline high-density bismuth germanate microcrystalline glass. Cutting, grinding and polishing the obtained glass ceramics to obtain the glass ceramics.
The above-described embodiments are intended to illustrate the present invention, not to limit it, and any modifications and variations made thereto are within the spirit of the invention and the scope of the appended claims.
Claims (2)
1. Precipitation of Bi 2 GeO 5 Preparation method of nanocrystalline high-density bismuth germanate microcrystalline glass, wherein Bi is separated out 2 GeO 5 The high-density bismuth germanate microcrystalline glass of the nanocrystalline comprises the following raw materials in percentage by mole:
GeO 2 : 40~50%
Bi 2 O 3 : 35~45%
Ga 2 O 3 : 0~10%
Na 2 CO 3 : 12~15%
Al 2 O 3 : 8~10%；
the sum of the mole percentages of the components of the raw materials is 100 percent;
the method is characterized by comprising the following steps of:
and (3) batching: by GeO 2 ，Bi 2 O 3 ，Ga 2 O 3 ，Na 2 CO 3 ，Al 2 O 3 Weighing raw materials with corresponding mass according to the mole percentage of the raw materials, and grinding and mixing uniformly in a mortar;
melting: pouring the glass raw materials which are ground and mixed uniformly into a crucible, and putting into a silicon carbide rod electric furnace for melting, wherein the melting temperature is 1000-1100 DEG C o C, melting time is 20-40 minutes;
and (3) forming: pouring the glass melt into a preheating furnace for 350-400 ℃ to be preheated o C, casting the cast iron mold;
annealing: the formed glass is put into a muffle furnace for annealing at the annealing temperature of 350-420 DEG C o C, annealing for 2-4 hours, then closing a muffle furnace power supply, and cooling to room temperature along with the furnace;
and (3) heat treatment: performing heat treatment for several hours in a crystallization temperature range;
polishing: cutting, grinding and polishing the glass after heat treatment to obtain the microcrystalline glass.
2. The method of manufacturing according to claim 1, wherein: the crystallization temperature range is 500-700 DEG C o C。
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| DE102005052090B4 (en) * | 2005-10-28 | 2014-06-26 | Schott Ag | Lead- and arsenic-free refractive optical glass, its use and method of making an optical element |
| CN102674690A (en) * | 2012-05-31 | 2012-09-19 | 中国科学院上海光学精密机械研究所 | 3 mu m rare earth ion doped bismuth-germinate laser glass and preparation method thereof |
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| RU2636090C1 (en) * | 2017-03-31 | 2017-11-20 | Федеральное государственное автономное образовательное учреждение высшего образования "Сибирский федеральный университет" | METHOD OF PRODUCING BISMUTH GERMANATE Bi2GeO5 |
| CN108585482A (en) * | 2018-05-08 | 2018-09-28 | 上海应用技术大学 | A kind of white light LEDs fluorescent glass piece and preparation method thereof |
| RU2687924C1 (en) * | 2018-06-26 | 2019-05-16 | Федеральное государственное автономное образовательное учреждение высшего образования "Сибирский федеральный университет" | METHOD FOR PRODUCING BISMUTH GERMANATE Bi2Ge3O9 |
| CN109369024B (en) * | 2018-12-20 | 2021-04-27 | 中国计量大学 | Precipitated BaEuF5Nanocrystalline germanosilicate microcrystalline glass and preparation method thereof |
| RU2724760C1 (en) * | 2020-02-06 | 2020-06-25 | Федеральное государственное автономное образовательное учреждение высшего образования "Сибирский федеральный университет" | Bismuth germanate-silicate production method |
| CN111533457A (en) * | 2020-04-30 | 2020-08-14 | 华南理工大学 | Bi with continuous and tunable ferroelectric property2GeO5Ferroelectric glass ceramics and preparation method thereof |
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