阅读说明：本技术 一种抗γ射线辐照暗化的锗酸盐玻璃及其制备方法与应用 (Gamma-ray irradiation darkening resistant germanate glass and preparation method and application thereof ) 是由 钱奇 刘桂榕 杨中民 于 2021-03-26 设计创作，主要内容包括：本发明公开了一种抗γ射线辐照暗化的锗酸盐玻璃及其制备方法与应用。所述抗γ射线辐照暗化的锗酸盐玻璃包括如下成份：BaO15～25wt％,Ga-2O-320～30wt％,Ln-xO-y1～5wt％,及GeO-2余量；其中,Ln-xO-y为可变价离子的氧化物,Ln为Nb、Ce或Sb其中的一种。通过在锗酸盐玻璃掺杂合适的可变价离子,包括铌离子、铈离子或锑离子,显著减少γ射线辐照玻璃诱导的玻璃结构缺陷,从而降低了锗酸盐玻璃的光吸收损耗。利用掺杂了这些可变价离子的锗酸盐玻璃制备激光器,可提高激光器的稳定性和使用寿命,使激光器适用于在太空或其它具有γ射线辐照的恶劣环境下工作。(The invention discloses a germanate glass capable of resisting gamma-ray irradiation darkening, and a preparation method and application thereof. The germanate glass capable of resisting gamma ray irradiation darkening comprises the following components: BaO 15-25 wt%, Ga 2 O 3 20～30wt％，Ln x O y 1 to 5 wt%, and GeO 2 The balance; wherein Ln x O y Is an oxide of variable valence ions, and Ln is one of Nb, Ce or Sb. By doping the germanate glass with suitable variable valence ions, including niobium ions, cerium ions or antimony ions, the glass structure defects induced by gamma-ray irradiation of the glass are obviously reduced, so that the light absorption loss of the germanate glass is reduced. The germanate glass doped with the variable valence ions is used for preparing the laser, so that the stability and the service life of the laser can be improved, and the laser is suitable for working in space or other severe environments with gamma ray irradiation.)

1. The germanate glass capable of resisting gamma ray irradiation darkening is characterized by comprising the following components:

BaO 15～25wt％，

Ga₂O₃ 20～30wt％，

Ln_xO_y1 to 5 wt%, and

GeO₂the balance;

wherein Ln_xO_yIs an oxide of variable valence ions, and Ln is one of Nb, Ce or Sb.

2. The method of making a germanate glass that is resistant to darkening by gamma irradiation of claim 1 comprising the steps of:

grinding raw material oxides, melting the raw material oxides into glass liquid, clarifying the glass liquid, transferring the glass liquid onto a glass steel plate, cooling and forming, and then annealing to obtain the gamma-ray irradiation darkening resistant germanate glass.

3. The method of claim 2, wherein the milling time is 10-30 min.

4. The method according to claim 2, wherein the melting temperature is 1300 to 1500 ℃.

5. The method according to claim 2, wherein the melting time is 1 to 3 hours.

6. The production method according to any one of claims 2 to 5, wherein the annealing is performed in an annealing furnace.

7. The preparation method according to claim 6, characterized in that the annealing is specifically: firstly, preserving heat for 1-3 h at 570-670 ℃, and then cooling to room temperature along with an annealing furnace.

8. Use of the germanate glass resistant to darkening by gamma irradiation of claim 1 in the manufacture of a laser.

9. The application of claim 8, wherein the laser is a 1.5-2 μm band fiber laser.

10. Use according to claim 8 or 9, wherein the fibre laser is used in space or other harsh environments with gamma irradiation.

Technical Field

The invention belongs to the field of glass optical fibers, and particularly relates to a germanate glass capable of resisting gamma-ray irradiation darkening, and a preparation method and application thereof.

Background

The germanate glass has lower phonon energy, high rare earth ion solubility, high laser damage resistance threshold and excellent chemical and mechanical properties, and is a very important matrix material for the mid-infrared fiber laser. However, when the germanate glass fiber laser is used in a high-energy ray irradiation environment, for example, in space applications and high-energy ray irradiation conditions, the high-energy rays cause a phenomenon in which the transmittance of the germanate glass fiber is reduced, and this phenomenon is also referred to as a darkening effect. This darkening effect causes optical absorption losses in the glass fibers and reduces the stability and lifetime of these fiber lasers.

It is known that certain metal ions, such as iron, manganese or chromium, doped into glass optical fibers may form new color centers, thereby inducing additional absorption loss by the optical fibers and making the optical fibers less resistant to high-energy radiation. However, not all metal ion doping can degrade the radiation resistance of the glass fiber. Some multi-valence metal ions can absorb charges and holes generated by high-energy ray induction through valence conversion, so that the formation of irradiation-induced color center defects is inhibited, and the irradiation resistance of the glass optical fiber is improved. Through years of research, it has been found that variable metal ions, including cerium, strontium, niobium and antimony, can enhance Yb³⁺And/or Er³⁺The radiation resistance of doped silicate and phosphate glasses for 1.0 μm and 1.5 μm fiber lasers. However, Tm is rarely studied³⁺The radiation resistance of doped germanate glass for 2.0 micron fiber laser.

Tm³⁺The doped germanate glass can be used for a 2.0 mu m optical fiber laser and has important application value in many fields such as laser radar, laser detection, laser medical treatment, environmental monitoring and the like. However, when a germanate glass-based narrow linewidth single frequency fiber laser is applied to space or other harsh environments with gamma irradiation, a darkening effect is easily generated, thereby deteriorating device performance and service life. Accordingly, there is a need for germanate glasses that are resistant to darkening by gamma irradiation and methods for making the same.

The Chinese patent application with publication number CN112094052A discloses a radiation-resistant quartz optical fiber preform core rod and a preparation method thereof, which can effectively improve the radiation resistance of core rod glass by sequentially carrying out deuterium loading, pre-radiation and thermal annealing pretreatment on the preform core rod. There are the following disadvantages: 1. the treatment process of the preform is complex and is easy to cause other problems; 2. the thermal annealing pretreatment requires a high temperature, so some glass optical fiber materials that are not heat-resistant cannot be subjected to the treatment process.

Disclosure of Invention

In order to overcome the defects and shortcomings of the prior art, the invention aims to provide the germanate glass capable of resisting gamma ray irradiation darkening and the preparation method thereof, and provides a key glass matrix material for the application of a 1.5-2 mu m wave band optical fiber laser in space and other severe environments with gamma ray irradiation.

When gamma-ray is irradiated with BaO-Ga₂O₃-GeO₂When the germanate glass is used as a basic component, free electrons and holes can be generated, even the chemical bonds are broken, and the defects of the glass structure can be generated, so that the transmittance of the germanate glass is reduced, and the absorption loss is generated; variable valence ions are doped in the germanate glass, and free electrons and holes can be continuously captured by utilizing the valence conversion process of the variable valence ions, so that the generation of structural defects of the glass is inhibited, and the absorption loss is reduced. The germanate glass is used for preparing the laser, so that the gamma ray irradiation darkening resistance of the laser can be improved, the stability of the laser is improved, and the service life of the laser is prolonged.

The purpose of the invention is realized by the following technical scheme:

the germanate glass capable of resisting gamma ray irradiation darkening comprises the following components:

BaO 15～25wt％，

Ga₂O₃ 20～30wt％，

Ln_xO_y1 to 5 wt%, and

GeO₂the balance;

wherein Ln_xO_yIs an oxide of variable valence ions, and Ln is one of Nb, Ce or Sb.

Preferably, the germanate glass capable of resisting darkening by gamma ray irradiation comprises the following components:

BaO 18wt％，

Ga₂O₃ 20wt％，

Ln_xO_y2 wt%, and

GeO₂and (4) the balance.

The preparation method of the germanate glass capable of resisting gamma ray irradiation darkening comprises the following steps:

grinding raw material oxides, melting the raw material oxides into glass liquid, clarifying the glass liquid, transferring the glass liquid onto a glass steel plate, cooling and forming, and then annealing to obtain the gamma-ray irradiation darkening resistant germanate glass.

Preferably, the grinding time is 10-30 min.

Preferably, the melting temperature is 1300-1500 ℃.

Preferably, the melting time is 1-3 h.

Preferably, the annealing is performed in an annealing furnace.

Further preferably, the annealing specifically comprises: firstly, preserving heat for 1-3 h at 570-670 ℃, and then cooling to room temperature along with an annealing furnace.

The germanate glass capable of resisting gamma ray irradiation darkening is applied to the preparation of lasers.

Preferably, the laser is a fiber laser with a wave band of 1.5-2 μm.

Preferably, the fiber laser can be used in space or other harsh environments with gamma ray irradiation.

The principle of the invention is as follows:

glass fibers, when irradiated with gamma radiation, produce bond breakage and the formation of free electrons and holes that, when combined with defects found in the glass itself, form color center defects. These color center defects can cause the transmittance of the glass fiber to be reduced and optical absorption losses to occur, thereby seriously affecting the stability and lifetime of the laser device. Proper variable valence ions are doped in the germanate glass, and valence conversion of the variable valence ions is utilized to absorb electrons and holes generated in the irradiation process so as to inhibit the formation of the color center defects, thereby improving the service stability and the service life of the fiber laser.

Compared with the prior art, the invention has the following remarkable beneficial effects:

(1) compared with the multicomponent germanate glass which is not doped with variable valence ions, the multicomponent germanate glass doped with variable valence ions prepared by the method has the advantages of small absorption loss and better radiation darkening resistance, and meanwhile, the germanate glass has good optical performance, mechanical processing performance (optical fiber perform can be prepared by adopting mechanical cold processing) and other performances;

(2) the variable valence ion doped multi-component germanate glass prepared by the invention can be used in space and other severe environments with gamma ray irradiation;

(3) according to the invention, the components of the multi-component germanate glass are designed, so that the internal structure defects of the glass network are regulated and controlled, the germanate glass with good irradiation resistance is finally obtained, and an idea is provided for improving irradiation darkening resistance of other types of glass.

Drawings

FIG. 1(a) is an absorption spectrum of a comparative germanate glass;

FIG. 1(b) is an EPR diagram of a comparative germanate glass;

FIG. 2(a) shows Nb doping in example 1⁵⁺The absorption spectrum of the germanate glass;

FIG. 2(b) shows Nb doping in example 1⁵⁺EPR map of the germanate glass of (a);

FIG. 3(a) is example 2 Ce-doping⁴⁺The absorption spectrum of the germanate glass;

FIG. 3(b) is example 2 Ce-doping⁴⁺EPR map of the germanate glass of (a);

FIG. 4(a) is Sb doping of example 3³⁺Germanate glassAbsorption spectrogram of glass;

FIG. 4(b) is Sb doping in EXAMPLE 3³⁺EPR map of the germanate glass of (a);

FIG. 5(a) shows Nb doping in example 4⁵⁺(4 wt%) absorption spectrum of germanate glass;

FIG. 5(b) shows Nb doping in example 4⁵⁺EPR profile of germanate glass (4 wt%).

Detailed Description

Specific examples of the present invention are further illustrated below with reference to examples, but the practice and protection of the present invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.

Comparative example

Preparation of undoped germanate glasses

The oxide composition of the undoped germanate glass is as follows:

BaO 18wt％，

Ga₂O₃20 wt%, and

GeO₂the balance;

weighing the oxides (the purity is more than or equal to 99.99 percent) according to the formula, transferring the oxides into an alumina crucible after fully and uniformly mixing to form a mixture, placing the mixture into a high-temperature well type furnace at 1400 ℃ for melting for 2h to obtain molten glass liquid, pouring the molten glass liquid onto a glass steel plate after the glass liquid is clarified for cooling and forming, then placing the glass into an annealing furnace which is heated to a temperature slightly lower than the glass transition temperature of the glass, preserving the heat at 620 ℃ for 2h, and then cooling the glass to room temperature along with the furnace.

The annealed sample was processed into a 20mmx20mmx2mm glass sheet and polished on both sides, and after polishing, it was irradiated with gamma rays at a dose of 50KGy, and then subjected to absorption spectroscopy and EPR test, as shown in fig. 1(a), (b) and. Undoped germanate glass exhibits significant absorption loss after irradiation and color center defects.

Example 1

By variable valence metal ions Nb⁵⁺(2 wt%) doped multicomponent germanate glass usingThe valence state conversion of the germanate glass absorbs free electrons and holes induced in the irradiation process, and inhibits the formation of irradiation-induced color center defects, thereby reducing the light absorption loss of the germanate glass and enhancing the stability of the laser taking the germanate glass as a matrix. Meanwhile, the variable valence ion doped multi-component germanate glass is ensured to have good optical performance, mechanical processing performance (mechanical cold processing can be adopted to prepare an optical fiber preform) and other performances.

Specifically, the oxide composition of the variable valence ion doped multicomponent germanate glass is as follows:

BaO 18wt％，

Ga₂O₃ 20wt％，

Nb₂O₅2 wt%, and

GeO₂the balance;

weighing the oxides (the purity is more than or equal to 99.99 percent) according to the formula, transferring the oxides into an alumina crucible after fully and uniformly mixing to form a mixture, placing the mixture into a high-temperature well type furnace at 1400 ℃ for melting for 2h to obtain molten glass liquid, pouring the molten glass liquid onto a glass steel plate after the glass liquid is clarified for cooling and forming, then placing the glass into an annealing furnace which is heated to a temperature slightly lower than the glass transition temperature of the glass, preserving the heat at 620 ℃ for 2h, and then cooling the glass to room temperature along with the furnace.

The annealed sample was processed into a 20mmx20mmx2mm glass sheet and polished on both sides, and after polishing, it was irradiated with gamma rays at a dose of 50KGy, and then subjected to absorption spectroscopy and EPR test, as shown in fig. 2(a), (b). Comparing FIGS. 1(a), (b), the undoped germanate glass shows significant absorption loss and color center defect after irradiation, while the Nb-doped germanate glass⁵⁺The ion germanate glass has small absorption loss after irradiation, and color center defects do not appear.

Example 2

By means of variable-valence metal ionsCe⁴⁺(2 wt%) doped multicomponent germanate glass usingThe valence state conversion of the germanate glass absorbs free electrons and holes induced in the irradiation process, and inhibits the formation of irradiation-induced color center defects, thereby reducing the light absorption loss of the germanate glass and enhancing the stability of the laser taking the germanate glass as a matrix. Meanwhile, the variable valence ion doped multi-component germanate glass is ensured to have good optical performance, mechanical processing performance (mechanical cold processing can be adopted to prepare an optical fiber preform) and other performances.

Specifically, the oxide composition of the variable valence ion doped multicomponent germanate glass is as follows:

BaO 18wt％，

Ga₂O₃ 20wt％，

CeO₂2 wt%, and

GeO₂the balance;

weighing the oxides (the purity is more than or equal to 99.99 percent) according to the formula, transferring the oxides into an alumina crucible after fully and uniformly mixing to form a mixture, placing the mixture into a high-temperature well type furnace at 1400 ℃ for melting for 2h to obtain molten glass liquid, pouring the molten glass liquid onto a glass steel plate after the glass liquid is clarified for cooling and forming, then placing the glass into an annealing furnace which is heated to a temperature slightly lower than the glass transition temperature of the glass, preserving the heat at 620 ℃ for 2h, and then cooling the glass to room temperature along with the furnace.

The annealed sample was processed into a 20mmx20mmx2mm glass sheet and polished on both sides, and after polishing, it was irradiated with gamma rays at a dose of 50KGy, and then subjected to absorption spectroscopy and EPR test, as shown in fig. 3(a), (b). Comparing FIGS. 1(a), (b), the undoped germanate glass showed significant absorption loss and color center defect after irradiation, while Ce was doped⁴⁺The ion germanate glass has small absorption loss after irradiation, and color center defects do not appear.

Example 3

By means of variable-valence metal ions Sb³⁺(2 wt%) doped multicomponent germaniumAcid salt glass, use ofThe valence state conversion of the germanate glass absorbs free electrons and holes induced in the irradiation process, and inhibits the formation of irradiation-induced color center defects, thereby reducing the light absorption loss of the germanate glass and enhancing the stability of the laser taking the germanate glass as a matrix. Meanwhile, the variable valence ion doped multi-component germanate glass is ensured to have good optical performance and mechanical processing performance (an optical fiber preform can be prepared by adopting mechanical cold processing) and equal performance.

Specifically, the oxide composition of the variable valence ion doped multicomponent germanate glass is as follows:

BaO 18wt％，

Ga₂O₃ 20wt％，

Sb₂O₃2 wt%, and

GeO₂the balance;

weighing the oxides (the purity is more than or equal to 99.99 percent) according to the formula, transferring the oxides into an alumina crucible after fully and uniformly mixing to form a mixture, placing the mixture into a high-temperature well type furnace at 1400 ℃ for melting for 2h to obtain molten glass liquid, pouring the molten glass liquid onto a glass steel plate after the glass liquid is clarified for cooling and forming, then placing the glass into an annealing furnace which is heated to a temperature slightly lower than the glass transition temperature of the glass, preserving the heat at 620 ℃ for 2h, and then cooling the glass to room temperature along with the furnace.

The annealed sample was processed into a 20mmx20mmx2mm glass sheet and polished on both sides, and after polishing, it was irradiated with gamma rays at a dose of 50KGy, and then subjected to absorption spectroscopy and EPR test, as shown in fig. 4(a), (b). Comparing FIGS. 1(a), (b), the undoped germanate glass showed significant absorption loss and color center defects after irradiation, while the doped Sb³⁺The ion germanate glass has small absorption loss after irradiation, and color center defects do not appear.

Example 4

By variable valence metal ions Nb⁵⁺(4 wt%) doped multicomponent germanate glass usingThe valence state conversion of the germanate glass absorbs free electrons and holes induced in the irradiation process, and inhibits the formation of irradiation-induced color center defects, thereby reducing the light absorption loss of the germanate glass and enhancing the stability of the laser taking the germanate glass as a matrix. Meanwhile, the variable valence ion doped multi-component germanate glass is ensured to have good optical performance, mechanical processing performance (mechanical cold processing can be adopted to prepare an optical fiber preform) and other performances.

Specifically, the oxide composition of the variable valence ion doped multicomponent germanate glass is as follows:

BaO 18wt％，

Ga₂O₃ 20wt％，

Nb₂O₅4 wt%, and

GeO₂the balance;

weighing the oxides (the purity is more than or equal to 99.99 percent) according to the formula, transferring the oxides into an alumina crucible after fully and uniformly mixing to form a mixture, placing the mixture into a high-temperature well type furnace at 1400 ℃ for melting for 2h to obtain molten glass liquid, pouring the molten glass liquid onto a glass steel plate after the glass liquid is clarified for cooling and forming, then placing the glass into an annealing furnace which is heated to a temperature slightly lower than the glass transition temperature of the glass, preserving the heat at 620 ℃ for 2h, and then cooling the glass to room temperature along with the furnace.

The annealed sample was processed into a 20mmx20mmx2mm glass sheet and polished on both sides, and after polishing, it was irradiated with gamma rays at a dose of 50KGy, and then subjected to absorption spectroscopy and EPR test, as shown in fig. 5(a), (b). Comparing FIGS. 1(a), (b), the undoped germanate glass shows significant absorption loss and color center defect after irradiation, while the Nb-doped germanate glass⁵⁺The ion germanate glass has small absorption loss after irradiation, and color center defects do not appear.

The above examples merely represent some embodiments of the present invention, which are described in more detail and in more detail, but are not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the claims.