阅读说明：本技术 一种宽红外透过波段的氟铟酸盐玻璃及其制备方法 (Fluorine indium acid salt glass with wide infrared transmission wave band and preparation method thereof ) 是由 姜益光 张龙飞 张龙 袁新强 王在洋 于 2021-01-27 设计创作，主要内容包括：本发明提出了一种宽红外透过波段的氟铟酸盐玻璃及其制备方法,属于玻璃技术领域,该玻璃的组分及含量范围如下：InF-3：25～35mol％、BaF-2-SrF-2-ZnF-2：55～65mol％、GaF-3-LaF-3：6～10mol％、ZrF-4:2～5mol％。本发明宽红外透过波段的氟铟酸盐玻璃具有好的成玻璃性能,玻璃热稳定性判据ΔT≥80℃,高的中红外透过率,透过波段在3.2-6μm的透过率T≥90％(样品厚7mm),以及宽的红外透过波段,透过截止波长为8.3μm(样品厚7mm,截止透过率为50％),是中红外光纤理想的基质材料。(The invention provides a fluorine indate glass with wide infrared transmission wave band and a preparation method thereof, belonging to the technical field of glass, wherein the glass comprises the following components in percentage by weight: InF 3 ：25～35mol％、BaF 2 ‑SrF 2 ‑ZnF 2 ：55～65mol％、GaF 3 ‑LaF 3 ：6～10mol％、ZrF 4 2 to 5 mol%. The wide infrared transmission waveband fluoroindate glass has good glass forming performance, the thermal stability criterion delta T of the glass is more than or equal to 80 ℃, the middle infrared transmittance is high, the transmittance T of the transmission waveband is more than or equal to 90 percent (the sample thickness is 7mm) at 3.2-6 mu m, and the wide infrared transmission waveband, the transmission cut-off wavelength is 8.3 mu m (the sample thickness is 7mm, the cut-off transmittance is 50 percent), so the wide infrared transmission waveband is an ideal matrix material for a middle infrared optical fiber.)

1. The wide infrared transmission waveband fluorine indate glass is characterized by comprising the following components in percentage by weight: InF₃：25～35mol％、BaF₂-SrF₂-ZnF₂：55～65mol％、GaF₃-LaF₃：6～10mol％、ZrF₄:2～5mol％。

2. The wide infrared transmission band fluoroindate glass of claim 1, wherein the BaF is₂The content range is 18-20 mol%.

3. The wide infrared transmission band fluoroindate glass of claim 1, wherein the SrF is₂The content range is 20-25 mol%.

4. The wide infrared transmission band fluoroindium acid of claim 1Salt glass, characterized in that the ZnF₂The content range is 18-20 mol%.

5. The wide infrared transmission band fluoroindate glass of claim 1, wherein the GaF is a glass of the type₃The content range is 5-7 mol%.

6. The wide infrared transmission band fluoroindate glass of claim 1, wherein the LaF is selected from the group consisting of₃The content range is 2-3 mol%.

7. The wide infrared transmission band fluoroindate glass of any one of claims 1 to 6, wherein Δ T ═ glass has a superconductor transition temperature (T ═ glass)_c) Glass transition temperature (T)_g)≥80℃。

8. A method for preparing the wide infrared transmission band fluoroindate glass according to any one of claims 1 to 7, comprising the steps of:

(1) weighing the batch materials according to the proportion of each component, and fully mixing;

(2) under the protection of inert gas, putting the mixed batch into a platinum crucible, and melting for 1-1.5 h in a melting furnace at 850-900 ℃;

(3) pouring the molten glass onto a brass template preheated to 250-270 ℃, and cooling to obtain the blocky fluoroindium silicate glass.

9. The method of claim 8, wherein the inert gas is nitrogen.

10. The method of manufacturing according to claim 8, wherein the temperature of the brass die plate is 260 ℃.

Technical Field

The invention relates to the technical field of glass, in particular to fluoroindate glass with a wide infrared transmission waveband and a preparation method thereof.

Background

The fluoroindium silicate glass is InF₃Conventional fluoride glasses, which are the main forming components, have been reported since 1980In the past, the wide attention of the scientific field is gained. The glass has a wider transmission waveband (5 mu m) than the zirconium fluoride glass, can break through the limitation of 4 mu m cutoff of optical fiber transmission of the zirconium fluoride glass, can meet the application requirement of a future longer waveband, and has lower phonon energy (509 cm)^-1) The material provides a lower phonon energy environment for rare earth ions, and is a core candidate material of a new generation of intermediate infrared transmission media and lasers.

However, the fluoroindium silicate glass has poor glass forming performance and is easy to crystallize, so that severe preparation conditions are required, and large-size fluoroindium glass with uniform performance is not easy to obtain in air, which limits the practical application range thereof.

Therefore, improvement of the glass forming properties of the fluoroindate glass is a critical issue, which needs to be started from the composition optimization of the fluoroindate glass, and a stable fluoroindate glass composition is the basis for the preparation of high quality fluoroindium glass. The component of the fluorine indium glass base is InF₃-BaF₂-SrF₂-ZnF₂On the basis of which the composition adjustment is carried out. Currently, there is no fixed and stable fluoroindate glass component system.

Disclosure of Invention

The invention mainly solves the technical problems of easy crystallization, easy volatilization and difficult uniform preparation under the air condition of the existing fluoroindate glass, and provides fluoroindate glass with wide infrared transmission band and good glass forming performance.

The technical scheme of the invention is realized as follows:

the invention provides a fluorine indate glass with wide infrared transmission wave band, which comprises the following components in percentage by weight: InF₃：25～35mol％、BaF₂-SrF₂-ZnF₂：55～65mol％、GaF₃-LaF₃：6～10mol％、ZrF₄:2～5mol％。

As a further improvement of the invention, saidBaF₂The content range is 18-20 mol%.

As a further improvement of the invention, the SrF₂The content range is 20-25 mol%.

As a further development of the invention, the ZnF₂The content range is 18-20 mol%.

As a further improvement of the invention, the GaF₃The content range is 5-7 mol%.

As a further improvement of the invention, the LaF₃The content range is 2-3 mol%.

As a further development of the invention, the superconductor transition temperature (T) of the glass_c) Glass transition temperature (T)_g)≥80℃。

The invention further provides a preparation method of the wide infrared transmission waveband fluorine indate glass, which is characterized by comprising the following steps:

(1) weighing the batch materials according to the proportion of each component, and fully mixing;

(2) under the protection of inert gas, putting the mixed batch into a platinum crucible, and melting for 1-1.5 h in a melting furnace at 850-900 ℃;

(3) pouring the molten glass onto a brass template preheated to 250-270 ℃, and cooling to obtain the blocky fluoroindium silicate glass.

As a further improvement of the invention, the inert gas is nitrogen.

As a further development of the invention, the temperature of the brass die plate is 260 ℃.

The invention has the following beneficial effects: the wide infrared transmission waveband fluoroindate glass has good glass forming performance, the thermal stability criterion delta T of the glass is more than or equal to 80 ℃, the middle infrared transmittance is high, the transmittance T of the transmission waveband is more than or equal to 90 percent (the sample thickness is 7mm) at 3.2-6 mu m, and the wide infrared transmission waveband, the transmission cut-off wavelength is 8.3 mu m (the sample thickness is 7mm, the cut-off transmittance is 50 percent), so the wide infrared transmission waveband is an ideal matrix material for a middle infrared optical fiber.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a graph of the differential thermal profile of a wide infrared transmission band fluoroindate glass prepared in example 3 of the present invention;

FIG. 2 is a graph showing the infrared transmittance of a wide infrared transmittance band fluoroindate glass prepared in example 3 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The glass compositions of 6 specific examples of the invention and 3 comparative examples are listed in table 1 below:

TABLE 1

The preparation method comprises the following steps:

(1) weighing the batch materials according to the proportion of each component, and fully mixing;

(2) under the protection of nitrogen gas, putting the mixed batch into a platinum crucible, and melting for 1.5h in a melting furnace at 870 ℃;

(3) and pouring the molten glass onto a brass template preheated to 260 ℃, and cooling to obtain the blocky fluoroindium silicate glass.

Test example 1

The performance of the fluoroindium silicate glasses prepared in examples 1 to 6 of the present invention and comparative examples 1 to 3 was measured, and the results are shown in Table 2.

The test method comprises the following steps: the characteristic temperature value of the glass sample is measured by a TG-DTA thermogravimetric analyzer, and the transmittance is measured by a Fourier transform infrared spectrometer.

TABLE 2

Compared with the prior art, the prepared fluorine indate glass with wide infrared transmission wave band has good glass forming performance, the criterion of glass thermal stability Delta T is more than or equal to 80 ℃, the middle infrared transmittance is high, the transmittance T of the transmission wave band at 3.2-6 mu m is more than or equal to 90% (the thickness of a sample is 7mm), and the transmission cut-off wavelength of the wide infrared transmission wave band is 8.3 mu m (the thickness of the sample is 7mm, and the cut-off transmittance is 50%), so that the fluorine indate glass is an ideal matrix material for the middle infrared optical fiber.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.