阅读说明：本技术 一种碲酸盐玻璃光纤及其制备方法 (Tellurate glass optical fiber and preparation method thereof ) 是由 张勇 楚学娟 王永丹 魏茂彬 刘惠莲 靳迦惠 夏一铭 梁珺 万起良 于 2021-01-19 设计创作，主要内容包括：本发明公开了一种碲酸盐玻璃光纤,包括纤芯玻璃和包覆在纤芯玻璃外侧的皮层玻璃；其中,纤芯玻璃的组分按摩尔百分比包括：TeO-2：80％,Nb-2O-5：10-12％,Bi-2O-3：3-5％,Tb-2O-3：3-4％,Gd-2O-3：1-2％,其中,各原料的重量百分比总和为100％。本发明还公开了上述碲酸盐玻璃光纤的制备方法,包括如下步骤：将圆柱形纤芯玻璃插入管状皮层玻璃中,拉丝得到碲酸盐玻璃光纤,其中,拉丝温度为380-400℃。本发明从降低声子能量、提高玻璃密度、增加发光强度等多个方面提高本发明的光学性能；并且其热稳定性、成玻性好,适合拉制成光纤,另外本发明没有使用Pb、Cd等重金属。(The invention discloses a tellurate glass optical fiber, which comprises fiber core glass and skin layer glass coated on the outer side of the fiber core glass; wherein, the fiber core glass comprises the following components in percentage by mole: TeO 2 ：80％，Nb 2 O 5 ：10‑12％，Bi 2 O 3 ：3‑5％，Tb 2 O 3 ：3‑4％，Gd 2 O 3 : 1-2 percent, wherein the sum of the weight percentages of the raw materials is 100 percent. The invention also discloses a preparation method of the tellurate glass optical fiber, which comprises the following steps: inserting the cylindrical fiber core glass into the tubular sheath glass, and drawing to obtain the tellurite glass optical fiber, wherein the drawing temperature is 380-400 ℃. The optical performance of the invention is improved from the aspects of reducing phonon energy, improving glass density, increasing luminous intensity and the like; the optical fiber has good thermal stability and glass forming property, is suitable for being drawn into optical fibers, and does not use heavy metals such as Pb, Cd and the like.)

1. The tellurate glass optical fiber is characterized by comprising fiber core glass and skin layer glass coated on the outer side of the fiber core glass; wherein, the fiber core glass comprises the following components in percentage by mole: TeO₂：80％，Nb₂O₅：10-12％，Bi₂O₃：3-5％，Tb₂O₃：3-4％，Gd₂O₃: 1-2 percent, wherein the sum of the weight percentages of the raw materials is 100 percent.

2. The tellurate glass fiber according to claim 1, wherein the sheath glass comprises, in mole percent: TeO₂：82％，Nb₂O₅：12-14％，Bi₂O₃：4-6％。

3. The tellurate glass optical fiber according to claim 1 or 2, characterized in that the components of the core glass, in terms of mole percentages, comprise: TeO₂：80％，Nb₂O₅：11％，Bi₂O₃：4％，Tb₂O₃：3.5％，Gd₂O₃：1.5％。

4. The tellurite glass optical fiber according to any of claims 1 to 3, wherein the composition of the sheath glass comprises, in mole percent: TeO₂：82％，Nb₂O₅：13％，Bi₂O₃：5％。

5. A method for manufacturing a tellurite glass optical fiber according to any of claims 1 to 4, comprising the steps of: inserting the cylindrical fiber core glass into the tubular sheath glass, and drawing to obtain the tellurite glass optical fiber, wherein the drawing temperature is 380-400 ℃.

6. The method for preparing the tellurate glass optical fiber according to claim 5, wherein the core glass and the skin glass are both prepared by the processes of mixing, grinding, melting, casting and annealing.

7. The method for preparing the tellurate glass optical fiber according to claim 6, wherein the melting temperature of the core glass and the cladding glass is 950-.

8. The method for preparing the tellurite glass fiber as defined in claim 6, wherein the annealing temperatures of the core glass and the cladding glass are both 320-340 ℃, and the annealing times are both 2-3 h.

9. The method for producing a tellurite glass optical fiber according to any one of claims 5 to 8, wherein the diameter of the core glass is the same as the inner diameter of the tubular sheath glass.

10. The production method for a tellurite glass optical fiber according to any one of claims 5 to 9, wherein one end of the tubular sheath glass is sealed.

Technical Field

The invention relates to the technical field of glass optical fibers, in particular to a tellurate glass optical fiber and a preparation method thereof.

Background

Tellurate glass is heavy metal oxide glass and has excellent performance of low melting point, high density, high refractive index, low phonon energy, low optical loss and other advantages; can be used for manufacturing optical fiber glass.

However, the tellurate glass has a low melting point, so that the tellurate glass has poor thermal stability, is easy to crystallize in the process of drawing an optical fiber, and causes the optical fiber to be easy to break and influence the optical performance of the optical fiber; and the thermal stability and glass forming property of the conventional tellurate glass are improved by adding heavy metals harmful to the environment, such as Pb, Cd and the like, but the popularization and the application of tellurate glass optical fibers are limited by the existence of the heavy metals.

Disclosure of Invention

Based on the technical problems in the background art, the invention provides a tellurate glass optical fiber and a preparation method thereof, and the optical performance of the tellurate glass optical fiber is improved in multiple aspects of reducing phonon energy, improving glass density, increasing luminous intensity and the like; the optical fiber has good thermal stability and glass forming property, is suitable for being drawn into optical fibers, does not use heavy metals such as Pb, Cd and the like, and improves the limitation of the application range of the optical fiber.

The invention provides a tellurate glass optical fiber, which comprises fiber core glass and skin layer glass coated on the outer side of the fiber core glass; wherein, the fiber core glass comprises the following components in percentage by mole: TeO₂：80％，Nb₂O₅：10-12％，Bi₂O₃：3-5％，Tb₂O₃：3-4％，Gd₂O₃: 1-2 percent, wherein the sum of the weight percentages of the raw materials is 100 percent.

Preferably, the sheath glass comprises the following components in mole percent: TeO₂：82％，Nb₂O₅：12-14％，Bi₂O₃：4-6％。

Preferably, the composition of the core glass comprises, in mole percent: TeO₂：80％，Nb₂O₅：11％，Bi₂O₃：4％，Tb₂O₃：3.5％，Gd₂O₃：1.5％。

Preferably, the sheath glass comprises the following components in mole percent: TeO₂：82％，Nb₂O₅：13％，Bi₂O₃：5％。

The invention also discloses a preparation method of the tellurate glass optical fiber, which comprises the following steps: inserting the cylindrical fiber core glass into the tubular sheath glass, and drawing to obtain the tellurite glass optical fiber, wherein the drawing temperature is 380-400 ℃.

Preferably, the core glass and the skin glass are both prepared by the processes of mixing, grinding, melting, casting and annealing.

Preferably, the melting temperature of the core glass and the melting temperature of the sheath glass are both 950-1050 ℃, and the holding time is both 60-90 min.

Preferably, the annealing temperature of the core glass and the annealing temperature of the sheath glass are both 320-340 ℃, and the annealing time is both 2-3 h.

Preferably, the diameter of the core glass is the same as the inner diameter of the tubular sheath glass.

Preferably, one end of the tubular sheath glass is sealed.

The surface layer glass also needs to be processed by punching holes to obtain tubular surface layer glass.

Has the advantages that:

the invention adjusts TeO₂、Nb₂O₅、Bi₂O₃The molar ratio of (a) to (b) in the glass enables the invention to keep the phonon energy low and to increase the glass density (both greater than 5 g/cm)³) And having a glass transition temperature Tg ofThe difference value of the starting crystallization temperature Tx is far more than 100 ℃, so that the optical fiber has enough thermal stability, prevents crystallization, improves the glass forming property and the mechanical property, is suitable for being drawn into an optical fiber, and avoids the influence of crystallization on the optical property in the drawing process; adding proper amount of Tb₂O₃、Gd₂O₃The mutual matching of the components improves the luminous performance of the invention; the optical performance of the invention is improved from the aspects of reducing phonon energy, improving glass density, increasing luminous intensity and the like; the optical fiber is suitable for being drawn into optical fiber, and has no heavy metal such as Pb, Cd and the like, so that the limitation of the application range of the optical fiber is improved.

Drawings

FIG. 1 is a DSC chart of the core glass of example 3.

Detailed Description

The technical solution of the present invention will be described in detail below with reference to specific examples.

Example 1

A tellurate glass optical fiber comprises fiber core glass and skin layer glass coated on the outer side of the fiber core glass; wherein, the fiber core glass comprises the following components in percentage by mole: TeO₂：80％，Nb₂O₅：12％，Bi₂O₃：3％，Tb₂O₃：4％，Gd₂O₃：1％；

The sheath glass comprises the following components in percentage by mole: TeO₂：82％，Nb₂O₅：14％，Bi₂O₃：4％。

The preparation method of the tellurite glass optical fiber comprises the following steps:

uniformly mixing all components of the fiber core glass, grinding, then preserving heat at 1050 ℃ for 60min, then adding into a mold with the temperature of 230 ℃ for molding, and then annealing at 340 ℃ for 2h to obtain cylindrical fiber core glass;

uniformly mixing all components of the skin layer glass, grinding, then preserving heat at 1050 ℃ for 60min, then adding into a mold poured at 230 ℃ for molding, and then annealing at 340 ℃ for 2h to obtain cylindrical skin layer glass; punching a hole in the central axis direction of the cylindrical skin glass to obtain tubular skin glass, and sealing one end of the tubular skin glass;

polishing the cylindrical fiber core glass to enable the diameter of the fiber core glass to be the same as the inner diameter of the tubular skin layer glass, then inserting the cylindrical fiber core glass into the tubular skin layer glass, and drawing at 400 ℃ to obtain the tellurate glass optical fiber.

Example 2

A tellurate glass optical fiber comprises fiber core glass and skin layer glass coated on the outer side of the fiber core glass; wherein, the fiber core glass comprises the following components in percentage by mole: TeO₂：80％，Nb₂O₅：10％，Bi₂O₃：5％，Tb₂O₃：3％，Gd₂O₃：2％；

The sheath glass comprises the following components in percentage by mole: TeO₂：82％，Nb₂O₅：12％，Bi₂O₃：6％。

The preparation method of the tellurite glass optical fiber comprises the following steps:

uniformly mixing all components of the fiber core glass, grinding, then preserving heat at 950 ℃ for 90min, then adding the mixture into a mold with the temperature of 230 ℃ for molding, and then annealing at 320 ℃ for 3h to obtain cylindrical fiber core glass;

uniformly mixing all components of the skin layer glass, grinding, then preserving heat at 950 ℃ for 90min, then adding into a mold with the temperature of 230 ℃ for molding, and then annealing at 320 ℃ for 3h to obtain cylindrical skin layer glass; punching a hole in the central axis direction of the cylindrical skin glass to obtain tubular skin glass, and sealing one end of the tubular skin glass;

and polishing the cylindrical fiber core glass to ensure that the diameter of the fiber core glass is the same as the inner diameter of the tubular skin layer glass, then inserting the cylindrical fiber core glass into the tubular skin layer glass, and drawing at 380 ℃ to obtain the tellurate glass optical fiber.

Example 3

A tellurate glass optical fiber comprises fiber core glass and skin layer glass coated on the outer side of the fiber core glass; in which groups of core glassesThe mol percentages of the components are as follows: TeO₂：80％，Nb₂O₅：11％，Bi₂O₃：4％，Tb₂O₃：3.5％，Gd₂O₃：1.5％；

The sheath glass comprises the following components in percentage by mole: TeO₂：82％，Nb₂O₅：13％，Bi₂O₃：5％。

The preparation method of the tellurite glass optical fiber comprises the following steps:

uniformly mixing all components of the fiber core glass, grinding, then preserving heat for 75min at 1000 ℃, adding into a mold with the temperature of 230 ℃ for molding, and then annealing at 330 ℃ for 2.5h to obtain cylindrical fiber core glass;

uniformly mixing all components of the skin layer glass, grinding, then preserving heat for 75min at 1000 ℃, adding into a mold with the temperature of 230 ℃ for molding, and then annealing at 330 ℃ for 2.5h to obtain cylindrical skin layer glass; punching a hole in the central axis direction of the cylindrical skin glass to obtain tubular skin glass, and sealing one end of the tubular skin glass;

polishing the cylindrical fiber core glass to enable the diameter of the fiber core glass to be the same as the inner diameter of the tubular skin layer glass, then inserting the cylindrical fiber core glass into the tubular skin layer glass, and drawing at 390 ℃ to obtain the tellurate glass optical fiber.

Experiment 1

The DSC detection of the core glass of the embodiment 3 is carried out, the result is shown in figure 1, figure 1 is the DSC spectrum of the core glass of the embodiment 3, and as can be seen from figure 1, the glass transition temperature Tg of the core glass of the embodiment 3 is 357 ℃, the crystallization starting temperature Tx is 518 ℃, the difference between the two is 143 ℃ and is far more than 100 ℃, and the glass forming property and the thermal stability are good.

Experiment 2

The core glasses of examples 1 to 3 were excited at 380nm, and the emission spectra thereof were examined to observe the maximum emission peak position and the emission intensity, and the results are shown in Table 1.

TABLE 1 test results

Detecting items	Maximum luminescence peak position nm	Luminous intensity a.u.
			Example 1	543	510
Example 2	543	403
			Example 3	543	477

As can be seen from the above table, the present invention has good luminous intensity.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.