A diamagnetic ultra-thin tellurite glass, a preparation method and application thereof

Abstract

The application discloses an inverse-magnetic ultra-thin tellurite glass as well as a preparation method and application thereof, and belongs to the technical field of tellurite glass. The molten glass liquid is drawn out from a slit opening in the middle of a side wall of a smelting furnace by using a melting-annealing method. The middle of the side wall of the smelting furnace is at a position with a distance of 1 / 2 of the height of the furnace body from the bottom. The height of the slit opening is 2.0 mm, the width of the slit opening is 600 mm, and the inclination angle of the slit opening is 45 DEG. The ultra-thin tellurite glass with a thickness of about 5 microns can be obtained by opening the slit opening in the middle of the smelting furnace and drawing the molten glass liquid out by using a drawing device, and the mechanical strength and the inverse-magnetic stability of the tellurite glass can be effectively improved.

Description

Technical Field

[0001] This invention belongs to the field of tellurite glass technology, and particularly relates to a diamagnetic ultrathin tellurite glass, its preparation method and application. Background Technology

[0002] Traditional silicate-phosphate glasses are characterized by high Vickers hardness and brittleness, making ultrathin fabrication (<100µm) difficult. They also exhibit poor diamagnetic properties. In contrast, TeO2-based tellurate glasses possess stronger diamagnetic properties than silicates, along with high refractive index and good infrared transmittance. While exhibiting excellent linear optical properties, their conventional components are prone to crystallization in ultrathin states, resulting in insufficient flexibility. Further advancements in fabrication processes are needed to achieve ultrathinness. Tellurate glasses typically exhibit high high-temperature viscosity, hindering their flowability within the temperature range required for slit drawing and making it difficult to form stable, uniform glass ribbons. Tellurate systems are prone to crystallization; improper cooling control during forming and annealing can easily lead to microcrystal precipitation, causing devitrification, embrittlement, and loss of flexibility. Introducing paramagnetic or ferromagnetic impurities such as iron and nickel during fabrication, or reducing some tellurium ions to paramagnetic metallic tellurium under a reducing atmosphere, will severely impair the glass's diamagnetic properties.

[0003] Therefore, how to provide a method for the stable preparation of ultrathin dimagnetic glass is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention proposes a dimagnetic ultrathin tellurate glass, its preparation method, and its applications.

[0005] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing diamagnetic ultrathin tellurate glass, using a melt-annealing method, in which molten glass is pulled out through a narrow slit opening in the middle of the side wall of a melting furnace; The middle part of the side wall of the smelting furnace is located at 1 / 2 the height of the furnace body from the bottom of the side wall; The slit opening is a horizontal slit opening with a height of 2.0 mm, a width of 600 mm, and an inclination angle of 45°.

[0006] More preferably, a platinum-rhodium alloy is used as the frame of the slit opening. The structural stability and absolute inertness of the platinum-rhodium alloy at high temperatures can produce ultra-thin glass with higher surface quality and purity that meets the requirements.

[0007] Preferably, it includes the following steps: (1) A slit opening is made in the middle of the side wall of the melting furnace as an outlet for molten glass, and a pulling device is installed at the slit opening; (2) The raw materials for diamagnetic ultrathin tellurate glass are mixed and melted to obtain molten glass liquid; (3) The molten glass liquid is pulled out from the slit opening by the pulling device and then annealed to obtain the antimagnetic ultrathin tellurite glass.

[0008] More preferably, the pulling forming in step (3) is: the molten glass liquid is slowly and evenly pulled out using the pulling device under the action of gravity.

[0009] Preferably, the upper and lower sides of the slit opening in step (1) are also provided with extrusion rollers.

[0010] Beneficial effects: The extrusion roller can forcefully extrude the pre-formed tellurate glass flowing out of the slit with a precise gap, correcting the problem of uneven thickness caused by slit discharge.

[0011] Preferably, the diamagnetic ultrathin tellurate glass in step (2) comprises the following molar percentages of raw materials: The composition is 70% TeO, 18-20% PbO, 0.5-2.5% B2O3, 8.5% ZnO, and 1% SiO2.

[0012] More preferably, it contains: 70% TeO2, 20% PbO, 0.5% B2O3, 8.5% ZnO and 1% SiO2.

[0013] Alternatively, it contains 70% TeO2, 19.5% PbO, 1% B2O3, 8.5% ZnO, and 1% SiO2.

[0014] Alternatively, it contains 70% TeO2, 19.0% PbO, 1.5% B2O3, 8.5% ZnO, and 1% SiO2.

[0015] Alternatively, it contains 70% TeO2, 18.5% PbO, 32% B2O, 8.5% ZnO, and 1% SiO2.

[0016] Alternatively, it contains 70% TeO2, 18.0% PbO, 2.5% B2O3, 8.5% ZnO, and 1% SiO2.

[0017] Preferably, the melting temperature in step (2) is 850°C and the melting time is 4 hours. Preferably, the stretching speed in step (3) is 15 mm / s.

[0018] Preferably, the annealing temperature in step (3) is 300°C.

[0019] A dimagnetic ultrathin tellurite glass prepared by the method described above.

[0020] Preferably, the thickness of the antimagnetic ultrathin tellurate glass is 5 μm.

[0021] Application of a dimagnetic ultrathin tellurate glass in microstructured optical fibers.

[0022] Compared with the prior art, the present invention has the following advantages and technical effects: This invention provides a novel diamagnetic ultrathin tellurate glass, its preparation method, and its applications. By creating a slit opening in the middle of a melting furnace and drawing the molten glass into shape, tellurate glass is prepared using a mid-drawing method. This yields ultrathin tellurate glass with a thickness of approximately 5 μm, effectively improving its mechanical strength and diamagnetic stability. Furthermore, impurities exist in the molten glass in the melting furnace, primarily distributed at the bottom and surface. The molten glass in the middle of the furnace has a higher purity than the upper and lower portions. Therefore, this invention, by creating a slit opening in the middle of the furnace sidewall for drawing, yields tellurate glass with higher purity, further ensuring the glass's performance. Attached Figure Description

[0023] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings: Figure 1 This is a schematic diagram of the side cross-sectional structure of the melting furnace used for preparing ultrathin glass by the pull method obtained in Examples 1 and 2; Figure 2 This is a schematic diagram of the slit opening and its tilt angle of the smelting furnace in Example 1; Figure 3 This is a schematic diagram of the ultrathin glass prepared by the pull method in Example 2. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0026] This invention provides a method for preparing diamagnetic ultrathin tellurite glass, which uses a melt-annealing method to pull molten glass out through a narrow slit opening in the middle of the side wall of a melting furnace; The middle part of the side wall of the smelting furnace is a horizontal slit located at 1 / 2 the height from the bottom of the furnace body. The slit opening has a height of 2.0 mm, a width of 600 mm, and an inclination angle of 45°.

[0027] In a more preferred embodiment, a platinum-rhodium alloy is used as the frame of the slit opening. The extremely high thermal stability and excellent chemical inertness of the platinum-rhodium alloy allow the molten glass to flow smoothly down its surface.

[0028] In a preferred embodiment, the specific steps include: (1) A slit opening is made in the middle of the side wall of the melting furnace as an outlet for molten glass, and a pulling device is installed at the slit opening; (2) The raw materials for diamagnetic ultrathin tellurate glass are mixed and melted to obtain molten glass liquid; (3) The molten glass liquid is pulled out from the slit opening by the pulling device and then annealed to obtain the antimagnetic ultrathin tellurite glass.

[0029] In a more preferred embodiment, the pulling process in step (3) is as follows: the molten glass liquid is slowly and evenly pulled out using the pulling device under the action of gravity.

[0030] In a preferred embodiment, the upper and lower sides of the slit opening in step (1) are also provided with extrusion rollers.

[0031] In a preferred embodiment, the diamagnetic ultrathin tellurate glass in step (2) comprises the following molar percentages of raw materials: The composition is 70% TeO, 18-20% PbO, 0.5-2.5% B2O3, 8.5% ZnO, and 1% SiO2.

[0032] More preferably, it contains: 70% TeO2, 20% PbO, 0.5% B2O3, 8.5% ZnO and 1% SiO2.

[0033] Alternatively, it contains 70% TeO2, 19.5% PbO, 1% B2O3, 8.5% ZnO, and 1% SiO2.

[0034] Alternatively, it contains 70% TeO2, 19.0% PbO, 1.5% B2O3, 8.5% ZnO, and 1% SiO2.

[0035] Alternatively, it contains 70% TeO2, 18.5% PbO, 32% B2O, 8.5% ZnO, and 1% SiO2.

[0036] Alternatively, it contains 70% TeO2, 18.0% PbO, 2.5% B2O3, 8.5% ZnO, and 1% SiO2.

[0037] In a preferred embodiment, the melting temperature in step (2) is 850°C and the melting time is 4 hours. In a preferred embodiment, the stretching speed in step (3) is 15 mm / s.

[0038] In a preferred embodiment, the annealing temperature in step (3) is 300°C.

[0039] This invention also provides a dimagnetic ultrathin tellurite glass prepared by the preparation method described above.

[0040] In a preferred embodiment, the thickness of the antimagnetic ultrathin tellurate glass is 5 μm.

[0041] This invention also provides an application of dimagnetic ultrathin tellurate glass in microstructured optical fibers.

[0042] All raw materials used in the embodiments of this invention were purchased through commercial channels; In the embodiments of this invention, room temperature or normal temperature refers to 25±3℃.

[0043] Example 1 A melting furnace for preparing diamagnetic ultrathin tellurate glass, such as Figure 1 and 2 As shown, a slit opening is made in the middle of the side wall of the smelting furnace. This slit, located at half the height from the bottom of the furnace body, has a height of 2.0 mm and a width of 600 mm. The opening angle θ of the slit opening is 45°, with the side wall below it as a reference. A platinum-rhodium alloy is embedded in the slit opening as its frame to protect the furnace. A squeeze roller and a traction roller are sequentially arranged at the slit opening; the squeeze roller is located on the upper and lower sides of the slit opening, and the traction roller serves as a pulling device.

[0044] Example 2 A diamagnetic ultrathin tellurate glass comprising the following molar percentages of raw materials: 70% TeO2, 20.0% PbO, 0.5% B2O3, 8.5% ZnO, and 1% SiO2.

[0045] A method for preparing diamagnetic ultrathin tellurate glass, such as Figure 1 As shown, it includes the following steps: (1) After mixing the above raw materials, put them into a crucible and melt them in the melting furnace of Example 1 at 850°C for 4 hours to fully clarify and homogenize them, and obtain molten glass liquid; (2) The speed at which the traction roller pulls the molten glass is set to 15 mm / s, and the parameters of the extrusion roller are set (using a platinum-rhodium alloy extrusion roller with a diameter of 25 mm, a linear speed of 5 mm / s, and a surface roughness Ra=0.01μm). The slit opening on the side wall of the melting furnace is opened, and the molten glass is slowly and evenly pulled out and shaped under the action of gravity. Then, annealing is performed at an external temperature of 300℃ to eliminate internal stress, thus obtaining a 5μm thick antimagnetic ultrathin tellurate glass. The actual object is shown in the figure. Figure 3 As shown.

[0046] Example 3 A type of antimagnetic ultrathin tellurate glass comprising the following raw materials in molar percentages: The composition is 70% TeO, 19.5% PbO, 31% B2O, 8.5% ZnO, and 1% SiO.

[0047] A method for preparing diamagnetic ultrathin tellurate glass, using the raw materials described in this embodiment, includes the following steps: (1) After mixing the above raw materials, put them into a crucible and melt them in the melting furnace of Example 1 at 850°C for 4 hours to fully clarify and homogenize them, and obtain molten glass liquid; (2) The speed at which the traction roller pulls the molten glass is set to 15 mm / s, and the parameters of the extrusion roller are set (using a platinum-rhodium alloy extrusion roller with a diameter of 25 mm, a linear speed of 5 mm / s, and a surface roughness Ra=0.01μm). The slit opening on the side wall of the melting furnace is opened, and the molten glass is slowly and evenly pulled out and shaped under the action of gravity. Then, it is annealed at an external temperature of 300℃ to eliminate internal stress, thus obtaining a 5μm thick antimagnetic ultrathin tellurate glass.

[0048] Example 4 A type of antimagnetic ultrathin tellurate glass comprising the following raw materials in molar percentages: The composition is 70% TeO, 19.0% PbO, 1.5% B2O3, 8.5% ZnO, and 1% SiO2.

[0049] A method for preparing diamagnetic ultrathin tellurate glass, using the raw materials described in this embodiment, with other process steps and parameters being the same as in Embodiment 2.

[0050] A method for preparing diamagnetic ultrathin tellurate glass, using the raw materials described in this embodiment, includes the following steps: (1) After mixing the above raw materials, put them into a crucible and melt them in the melting furnace of Example 1 at 850°C for 4 hours to fully clarify and homogenize them, and obtain molten glass liquid; (2) The speed at which the traction roller pulls the molten glass is set to 15 mm / s, and the parameters of the extrusion roller are set (using a platinum-rhodium alloy extrusion roller with a diameter of 25 mm, a linear speed of 5 mm / s, and a surface roughness Ra=0.01μm). The slit opening on the side wall of the melting furnace is opened, and the molten glass is slowly and evenly pulled out and shaped under the action of gravity. Then, it is annealed at an external temperature of 300℃ to eliminate internal stress, thus obtaining a 5μm thick antimagnetic ultrathin tellurate glass.

[0051] Example 5 A type of antimagnetic ultrathin tellurate glass comprising the following raw materials in molar percentages: The composition is 70% TeO, 18.5% PbO, 32% B2O, 8.5% ZnO, and 1% SiO.

[0052] A method for preparing diamagnetic ultrathin tellurate glass, using the raw materials described in this embodiment, includes the following steps: (1) After mixing the above raw materials, put them into a crucible and melt them in the melting furnace of Example 1 at 850°C for 4 hours to fully clarify and homogenize them, and obtain molten glass liquid; (2) The speed at which the traction roller pulls the molten glass is set to 15 mm / s, and the parameters of the extrusion roller are set (using a platinum-rhodium alloy extrusion roller with a diameter of 25 mm, a linear speed of 5 mm / s, and a surface roughness Ra=0.01μm). The slit opening on the side wall of the melting furnace is opened, and the molten glass is slowly and evenly pulled out and shaped under the action of gravity. Then, it is annealed at an external temperature of 300℃ to eliminate internal stress, thus obtaining a 5μm thick antimagnetic ultrathin tellurate glass.

[0053] Example 6 A type of antimagnetic ultrathin tellurate glass comprising the following raw materials in molar percentages: The composition is 70% TeO, 18.0% PbO, 2.5% B2O, 8.5% ZnO, and 1% SiO.

[0054] A method for preparing diamagnetic ultrathin tellurate glass, using the raw materials described in this embodiment, includes the following steps: (1) After mixing the above raw materials, put them into a crucible and melt them in the melting furnace of Example 1 at 850°C for 4 hours to fully clarify and homogenize them, and obtain molten glass liquid; (2) The speed at which the traction roller pulls the molten glass is set to 15 mm / s, and the parameters of the extrusion roller are set (using a platinum-rhodium alloy extrusion roller with a diameter of 25 mm, a linear speed of 5 mm / s, and a surface roughness Ra=0.01μm). The slit opening on the side wall of the melting furnace is opened, and the molten glass is slowly and evenly pulled out and shaped under the action of gravity. Then, it is annealed at an external temperature of 300℃ to eliminate internal stress, thus obtaining a 5μm thick antimagnetic ultrathin tellurate glass.

[0055] Technical effects: The density, thermal stability, coefficient of thermal expansion, microstructure uniformity, and diamagnetic properties (magnetic susceptibility) of the tellurate glasses obtained in Examples 2-6 were tested using the Archimedes displacement method, thermal stability analysis (DSC), and room temperature vibrating sample magnetometer (VSM) method, respectively. The results are shown in Table 1. It can be seen that the tellurate glass obtained in Example 6 has a higher density and a larger coefficient of thermal expansion. Furthermore, the tellurate glasses obtained in Examples 2-6 exhibit good diamagnetic properties. With the assistance of PbO, B2O3, and SiO2, as the PbO content decreases and the B2O3 content increases, the microscopic uniformity and chemical stability of the glass improve. The tellurate glass obtained in Example 6 also exhibits the best flexibility, higher density, and a larger coefficient of thermal expansion. This invention, using this process and material ratio, can prepare ultrathin tellurate glass strips with a thickness of 5 μm, which can be used in the field of microstructured optical fibers.

[0056] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing diamagnetic ultrathin tellurate glass, using a melt-annealing method, characterized in that, The molten glass is pulled out through a narrow slit opening in the middle of the side wall of the melting furnace; The middle part of the side wall of the smelting furnace is located at 1 / 2 the height of the furnace body from the bottom of the side wall. The slit opening has a height of 2.0 mm, a width of 600 mm, and an inclination angle of 45°.

2. The method for preparing diamagnetic ultrathin tellurate glass according to claim 1, characterized in that, Specifically, the following steps are included: (1) A slit opening is made in the middle of the side wall of the melting furnace as an outlet for molten glass, and a pulling device is installed at the slit opening; (2) The raw materials for diamagnetic ultrathin tellurate glass are mixed and melted to obtain molten glass liquid; (3) The molten glass liquid is pulled out from the slit opening by the pulling device and then annealed to obtain the antimagnetic ultrathin tellurite glass.

3. The method for preparing diamagnetic ultrathin tellurate glass according to claim 2, characterized in that, In step (1), the upper and lower sides of the slit opening are also provided with extrusion rollers.

4. The method for preparing diamagnetic ultrathin tellurate glass according to claim 2, characterized in that, The diamagnetic ultrathin tellurate glass described in step (2) comprises the following molar percentages of raw materials: TeO2 70%, PbO 18-20%, B2O3 0.5-2.5%, ZnO 8.5% and SiO2 1%.

5. The method for preparing diamagnetic ultrathin tellurate glass according to claim 2, characterized in that, The melting temperature in step (2) is 850°C and the melting time is 4 hours.

6. The method for preparing diamagnetic ultrathin tellurate glass according to claim 2, characterized in that, The stretching speed described in step (3) is 15 mm / s.

7. The method for preparing diamagnetic ultrathin tellurate glass according to claim 2, characterized in that, The annealing temperature in step (3) is 300°C.

8. A dimagnetic ultrathin tellurate glass prepared by the preparation method according to any one of claims 1-7.

9. The diamagnetic ultrathin tellurate glass according to claim 8, characterized in that, The thickness of the antimagnetic ultrathin tellurate glass is 5 μm.

10. An application of the dimagnetic ultrathin tellurate glass as described in claim 8 in microstructure optical fibers.

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