A fluorine-zinc-aluminum-based glass ceramic containing a ZnF2 crystal phase and a preparation method thereof
By strictly designing the fluoride glass composition and using melt quenching and heat treatment methods, a fluorine-zinc-aluminum-based microcrystalline glass containing the ZnF2 crystalline phase was prepared, which solved the problems of insufficient transmittance and luminescence performance in the existing technology and achieved enhanced transmittance and luminescence in the visible and mid-infrared bands.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HARBIN ENG UNIV
- Filing Date
- 2024-01-17
- Publication Date
- 2026-06-02
AI Technical Summary
Existing technologies make it difficult to prepare fluorine-zinc-aluminum-based microcrystalline glass containing a single ZnF2 crystal phase, resulting in insufficient transmittance and luminescence performance in the visible and mid-infrared bands.
By strictly designing the composition ratio of the fluoride glass system, the precursor fluorine-zinc-aluminum-based glass was obtained by melt quenching, and the microcrystalline glass containing ZnF2 crystalline phase was prepared by heat treatment.
Good transmittance of fluorine-zinc-aluminum-based microcrystalline glass with a single ZnF2 crystal phase in the visible and mid-infrared bands was achieved, and the upconversion and mid-infrared luminescence effects were enhanced after doping with rare earth elements.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of luminescent materials technology, and relates to a fluorine-zinc-aluminum based microcrystalline glass containing ZnF2 crystal phase and its preparation method, and more particularly to a multi-component fluoride microcrystalline glass with controllable precipitation of single crystal phase and its preparation method. Background Technology
[0002] Glass-ceramics, also known as microcrystalline glass, are polycrystalline solid materials containing a large amount of microcrystalline and glassy phases, obtained by controlling the crystallization of a base glass with a specific composition during heating. Microcrystalline glass is a composite material containing both crystalline and glassy phases. In recent years, microcrystalline glass has attracted widespread attention due to its unique properties, and its research spans multiple disciplines including physics, chemistry, and materials science.
[0003] Fluorinated zinc aluminum glass is a type of fluoride multicomponent glass made by firing zinc fluoride and aluminum fluoride in high proportions. Among various glass matrices, fluorides offer significant advantages. Compared to microcrystalline glasses with oxide and sulfide matrices, fluoride microcrystalline glasses feature lower phonon energy, wider transmission windows, and higher rare-earth ion doping concentrations, making them well-suited for applications in fiber optic / glass lighting displays and high-power mid-infrared fiber laser research.
[0004] Compared to oxide or fluoride oxide glasses, fluoride glasses lack traditional network formations in their glass systems. Therefore, fluoride microcrystals prepared by heat treatment cannot controllably precipitate a specific single crystalline phase. The precipitation of multiple crystalline phases results in materials lacking specific application value and development prospects. Thus, the preparation of fluoride microcrystals containing a single crystalline phase through rigorous compositional design is of significant importance.
[0005] Therefore, those skilled in the art are dedicated to developing a fluorine-zinc-aluminum based microcrystalline glass containing the ZnF2 crystalline phase and its preparation method, in order to overcome the problems existing in the prior art. Summary of the Invention
[0006] In view of the above-mentioned deficiencies of the prior art, the technical problem to be solved by the present invention is how to provide a fluorine-zinc-aluminum based microcrystalline glass containing a ZnF2 crystalline phase and its preparation method. This microcrystalline glass has a single ZnF2 crystalline phase, and upconversion and mid-infrared luminescence enhancement can be achieved through rare earth doping.
[0007] To achieve the above objectives, the present invention provides a fluorine-zinc-aluminum-based microcrystalline glass containing a ZnF2 crystalline phase, wherein the molar percentages of its raw material components are: ZnF2 25 to 35 mol%, BaF2 10 to 20 mol%, YF3 10 to 20 mol%, SrF2 5 to 15 mol%, AlF3 25 to 35 mol%, and ErF3 0 to 10 mol%. The fluorine-zinc-aluminum-based microcrystalline glass containing the ZnF2 crystalline phase is prepared by obtaining the precursor fluorine-zinc-aluminum-based glass through a melt-quenching method, followed by heat treatment.
[0008] The present invention also provides a method for preparing the fluorine-zinc-aluminum-based microcrystalline glass containing the ZnF2 crystalline phase as described above, the method comprising the following steps:
[0009] Step 1: In a glove box filled with an inert gas environment, weigh the raw materials according to the raw material composition ratio of the fluorine zinc aluminum-based microcrystalline glass containing ZnF2 crystal phase, and add ammonium bifluoride with a specific gravity of 40% of the raw materials. After grinding thoroughly in an agate mortar, transfer the raw materials to a platinum crucible.
[0010] Step 2: Place the platinum crucible containing the mixed glass raw materials in a muffle furnace under an air atmosphere for preheating. Then, after cooling the preheated glass liquid, transfer it to a glove box filled with an inert gas environment for reheating to obtain molten glass liquid.
[0011] Step 3: Use platinum crucible tongs to hold the heated platinum crucible containing molten glass, pour the molten glass into a brass mold, keep it at a certain temperature, and then cool it to room temperature in the furnace to complete the annealing process.
[0012] Step 4: Place the annealed glass into a precision annealing furnace for heat treatment to obtain fluorine-zinc-aluminum-based microcrystalline glass containing the ZnF2 crystalline phase.
[0013] Furthermore, the preheating in the muffle furnace in step 2 specifically involves preheating at a temperature of 900–950°C for 30–60 minutes.
[0014] Furthermore, the preheating in the muffle furnace in step 2 specifically involves preheating at 950°C for 30 minutes.
[0015] Furthermore, the reheating of the glove box in step 2 specifically involves heating at a temperature of 900–950°C for 2–3 hours.
[0016] Furthermore, the reheating of the glove box in step 2 specifically involves heating at 950°C for 3 hours.
[0017] Furthermore, step 3 is carried out in an environment filled with inert gas, the brass mold has been preheated to 300-315°C, and the heat preservation time is 3-5 hours.
[0018] Furthermore, in step 3, the brass mold has been preheated to 315°C, and the heat preservation time is 5 hours.
[0019] Furthermore, the heat treatment in step 4 specifically involves heat treatment at a temperature of 455–460°C for 1–3 hours.
[0020] Furthermore, the heat treatment in step 4 specifically involves heat treatment at 455°C for 3 hours.
[0021] Compared with the prior art, the present invention has at least the following beneficial effects:
[0022] This invention, through precise design of the component ratios of the fluoride glass system, uses a melt-quenching method to obtain the precursor fluorine-zinc-aluminum-based glass, and then uses heat treatment to prepare fluoride microcrystalline glass containing the ZnF2 crystalline phase. Compared with existing technologies, it can obtain fluoride microcrystalline glass containing a single ZnF2 crystalline phase. The obtained material has good transmittance in the visible and mid-infrared bands, and after doping with rare earth elements, it can achieve enhanced upconversion and mid-infrared luminescence. In addition, the preparation steps of this invention are simple and easy to operate.
[0023] The following will further explain the concept, specific structure, and technical effects of the present invention in conjunction with the accompanying drawings, so as to fully understand the purpose, features, and effects of the present invention. Attached Figure Description
[0024] Figure 1 These are X-ray diffraction patterns of the fluorine-zinc-aluminum-based microcrystalline glass containing the ZnF2 crystalline phase prepared in Examples 1 and 2 of the present invention, and the matrix glass prepared in Comparative Example 1.
[0025] Figure 2 This is the transmission spectrum of the fluorine-zinc-aluminum-based microcrystalline glass containing the ZnF2 crystalline phase prepared in Example 1 of the present invention;
[0026] Figure 3 The upconversion emission spectra of the fluorine-zinc-aluminum-based microcrystalline glass containing the ZnF2 crystalline phase prepared in Example 1 of the present invention and the matrix glass prepared in Comparative Example 1 are obtained under excitation at a wavelength of 980 nm.
[0027] Figure 4 The emission spectra at 1.5 μm under 980 nm wavelength excitation are those of the fluorine-zinc-aluminum based microcrystalline glass containing ZnF2 crystal phase prepared in Example 1 of the present invention and the matrix glass prepared in Comparative Example 1.
[0028] Figure 5The emission spectra at 2.7 μm under 980 nm wavelength excitation are those of the fluorine-zinc-aluminum based microcrystalline glass containing ZnF2 crystal phase prepared in Example 1 of the present invention and the matrix glass prepared in Comparative Example 1.
[0029] Figure 6 The emission spectra at 3.5 μm under 650 nm wavelength excitation are those of the fluorine-zinc-aluminum based microcrystalline glass containing ZnF2 crystal phase prepared in Example 1 of the present invention and the substrate glass prepared in Comparative Example 1. Detailed Implementation
[0030] The following description, with reference to the accompanying drawings, illustrates several preferred embodiments of the present invention to make its technical content clearer and easier to understand. The present invention can be embodied in many different forms, and the scope of protection of the present invention is not limited to the embodiments mentioned herein.
[0031] Example 1
[0032] Glass component raw material preparation: In a glove box filled with inert gas, weigh 20g of raw material according to the molar percentage of the glass component distribution ratio 30ZnF2-15BaF2-12YF3-10SrF2-30AlF3-3ErF3, and add an additional 8g of ammonium bifluoride. Grind thoroughly in an agate mortar and transfer to a platinum crucible.
[0033] Glass melting: Platinum crucible containing mixed glass raw materials is placed in a muffle furnace at 950°C in air atmosphere and preheated for 30 minutes. The preheated glass liquid is then cooled and transferred to a glove box filled with inert gas environment and heated at the same temperature of 950°C for 3 hours to obtain molten glass liquid.
[0034] Glass casting and annealing: Platinum crucible containing molten glass is held in platinum crucible clamped by platinum crucible tongs and poured into a brass mold that has been preheated to 315°C. The mold is held at that temperature for 5 hours and then cooled to room temperature in the furnace to achieve the annealing process.
[0035] Glass heat treatment: The annealed glass is placed in a precision annealing furnace for heat treatment for 3 hours at a temperature of 455℃ to obtain fluorine-zinc-aluminum-based microcrystalline glass containing the ZnF2 crystalline phase.
[0036] Example 2
[0037] Glass component raw material preparation: In a glove box filled with inert gas, weigh 20g of raw material according to the molar percentage of the glass component distribution ratio 30ZnF2-15BaF2-15YF3-10SrF2-30AlF3, and add an additional 8g of ammonium bifluoride. After grinding thoroughly in an agate mortar, transfer to a platinum crucible.
[0038] Glass melting: Platinum crucible containing mixed glass raw materials is placed in a muffle furnace at 950°C in air atmosphere and preheated for 30 minutes. The preheated glass liquid is then cooled and transferred to a glove box filled with inert gas environment and heated at the same temperature of 950°C for 3 hours to obtain molten glass liquid.
[0039] Glass casting and annealing: Platinum crucible containing molten glass is held in platinum crucible clamped by platinum crucible tongs and poured into a brass mold that has been preheated to 315°C. The mold is held at that temperature for 5 hours and then cooled to room temperature in the furnace to achieve the annealing process.
[0040] Glass heat treatment: The annealed glass is placed in a precision annealing furnace for heat treatment for 3 hours at a temperature of 455℃ to obtain fluorine-zinc-aluminum-based microcrystalline glass containing the ZnF2 crystalline phase.
[0041] Comparative Example 1
[0042] Glass component raw material preparation: In a glove box filled with inert gas, weigh 20g of raw material according to the molar percentage of the glass component distribution ratio 30ZnF2-15BaF2-12YF3-10SrF2-30AlF3-3ErF3, and add an additional 8g of ammonium bifluoride. Grind thoroughly in an agate mortar and transfer to a platinum crucible.
[0043] Glass melting: Platinum crucible containing mixed glass raw materials is placed in a muffle furnace at 950°C in air atmosphere and preheated for 30 minutes. The preheated glass liquid is then cooled and transferred to a glove box filled with inert gas environment and heated at the same temperature of 950°C for 3 hours to obtain molten glass liquid.
[0044] Glass casting and annealing: Platinum crucible containing molten glass is held in platinum crucible clamps after heating. The molten glass is then poured into a brass mold that has been preheated to 315°C and held at that temperature for 5 hours before being cooled to room temperature in the furnace to achieve the annealing process. After annealing, fluorine-zinc-aluminum matrix glass is obtained.
[0045] Figure 1 The X-ray diffraction patterns of the fluorine-zinc-aluminum based microcrystalline glass containing the ZnF2 crystalline phase prepared in Examples 1 and 2, and the matrix glass prepared in Comparative Example 1 are shown. The characteristic diffraction peaks of ZnF2 can be seen in the figures, indicating that the crystalline phase in the fluorine-zinc-aluminum based microcrystalline glass after heat treatment is the ZnF2 crystalline phase.
[0046] Figure 2 The transmission spectrum of the fluorine-zinc-aluminum-based microcrystalline glass containing the ZnF2 crystalline phase prepared in Example 1 shows that it is transparent from the visible light to the mid-infrared band.
[0047] Figure 3The upconversion emission spectra of the fluorine-zinc-aluminum based microcrystalline glass containing the ZnF2 crystalline phase prepared in Example 1 and the substrate glass prepared in Comparative Example 1 are shown under 980 nm wavelength excitation. It can be seen that the upconversion emission intensity of the fluorine-zinc-aluminum based microcrystalline glass containing the ZnF2 crystalline phase is significantly enhanced.
[0048] Figure 4 and Figure 5 The emission spectra of the fluorine-zinc-aluminum based microcrystalline glass containing ZnF2 crystal phase prepared in Example 1 and the substrate glass prepared in Comparative Example 1 at 1.5 μm and 2.7 μm under 980 nm wavelength excitation are shown respectively. It can be seen that the emission intensity of the fluorine-zinc-aluminum based microcrystalline glass containing ZnF2 crystal phase is significantly enhanced at 1.5 μm and 2.7 μm.
[0049] Figure 6 The emission spectra of the fluorine-zinc-aluminum based microcrystalline glass containing the ZnF2 crystal phase prepared in Example 1 and the substrate glass prepared in Comparative Example 1 at 3.5 μm under excitation at a wavelength of 650 nm are shown. It can be seen that the emission intensity of the fluorine-zinc-aluminum based microcrystalline glass containing the ZnF2 crystal phase at 3.5 μm is enhanced.
[0050] As can be seen from the above embodiments, heat treatment of the fluorine-zinc-aluminum matrix glass results in fluorine-zinc-aluminum microcrystalline glass containing a single ZnF2 crystal phase, thereby enhancing the luminescent properties of the glass.
[0051] The fluorine-zinc-aluminum-based microcrystalline glass containing a single ZnF2 crystal phase of the present invention has a more obvious upconversion and mid-infrared luminescence enhancement effect compared with the substrate glass, and can be applied to fiber optic / glass lighting displays and high-power mid-infrared fiber lasers.
[0052] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.
Claims
1. A fluorine-zinc-aluminum based microcrystalline glass containing a ZnF2 crystalline phase, characterized in that, The molar percentages of its raw material components are: ZnF2 25 to 35 mol%, BaF2 10 to 20 mol%, YF3 10 to 20 mol%, SrF2 5 to 15 mol%, AlF3 25 to 35 mol%, ErF3 0 to 10 mol%. The fluorine-zinc-aluminum-based microcrystalline glass containing the ZnF2 crystalline phase is prepared by obtaining the precursor fluorine-zinc-aluminum-based glass through melt quenching and then by heat treatment. The fluorine-zinc-aluminum-based microcrystalline glass containing the ZnF2 crystalline phase has a single ZnF2 crystalline phase.
2. A method for preparing a fluorine-zinc-aluminum-based microcrystalline glass containing a ZnF2 crystalline phase as described in claim 1, characterized in that, The method includes the following steps: Step 1: In a glove box filled with an inert gas environment, weigh the raw materials according to the raw material composition ratio of the fluorine zinc aluminum-based microcrystalline glass containing ZnF2 crystal phase, and add ammonium bifluoride with a specific gravity of 40% of the raw materials. After grinding thoroughly in an agate mortar, transfer the raw materials to a platinum crucible. Step 2: Place the platinum crucible containing the mixed glass raw materials in a muffle furnace under an air atmosphere for preheating. Then, after cooling the preheated glass liquid, transfer it to a glove box filled with an inert gas environment for reheating to obtain molten glass liquid. The preheating in the muffle furnace in step 2 specifically involves preheating at 950°C for 30 minutes. The reheating of the glove box in step 2 specifically involves heating at 950°C for 3 hours. Step 3: Using platinum crucible tongs, hold the heated platinum crucible containing molten glass, pour the molten glass into a brass mold, keep it at a certain temperature, and then cool it to room temperature in the furnace to complete the annealing process. In step 3, the brass mold has been preheated to 315°C, and the heat preservation time is 5 hours. Step 4: Place the annealed glass into a precision annealing furnace for heat treatment to obtain the fluorine-zinc-aluminum-based microcrystalline glass containing a single ZnF2 crystal phase. The heat treatment in step 4 specifically involves heat treatment at 455~460℃ for 1~3 hours.
3. The method for preparing fluorine-zinc-aluminum based microcrystalline glass containing ZnF2 crystalline phase as described in claim 2, characterized in that, The heat treatment in step 4 specifically involves heat treatment at 455°C for 3 hours.