A radiation-resistant fluorophosphate glass and its preparation method

Abstract

This invention provides a radiation-resistant fluorophosphate glass and its preparation method, relating to the field of glass preparation technology. The fluorophosphate glass, by weight, comprises the following raw materials: Ba(PO3)2 30-48 parts, Sr(PO3)2 6-12 parts, Al(PO3)3 10-16 parts, AlF3 4-8 parts, MgF2 4-8 parts, BaF2 4-10 parts, SrF2 6-10 parts, LiF1-4 parts, and Ce-Gd@LaF3 nanocomposite 0.5-2.0 parts. The Ce-Gd@LaF3 nanocomposite is prepared by the following method: a Ce-Gd co-doped nanocomposite is synthesized using Ce(NO3)3·6H2O and Gd(NO3)3·6H2O, and then LaF3 is coated onto the surface of the Ce-Gd co-doped nanocomposite to obtain the Ce-Gd@LaF3 nanocomposite. A method for preparing a radiation-resistant fluorophosphate glass includes Ce-Gd co-doped nanocomposite synthesis, LaF3 coating, and melting of the co-doped fluorophosphate glass. This invention provides a radiation-resistant fluorophosphate glass with excellent radiation resistance, mechanical properties, and optical properties.

Description

Technical Field

[0001] This invention relates to the field of glass preparation technology, specifically to a radiation-resistant fluorophosphate glass and its preparation method. Background Technology

[0002] In the field of optics, numerous research and applications rely on high-performance glass systems, including early laser glasses for solid-state lasers and more recent fiber amplifiers and upconversion luminescent materials. Fluorophosphate glass, as an emerging glass material, has become a research focus in fields such as luminescent materials and infrared optics due to its low phonon energy and strong ionic bonding. Rare earth ions can be highly doped into fluorophosphate glass, resulting in a wide luminescence range extending from the visible light spectrum to the mid-infrared region. Fluorophosphate glass plays a particularly important role in the research of upconversion luminescent materials and fluorophosphate glass fiber lasers.

[0003] The patent application number 201911024167.0 proposes a radiation-resistant fluorophosphate glass and its preparation method. Although the patent improves the radiation resistance of the glass by doping CeO2 into the fluorophosphate glass, the addition of CeO2 may cause the glass to have a high refractive index, resulting in interface scattering, high brittleness, and easy crack propagation. This reduces the optical and mechanical properties of the glass to a certain extent, and therefore still has certain limitations.

[0004] In summary, although the existing technical solutions have improved some properties of fluorophosphate glass to a certain extent, the following technical problems still exist: poor radiation resistance and inability to simultaneously achieve good mechanical and optical properties. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, this invention provides a radiation-resistant fluorophosphate glass and its preparation method, achieving the following objectives: to achieve efficient doping of Ce-Gd@LaF3 nanocomposite in fluorophosphate glass, thereby preparing a fluorophosphate glass with high radiation resistance, excellent mechanical properties, and optical properties.

[0006] To achieve the above objectives, the following technical solution is adopted:

[0007] A radiation-resistant fluorophosphate glass, by weight, comprises the following raw materials: 30-48 parts Ba(PO3)2, 6-12 parts Sr(PO3)2, 10-16 parts Al(PO3)3, 4-8 parts AlF3, 4-8 parts MgF2, 4-10 parts BaF2, 6-10 parts SrF2, 1-4 parts LiF, and 0.5-2.0 parts Ce-Gd@LaF3 nanocomposite.

[0008] Preferably, the fluorophosphate glass of the present invention, by weight, comprises the following raw materials: 36-44 parts Ba(PO3)2, 7-11 parts Sr(PO3)2, 12-15 parts Al(PO3)3, 5-7 parts AlF3, 6-7 parts MgF2, 5-9 parts BaF2, 7-9 parts SrF2, 3.5 parts LiF2, and 0.7-1.6 parts Ce-Gd@LaF3 nanocomposite.

[0009] The Ce-Gd@LaF3 nanocomposite was prepared by the following method: Ce-Gd co-doped nanocomposite was synthesized with Ce(NO3)3·6H2O and Gd(NO3)3·6H2O, and then LaF3 was coated on the surface of the Ce-Gd co-doped nanocomposite to obtain the Ce-Gd@LaF3 nanocomposite.

[0010] This invention also provides a method for preparing radiation-resistant fluorophosphate glass, comprising the following steps:

[0011] Step 1: Synthesis of Ce-Gd co-doped nanocomposites

[0012] Dissolve Ce(NO3)3·6H2O and Gd(NO3)3·6H2O in deionized water in a specific ratio to prepare a metal nitrate solution with a total metal ion concentration of 0.20-0.25 mol / L, wherein the mass ratio of Ce(NO3)3·6H2O to Gd(NO3)3·6H2O is 1:(0.5-0.7). After stirring the metal nitrate solution thoroughly, slowly add 0.4-0.6 mol / L NH4HCO3 solution to adjust the pH of the reaction system to 9.0-9.5, forming Ce-Gd hydroxide precipitate. After complete precipitation, incubate in a water bath at 60-65℃ for 10-12 hours. After incubation, centrifuge at 8000-9000 rpm for 15-20 minutes. The Ce-Gd hydroxide precipitate was then dried in an oven at 80-85℃ for 11-12 hours, ground, and then transferred to a tube furnace and calcined at 500-550℃ for 3-3.5 hours under a N2 atmosphere to obtain the Ce-Gd co-doped nanocomposite.

[0013] Step 2: LaF3 coating

[0014] Dissolve La(NO3)3·6H2O in anhydrous ethanol to prepare a 0.10-0.12 mol / L La(NO3)3 solution, and dissolve NH4F in anhydrous ethanol to prepare a 0.14-0.16 mol / L NH4F solution.

[0015] Ce-Gd co-doped nanocomposites were added to La(NO3)3 solution and ultrasonically dispersed until homogeneous. Then, NH4F solution was added dropwise to the reaction system, and the reaction was carried out at room temperature for 2-2.5 h. The mass ratio of Ce-Gd co-doped nanocomposites, NH4F solution, and La(NO3)3 solution was (15-18):(3-3.6):1. After the reaction, the initial coated particles were obtained by centrifugation at 10000-11000 rpm for 20-30 min. The initial coated particles were then annealed at 350-360℃ for 1-1.5 h in a N2 atmosphere to obtain Ce-Gd@LaF3 nanocomposites.

[0016] Step 3: Melting of co-doped fluorophosphate glass

[0017] After heating the high-temperature furnace to 800-850℃, Ba(PO3)2, Sr(PO3)2, Al(PO3)3, AlF3, MgF2, BaF2, SrF2, and LiF are mixed evenly and divided into three equal parts. The mixture is added to the high-temperature furnace in three batches, with an interval of 10-15 minutes between each batch. After all the mixture has been added, it is melted under a N2 atmosphere for 60-70 minutes. Then, Ce-Gd@LaF3 nanocomposite is added, mixed evenly, and allowed to stand for 30-40 minutes to obtain a clear and homogenized glass melt.

[0018] The clarified and homogenized molten glass is poured into a preheated copper mold at 300-350℃; then it is transferred to liquid nitrogen for quenching to form a transparent glass block, which is then annealed to obtain Ce-Gd@LaF3 co-doped fluorophosphate glass. The annealing process involves heating the glass block to 450-500℃ at a rate of 1-2℃ / min, holding it at that temperature for 5-6 hours, and then cooling it to room temperature at a rate of 1-1.5℃ / min.

[0019] The beneficial effects of this invention are as follows:

[0020] (1) The present invention provides a radiation-resistant fluorophosphate glass with excellent radiation resistance, achieving a radiation dose resistance of 1.01 × 10⁻⁶. 5 -1.62×10 5 Rad(Si) still maintains high light transmittance after being irradiated with a dose of 50 Krad(Si) gamma rays. The radiation resistance is greatly improved by incorporating Ce-Gd@LaF3 nanocomposite into fluorophosphate glass.

[0021] (2) The present invention provides a radiation-resistant fluorophosphate glass with good optical properties, a dispersion value of 0.00674-0.00703, and a refractive index n. dWith a value of 1.51587-1.51692, the low dispersion value and low refractive index can significantly reduce chromatic aberration in the optical system and reduce the degree of light bending at the interface. The transmittance reaches 90.9-92.2%. High transmittance means that the loss of light when passing through the glass is minimal and the light passes through more uniformly.

[0022] (3) The radiation-resistant fluorophosphate glass of the present invention has good mechanical properties, with a hardness of 529-588 Hv and a fracture toughness of 0.09-1.12 MPa·m. 1 / 2 The high hardness and fracture toughness can ensure the integrity of the glass surface and the processing precision, and improve the impact resistance and crack resistance. Attached Figure Description

[0023] Appendix Figure 1 This is a graph showing the light transmittance of the radiation-resistant fluorophosphate glass of the present invention before and after radiation.

[0024] Appendix Figure 2 A is a transmission electron microscope image of the Ce-Gd co-doped nanocomposite prepared in this invention.

[0025] Appendix Figure 2 B is a transmission electron microscope image of the Ce-Gd@LaF3 nanocomposite prepared in this invention. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of the present invention clearer, the embodiments of the present invention will be described in further detail below. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0027] Example 1: A radiation-resistant fluorophosphate glass and its preparation method

[0028] A radiation-resistant fluorophosphate glass, by weight, comprises the following raw materials: 30 parts Ba(PO3)2, 12 parts Sr(PO3)2, 16 parts Al(PO3)3, 4 parts AlF3, 4 parts MgF2, 10 parts BaF2, 10 parts SrF2, 1 part LiF, and 0.5 parts Ce-Gd@LaF3 nanocomposite.

[0029] A method for preparing a radiation-resistant fluorophosphate glass, comprising the following steps:

[0030] Step 1: Synthesis of Ce-Gd co-doped nanocomposites

[0031] Ce(NO3)3·6H2O and Gd(NO3)3·6H2O were dissolved in deionized water in a specific ratio to prepare a metal nitrate solution with a total metal ion concentration of 0.20 mol / L, wherein the mass ratio of Ce(NO3)3·6H2O to Gd(NO3)3·6H2O was 1:0.5. After the metal nitrate solution was stirred evenly, a 0.4 mol / L NH4HCO3 solution was slowly added dropwise to adjust the pH of the reaction system to 9.0, forming a Ce-Gd hydroxide precipitate. After the precipitation was complete, the mixture was kept in a water bath at 60℃ for 10 h. After the incubation was complete, the mixture was centrifuged at 8000 rpm for 15 min. The Ce-Gd hydroxide precipitate was then dried in an oven at 80℃ for 11 h, ground, and then calcined in a tube furnace at 500℃ for 3.5 h under a N2 atmosphere to obtain a Ce-Gd co-doped nanocomposite.

[0032] Step 2: LaF3 coating

[0033] Dissolve La(NO3)3·6H2O in anhydrous ethanol to prepare a 0.10 mol / L La(NO3)3 solution, and dissolve NH4F in anhydrous ethanol to prepare a 0.14 mol / L NH4F solution.

[0034] Ce-Gd co-doped nanocomposites were added to La(NO3)3 solution and ultrasonically dispersed until homogeneous. Then, NH4F solution was added dropwise to the reaction system, and the reaction was carried out at room temperature for 2 h. The mass ratio of Ce-Gd co-doped nanocomposites, NH4F solution, and La(NO3)3 solution was 15:3:1. After the reaction, the initial coated particles were obtained by centrifugation at 10,000 rpm for 20 min. The initial coated particles were then annealed at 350 °C for 1.5 h in a N2 atmosphere to obtain Ce-Gd@LaF3 nanocomposites.

[0035] Step 3: Melting of co-doped fluorophosphate glass

[0036] After the high-temperature furnace is heated to 800℃, Ba(PO3)2, Sr(PO3)2, Al(PO3)3, AlF3, MgF2, BaF2, SrF2, and LiF are mixed evenly and divided into three equal parts. The mixture is added to the high-temperature furnace in three batches, with an interval of 10 minutes between each batch. After all the mixture is added, it is melted under a N2 atmosphere for 60 minutes. Then, Ce-Gd@LaF3 nanocomposite is added, mixed evenly, and allowed to stand for 30 minutes to obtain a clear and homogenized glass melt.

[0037] The clarified and homogenized molten glass was poured into a preheated copper mold at 300°C; then transferred to liquid nitrogen for quenching to form a transparent glass block, which was then annealed to obtain Ce-Gd@LaF3 co-doped fluorophosphate glass. The annealing process involved heating the glass block to 450°C at a rate of 1°C / min, holding it at that temperature for 5 hours, and then cooling it to room temperature at a rate of 1°C / min.

[0038] Example 2: A radiation-resistant fluorophosphate glass and its preparation method

[0039] A radiation-resistant fluorophosphate glass, by weight, comprises the following raw materials: 36 parts Ba(PO3)2, 11 parts Sr(PO3)2, 15 parts Al(PO3)3, 5 parts AlF3, 6 parts MgF2, 9 parts BaF2, 9 parts SrF2, 2 parts LiF2, and 0.7 parts Ce-Gd@LaF3 nanocomposite.

[0040] A method for preparing a radiation-resistant fluorophosphate glass, comprising the following steps:

[0041] Step 1: Synthesis of Ce-Gd co-doped nanocomposites

[0042] Ce(NO3)3·6H2O and Gd(NO3)3·6H2O were dissolved in deionized water in a specific ratio to prepare a metal nitrate solution with a total metal ion concentration of 0.20 mol / L, wherein the mass ratio of Ce(NO3)3·6H2O to Gd(NO3)3·6H2O was 1:0.5. After stirring the metal nitrate solution for 30 min, a 0.45 mol / L NH4HCO3 solution was slowly added dropwise to adjust the pH of the reaction system to 9.0, generating Ce-Gd hydroxide precipitate. After complete precipitation, the solution was kept in a water bath at 60℃ for 10.5 h. After the incubation period, the solution was centrifuged at 8000 rpm for 16 min. The Ce-Gd hydroxide precipitate was then dried in an oven at 80℃ for 11 h, ground, and then calcined in a tube furnace at 500℃ for 3.5 h under a N2 atmosphere to obtain the Ce-Gd co-doped nanocomposite.

[0043] Step 2: LaF3 coating

[0044] Dissolve La(NO3)3·6H2O in anhydrous ethanol to prepare a 0.10 mol / L La(NO3)3 solution, and dissolve NH4F in anhydrous ethanol to prepare a 0.14 mol / L NH4F solution.

[0045] Ce-Gd co-doped nanocomposite was added to La(NO3)3 solution and ultrasonically dispersed until homogeneous. Then, NH4F solution was added dropwise to the reaction system, and the reaction was carried out at room temperature for 2 h. The mass ratio of Ce-Gd co-doped nanocomposite, NH4F solution, and La(NO3)3 solution was 16:3.3:1. After the reaction, the initial coated particles were obtained by centrifugation at 10,000 rpm for 20 min. The initial coated particles were then annealed at 350 °C for 1.5 h in a N2 atmosphere to obtain Ce-Gd@LaF3 nanocomposite.

[0046] Step 3: Melting of co-doped fluorophosphate glass

[0047] After the high-temperature furnace is heated to 800℃, Ba(PO3)2, Sr(PO3)2, Al(PO3)3, AlF3, MgF2, BaF2, SrF2, and LiF are mixed evenly and divided into three equal parts. The mixture is added to the high-temperature furnace in three batches, with an interval of 12 minutes between each batch. After all the mixture is added, it is melted under a N2 atmosphere for 60 minutes. Then, Ce-Gd@LaF3 nanocomposite is added and mixed evenly. The mixture is allowed to stand for 30 minutes to obtain a clear and homogenized glass melt.

[0048] The clarified and homogenized molten glass was poured into a preheated copper mold at 300°C; then transferred to liquid nitrogen for quenching to form a transparent glass block, which was then annealed to obtain Ce-Gd@LaF3 co-doped fluorophosphate glass. The annealing process involved heating the glass block to 450°C at a rate of 1°C / min, holding it at that temperature for 5.5 hours, and then cooling it to room temperature at a rate of 1°C / min.

[0049] Example 3: A radiation-resistant fluorophosphate glass and its preparation method

[0050] A radiation-resistant fluorophosphate glass, by weight, comprises the following raw materials: 240 parts Ba(PO3)2, 29 parts Sr(PO3)2, 13 parts Al(PO3)3, 6 parts AlF3, 6.5 parts MgF2, 7 parts BaF2, 28 parts SrF2, 3 parts LiF3, and 1.2 parts Ce-Gd@LaF3 nanocomposite.

[0051] A method for preparing a radiation-resistant fluorophosphate glass, comprising the following steps:

[0052] Step 1: Synthesis of Ce-Gd co-doped nanocomposites

[0053] Ce(NO3)3·6H2O and Gd(NO3)3·6H2O were dissolved in deionized water in a specific ratio to prepare a metal nitrate solution with a total metal ion concentration of 0.25 mol / L, wherein the mass ratio of Ce(NO3)3·6H2O to Gd(NO3)3·6H2O was 1:0.6. After the metal nitrate solution was stirred evenly, a 0.5 mol / L NH4HCO3 solution was slowly added dropwise to adjust the pH of the reaction system to 9.0, forming a Ce-Gd hydroxide precipitate. After the precipitation was complete, the mixture was kept in a water bath at 65℃ for 11 h. After the incubation period, the mixture was centrifuged at 8500 rpm for 18 min. The Ce-Gd hydroxide precipitate was then dried in an oven at 83℃ for 11.5 h, ground, and then calcined in a tube furnace at 530℃ for 3 h under a N2 atmosphere to obtain a Ce-Gd co-doped nanocomposite.

[0054] Step 2: LaF3 coating

[0055] Dissolve La(NO3)3·6H2O in anhydrous ethanol to prepare a 0.11 mol / L La(NO3)3 solution, and dissolve NH4F in anhydrous ethanol to prepare a 0.15 mol / L NH4F solution.

[0056] Ce-Gd co-doped nanocomposite was added to La(NO3)3 solution and ultrasonically dispersed until homogeneous. Then, NH4F solution was added dropwise to the reaction system, and the reaction was carried out at room temperature for 2.5 h. The mass ratio of Ce-Gd co-doped nanocomposite, NH4F solution, and La(NO3)3 solution was 16:3.3:1. After the reaction, the initially coated particles were obtained by centrifugation at 11000 rpm for 25 min. The initially coated particles were then annealed at 350 °C for 1.5 h in a N2 atmosphere to obtain Ce-Gd@LaF3 nanocomposite.

[0057] Step 3: Melting of co-doped fluorophosphate glass

[0058] After the high-temperature furnace is heated to 830℃, Ba(PO3)2, Sr(PO3)2, Al(PO3)3, AlF3, MgF2, BaF2, SrF2, and LiF are mixed evenly and divided into three equal parts. The mixture is added to the high-temperature furnace in three batches, with an interval of 12 minutes between each batch. After all the mixture is added, it is melted under a N2 atmosphere for 65 minutes. Then, Ce-Gd@LaF3 nanocomposite is added and mixed evenly. The mixture is allowed to stand for 35 minutes to obtain a clear and homogenized glass melt.

[0059] The clarified and homogenized molten glass was poured into a preheated copper mold at 320°C; then transferred to liquid nitrogen for quenching to form a transparent glass block, which was then annealed to obtain Ce-Gd@LaF3 co-doped fluorophosphate glass. The annealing process involved heating the glass block to 480°C at a rate of 1.5°C / min, holding it at that temperature for 5.5 hours, and then cooling it to room temperature at a rate of 1.5°C / min.

[0060] Example 4: A radiation-resistant fluorophosphate glass and its preparation method

[0061] A radiation-resistant fluorophosphate glass, by weight, comprises the following raw materials: 44 parts Ba(PO3)2, 27 parts Sr(PO3)2, 12 parts Al(PO3)3, 37 parts AlF3, 27 parts MgF2, 25 parts BaF2, 27 parts SrF2, 3.5 parts LiF, and 1.6 parts Ce-Gd@LaF3 nanocomposite.

[0062] A method for preparing a radiation-resistant fluorophosphate glass, comprising the following steps:

[0063] Step 1: Synthesis of Ce-Gd co-doped nanocomposites

[0064] Ce(NO3)3·6H2O and Gd(NO3)3·6H2O were dissolved in deionized water in a specific ratio to prepare a metal nitrate solution with a total metal ion concentration of 0.25 mol / L, wherein the mass ratio of Ce(NO3)3·6H2O to Gd(NO3)3·6H2O was 1:0.7. After stirring the metal nitrate solution evenly, a 0.55 mol / L NH4HCO3 solution was slowly added dropwise to adjust the pH of the reaction system to 9.5, generating Ce-Gd hydroxide precipitate. After complete precipitation, the solution was kept in a water bath at 65℃ for 11.5 h. After the incubation period, the solution was centrifuged at 9000 rpm for 19 min. The Ce-Gd hydroxide precipitate was then dried in an oven at 84℃ for 12 h, ground, and then calcined in a tube furnace at 550℃ for 3 h under a N2 atmosphere to obtain the Ce-Gd co-doped nanocomposite.

[0065] Step 2: LaF3 coating

[0066] Dissolve La(NO3)3·6H2O in anhydrous ethanol to prepare a 0.12 mol / L La(NO3)3 solution, and dissolve NH4F in anhydrous ethanol to prepare a 0.16 mol / L NH4F solution.

[0067] Ce-Gd co-doped nanocomposite was added to La(NO3)3 solution and ultrasonically dispersed until homogeneous. Then, NH4F solution was added dropwise to the reaction system, and the reaction was carried out at room temperature for 2.5 h. The mass ratio of Ce-Gd co-doped nanocomposite, NH4F solution, and La(NO3)3 solution was 17:3.5:1. After the reaction, the initial coated particles were obtained by centrifugation at 11000 rpm for 30 min. The initial coated particles were then annealed at 360 °C for 1 h in a N2 atmosphere to obtain Ce-Gd@LaF3 nanocomposite.

[0068] Step 3: Melting of co-doped fluorophosphate glass

[0069] After the high-temperature furnace is heated to 830℃, Ba(PO3)2, Sr(PO3)2, Al(PO3)3, AlF3, MgF2, BaF2, SrF2, and LiF are mixed evenly and divided into three equal parts. The mixture is added to the high-temperature furnace in three batches, with an interval of 12 minutes between each batch. After all the mixture is added, it is melted under a N2 atmosphere for 70 minutes. Then, Ce-Gd@LaF3 nanocomposite is added and mixed evenly. The mixture is allowed to stand for 40 minutes to obtain a clear and homogenized glass melt.

[0070] The clarified and homogenized molten glass was poured into a preheated copper mold at 350°C; then transferred to liquid nitrogen for quenching to form a transparent glass block, which was then annealed to obtain Ce-Gd@LaF3 co-doped fluorophosphate glass. The annealing process involved heating the glass block to 500°C at a heating rate of 2°C / min, holding it at that temperature for 5.5 hours, and then cooling it to room temperature at a cooling rate of 1.5°C / min.

[0071] Example 5: A radiation-resistant fluorophosphate glass and its preparation method

[0072] A radiation-resistant fluorophosphate glass, by weight, comprises the following raw materials: 248 parts Ba(PO3)2, 26 parts Sr(PO3)2, 10 parts Al(PO3)3, 38 parts AlF3, 28 parts MgF2, 4 parts BaF2, 26 parts SrF2, 4 parts LiF, and 2.0 parts Ce-Gd@LaF3 nanocomposite.

[0073] A method for preparing a radiation-resistant fluorophosphate glass, comprising the following steps:

[0074] Step 1: Synthesis of Ce-Gd co-doped nanocomposites

[0075] Ce(NO3)3·6H2O and Gd(NO3)3·6H2O were dissolved in deionized water in a specific ratio to prepare a metal nitrate solution with a total metal ion concentration of 0.25 mol / L, wherein the mass ratio of Ce(NO3)3·6H2O to Gd(NO3)3·6H2O was 1:0.7. After the metal nitrate solution was stirred evenly, a 0.6 mol / L NH4HCO3 solution was slowly added dropwise to adjust the pH of the reaction system to 9.5, generating Ce-Gd hydroxide precipitate. After precipitation was complete, the mixture was kept in a water bath at 65℃ for 12 h. After the incubation period, the mixture was centrifuged at 9000 rpm for 20 min. The Ce-Gd hydroxide precipitate was then dried in an oven at 85℃ for 12 h, ground, and then calcined in a tube furnace at 550℃ for 3 h under a N2 atmosphere to obtain the Ce-Gd co-doped nanocomposite.

[0076] Step 2: LaF3 coating

[0077] Dissolve La(NO3)3·6H2O in anhydrous ethanol to prepare a 0.12 mol / L La(NO3)3 solution, and dissolve NH4F in anhydrous ethanol to prepare a 0.16 mol / L NH4F solution.

[0078] Ce-Gd co-doped nanocomposite was added to La(NO3)3 solution and ultrasonically dispersed until homogeneous. Then, NH4F solution was added dropwise to the reaction system, and the reaction was carried out at room temperature for 2.5 h. The mass ratio of Ce-Gd co-doped nanocomposite, NH4F solution, and La(NO3)3 solution was 18:3.6:1. After the reaction, the initially coated particles were obtained by centrifugation at 11000 rpm for 30 min. The initially coated particles were then annealed at 360 °C for 1 h in a N2 atmosphere to obtain Ce-Gd@LaF3 nanocomposite.

[0079] Step 3: Melting of co-doped fluorophosphate glass

[0080] After the high-temperature furnace is heated to 850℃, Ba(PO3)2, Sr(PO3)2, Al(PO3)3, AlF3, MgF2, BaF2, SrF2, and LiF are mixed evenly and divided into three equal parts. The mixture is added to the high-temperature furnace in three batches, with an interval of 15 minutes between each batch. After all the mixture is added, it is melted under a N2 atmosphere for 70 minutes. Then, Ce-Gd@LaF3 nanocomposite is added and mixed evenly. The mixture is allowed to stand for 40 minutes to obtain a clear and homogenized glass melt.

[0081] The clarified and homogenized molten glass was poured into a preheated copper mold at 350°C; then transferred to liquid nitrogen for quenching to form a transparent glass block, which was then annealed to obtain Ce-Gd@LaF3 co-doped fluorophosphate glass. The annealing process involved heating the glass block to 500°C at a heating rate of 2°C / min, holding it at that temperature for 6 hours, and then cooling it to room temperature at a cooling rate of 1.5°C / min.

[0082] Example 6 Performance Test

[0083] (a) The optical properties of the fluorophosphate glass prepared in Examples 1-5 were tested, including dispersion value, refractive index and transmittance. The specific test results are shown in Table 1.

[0084] Table 1

[0085]

[0086] As shown in Table 1, Examples 1-5 exhibit good optical performance, with dispersion values ​​ranging from 0.00674 to 0.00703 and refractive index n. d The dispersion value reaches 1.51587-1.51692, and the light transmittance reaches 90.9-92.2%. A low dispersion value means that the glass has a small difference in refractive index for different wavelengths of light, which can significantly reduce chromatic aberration in the optical system. A low refractive index can reduce the degree of light bending at the interface, allowing for the design of thinner or less curved lenses, thereby reducing the size and weight of the optical system. High light transmittance means that the loss of light when passing through the glass is minimal, the light transmission is more uniform, and it performs better in low-light environments.

[0087] (ii) The mechanical properties of hardness and fracture toughness of the fluorophosphate glass prepared in Examples 1-5 were tested. The samples were prepared as square specimens with a side length of 40 mm and a thickness of 1 mm. The specific test results are shown in Table 2.

[0088] Table 2

[0089]

[0090] As shown in Table 2, Examples 1-5 exhibit good mechanical properties, with a hardness of 529-588 Hv and a fracture toughness of 0.09-1.12 MPa·m. 1 / 2 Hardness and fracture toughness are core indicators for measuring the mechanical properties and reliability of fluorophosphate glass, and are of great significance for its application in radiation-resistant optical devices. Higher hardness and fracture toughness can ensure the integrity of the glass surface and processing accuracy, and improve its impact resistance and crack resistance.

[0091] (III) The radiation resistance of the fluorophosphate glass prepared in Examples 1-5 was tested at an irradiation dose rate of 40 rad(Si) / s. The specific test results are shown in Table 3.

[0092] Table 3

[0093]

[0094] As shown in Table 3, Examples 1-5 exhibit excellent radiation resistance, with a radiation dose resistance of 1.01 × 10⁻⁶. 5 -1.62×10 5 Radiation resistance of rad(Si) is greatly improved by incorporating Ce-Gd@LaF3 nanocomposite into fluorophosphate glass.

[0095] (iv) Testing the transmittance of the radiation-resistant fluorophosphate glass of this invention before and after irradiation with 50 klad(Si) gamma rays. The test results of the transmittance before and after irradiation are as follows: Figure 1 As shown, after being irradiated with a dose of 50 klad(Si) gamma rays, the radiation-resistant fluorophosphate glass of this invention still maintains a high light transmittance.

[0096] In summary, the testing and analysis of optical, mechanical, and radiation resistance properties demonstrate that the radiation-resistant fluorophosphate glass of this invention possesses excellent optical, mechanical, and radiation resistance properties. It is particularly suitable for applications in aerospace optics, nuclear industry and radiation detection, precision optical instruments, and special lenses.

[0097] Obviously, there are many other possible implementation methods under the concept of this invention. It should be stated here that any changes made under the inventive concept of this invention will fall within the protection scope of this invention.

Claims

1. A radiation-resistant fluorophosphate glass, characterized in that: The fluorophosphate glass, by weight, comprises the following raw materials: 30-48 parts Ba(PO3)2, 6-12 parts Sr(PO3)2, 10-16 parts Al(PO3)3, 4-8 parts AlF3, 4-8 parts MgF2, 4-10 parts BaF2, 6-10 parts SrF2, 1-4 parts LiF, and 0.5-2.0 parts Ce-Gd@LaF3 nanocomposite. The method for preparing the fluorophosphate glass includes the steps of synthesizing Ce-Gd co-doped nanocomposite, LaF3 coating, and melting co-doped fluorophosphate glass. The Ce-Gd co-doped nanocomposite was synthesized by dissolving Ce(NO3)3·6H2O and Gd(NO3)3·6H2O in deionized water, stirring until homogeneous, adjusting the pH of the reaction system to alkaline to generate Ce-Gd hydroxide precipitate, which was then heated in a water bath, centrifuged, dried, and then calcined in a tube furnace. The LaF3 coating process involves dissolving La(NO3)3·6H2O and NH4F in anhydrous ethanol to form La(NO3)3 and NH4F solutions, respectively. The Ce-Gd co-doped nanocomposite is then added to the La(NO3)3 solution and dispersed evenly. The NH4F solution is then added dropwise. After the reaction is complete, the nanocomposite is centrifuged to obtain the initial coated particles. The initial coated particles are then annealed to obtain the Ce-Gd@LaF3 nanocomposite. The co-doped fluorophosphate glass melting process involves heating the glass in a high-temperature furnace to 800-850°C, then mixing Ba(PO3)2, Sr(PO3)2, Al(PO3)3, AlF3, MgF2, BaF2, SrF2, and LiF evenly, adding the mixture to the furnace, and melting it under a N2 atmosphere for 60-70 minutes. Ce-Gd@LaF3 nanocomposite is then added, mixed evenly, and allowed to stand for 30-40 minutes to obtain a clear and homogenized glass melt.

2. The radiation-resistant fluorophosphate glass according to claim 1, characterized in that: The fluorophosphate glass, by weight, comprises the following raw materials: 36-44 parts Ba(PO3)2, 7-11 parts Sr(PO3)2, 12-15 parts Al(PO3)3, 5-7 parts AlF3, 6-7 parts MgF2, 5-9 parts BaF2, 7-9 parts SrF2, 2-3.5 parts LiF2, and 0.7-1.6 parts Ce-Gd@LaF3 nanocomposite.

3. The radiation-resistant fluorophosphate glass according to claim 1, characterized in that: The mass ratio of Ce(NO3)3·6H2O to Gd(NO3)3·6H2O is 1:(0.5-0.7).

4. The radiation-resistant fluorophosphate glass according to claim 1, characterized in that: The calcination process involves a calcination temperature of 500-550℃ and a calcination time of 3-3.5 hours.

5. The radiation-resistant fluorophosphate glass according to claim 1, characterized in that: In the synthesis step of the Ce-Gd co-doped nanocomposite, the pH value of the reaction system was adjusted by using NH4HCO3 solution to adjust the pH value of the reaction system to 9.0-9.

5.

6. The radiation-resistant fluorophosphate glass according to claim 1, characterized in that: The initial annealing of the LaF3 coated particles in the process is carried out at a temperature of 350-360℃ for 1-1.5 hours.

7. The radiation-resistant fluorophosphate glass according to claim 1, characterized in that: The co-doped fluorophosphate glass melting step further includes: pouring the clarified and homogenized glass melt into a preheated copper mold, then transferring it to liquid nitrogen for quenching to form a transparent glass block, and then performing annealing treatment; the temperature of the preheated copper mold is 300-350℃.

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