A terbium-doped fluorescent glass and a method for regulating the intensity of the violet emission band thereof

Abstract

The application belongs to the technical field of fluorescent glass, and relates to a terbium-doped fluorescent glass and a method for regulating the intensity of a purple light emission band of the fluorescent glass. The effective component is calculated by mole fraction, and the effective component comprises: SiO2 45-55 parts, a first oxide 8-16 parts, a second oxide 10-20 parts, ZnO 5-12 parts, a fluoride 10-20 parts, and Tb4O7 0.05-0.1 parts; wherein the first oxide is one or more of Al2O3, B2O3, P2O5 and Li2O; the second oxide is CaO and / or Na2O; and the fluoride is CaF2 and / or NaF. 3+ ions 5 D3 excited state to the ground state, thereby adjusting the fluorescent performance of the fluorescent glass, avoiding the addition of rare earth elements or noble metals, and being low in cost.

Description

Technical Field

[0001] This invention belongs to the field of fluorescent glass technology, and relates to a terbium-doped fluorescent glass and a method for controlling the intensity of its violet emission band. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Tb 3+ Doped fluorescent glasses exhibit high luminescence intensity and good transparency, making them valuable for applications in X-ray imaging, scintillation materials, nuclear technology, LED lighting, and display devices. Tb 3+ The fluorescence emission of doped glass mainly originates from Tb 3+ ion 5 D3 and 5 The electronic transition from the D4 excited state to the ground state mainly produces violet, blue, green, orange, and red light emission bands. Tb 3+ Ion-doped fluorescent glasses generally exhibit the following emission bands in the visible light region of 400-650 nm, with emission peak positions located at ~415 nm respectively. 5 D3→ 7 F5), ~437nm ( 5 D3→ 7 F4), ~488nm 5 D4→ 7 F6), ~543nm ( 5 D4→ 7 F5), ~585nm 5 D4→ 7 F4), ~623nm ( 5 D4→ 7 F3).

[0004] According to the inventor's research and understanding, current technologies for Tb 3+ The modulation of the luminescence properties of ion-doped fluorescent glasses mainly involves Gd 3+ Ce 3+ For Tb 3+ Sensitization and the local enhancement effect of silver nanoparticles can improve fluorescence intensity. However, this method of adding rare earth elements or noble metals to modify the luminescence properties of fluorescent glasses is costly. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a terbium-doped fluorescent glass and a method for controlling the intensity of its violet emission band. The terbium-doped fluorescent glass provided by this invention can control the Tb content by adjusting the matrix composition.3+ ion 5 The electronic transition from the D3 excited state to the ground state is used to adjust the fluorescence properties of fluorescent glass, avoiding the need to add rare earth elements or precious metals, thus reducing costs.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows:

[0007] On the one hand, a terbium-doped fluorescent glass, based on the molar parts of the effective components, includes: 45-55 parts of SiO2, 8-16 parts of the first oxide, 10-20 parts of the second oxide, 5-12 parts of ZnO, 10-20 parts of fluoride, and 0.05-0.1 parts of Tb4O7;

[0008] Wherein, the first oxide is one or more of Al2O3, B2O3, P2O5, and Li2O; the second oxide is CaO and / or Na2O; and the fluoride is CaF2 and / or NaF.

[0009] Its preparation method includes the following steps:

[0010] Mix all raw materials evenly according to the molar ratio of the effective components to obtain glass batch material;

[0011] The glass batch is heated to 1450-1550°C and melted to obtain molten glass.

[0012] The molten glass is cooled and shaped, and then annealed at 420-500°C to obtain the final product.

[0013] This invention, by adjusting the component ratios of the first oxide, selecting the second oxide, and choosing the fluoride in the glass matrix, can achieve Tb based on the aforementioned preparation method. 3+ ion 5 Electronic transitions from the D3 excited state to the ground state can be modulated to adjust the fluorescence properties of the material; by precisely designing the glass matrix composition, crystal precipitation during the cooling process of the glass melt can be achieved, modulating the Tb-derived fluorescence. 3+5 D3→ 7 F5 and 5 D3→ 7 The electron transition of F4 causes a change in the intensity of the corresponding emission band.

[0014] The fluorescent glass provided by this invention has excellent optical properties. The fluorescent glass prepared by this method has uniform light emission, is easy to process, and has high luminous efficiency. Therefore, on the other hand, the technical solution is: the application of the above-mentioned terbium-doped fluorescent glass in LED light-emitting devices, artistic decoration, color display, X-ray imaging, scintillation materials or nuclear technology.

[0015] Thirdly, a method for controlling the intensity of the violet emission band of a terbium-doped fluorescent glass includes the following steps:

[0016] The raw materials are mixed evenly according to the molar ratio of the effective components, and the composition of the first oxide, the second oxide and the fluoride in the effective components are adjusted to obtain the glass batch material.

[0017] The glass batch is heated to 1450-1550°C and melted to obtain molten glass.

[0018] The molten glass is cooled and shaped, and then annealed at 420-500°C to obtain the final product.

[0019] The raw materials, based on the effective components, have a molar ratio of SiO2, the first oxide, the second oxide, ZnO, fluoride, and Tb4O7 of 45–55:8–16:10–20:5–12:10–20:0.05–0.1; the first oxide is selected from one or more combinations of Al2O3, B2O3, P2O5, and Li2O; the second oxide is selected from one or two combinations of CaO and Na2O; and the fluoride is selected from one or two combinations of CaF2 and NaF.

[0020] The beneficial effects of this invention are as follows:

[0021] This invention uses SiO2-first oxide-second oxide-ZnO-fluoride as a glass matrix, doped with rare earth ions Tb. 3+ As the luminescent center, fluorescent glass, manufactured through melting, cooling, and annealing, can efficiently absorb excitation light and emit visible light under ultraviolet excitation. This invention, through the selection and formulation of the first oxide, second oxide, and fluoride components, can alter Tb. 3+ ion 5 The electronic transition from the D3 excited state to the ground state is used to adjust the fluorescence properties of the fluorescent glass. Precise design of the composition of the first oxide, second oxide, and fluoride allows for crystal precipitation during the cooling process of the glass melt, thus controlling the fluorescence properties derived from Tb. 3+5 D3→ 7 F5 and 5 D3→ 7 The electron transition of F4 alters the intensity of the corresponding emission band. The various components of this invention complement each other, working synergistically to enable the glass of this invention to exhibit controllable fluorescence properties. Attached Figure Description

[0022] 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 improper limitation of the invention.

[0023] Figure 1 The emission spectra of the glasses prepared in Examples 1, 2 and 3 under excitation at a wavelength of 378 nm are shown.

[0024] Figure 2 The emission spectra of the glasses prepared in Examples 4 and 5 under excitation at a wavelength of 378 nm are shown.

[0025] Figure 3 The emission spectra of the glasses prepared in Examples 1 and 6 under excitation at a wavelength of 378 nm are shown.

[0026] Figure 4 The emission spectra of the glasses prepared in Examples 6 and 7 under excitation at a wavelength of 378 nm.

[0027] Figure 5 X-ray diffraction patterns of the glasses prepared in Examples 6 and 7.

[0028] Figure 6 The emission spectra of the glasses prepared in Examples 1 and 8 under excitation at a wavelength of 378 nm are shown.

[0029] Figure 7 X-ray diffraction patterns of the glasses prepared in Examples 1 and 8. Detailed Implementation

[0030] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0031] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0032] Given the existing Tb 3+ The luminescence properties of ion-doped fluorescent glasses need to be modulated by adding Gd. 3+ Ce 3+ Rare earth elements or precious metals such as silver nanoparticles are used, but their cost is relatively high. This invention proposes a method for controlling the intensity of terbium-doped fluorescent glass and its ultraviolet emission band.

[0033] A typical embodiment of the present invention provides a terbium-doped fluorescent glass, comprising, by molar parts of effective components: 45-55 parts of SiO2, 8-16 parts of the first oxide, 10-20 parts of the second oxide, 5-12 parts of ZnO, 10-20 parts of fluoride, and 0.05-0.1 parts of Tb4O7;

[0034] Wherein, the first oxide is one or more of Al2O3, B2O3, P2O5, and Li2O; the second oxide is CaO and / or Na2O; and the fluoride is CaF2 and / or NaF.

[0035] Its preparation method includes the following steps:

[0036] Mix all raw materials evenly according to the molar ratio of the effective components to obtain glass batch material;

[0037] The glass batch is heated to 1450-1550°C and melted to obtain molten glass.

[0038] The molten glass is cooled and shaped, and then annealed at 420-500°C to obtain the final product.

[0039] In this invention, the raw material with B2O3 as the effective component can be boric acid, etc.; the raw material with Al2O3 as the effective component can be alumina, aluminum hydroxide, etc.; the raw material with P2O5 as the effective component can be ammonium dihydrogen phosphate, diammonium hydrogen phosphate, etc.; the raw material with ZnO as the effective component can be zinc oxide, zinc carbonate, etc.; the raw material with CaO as the effective component can be calcium carbonate, etc.; the raw material with Na2O as the effective component can be sodium carbonate, etc.; and the raw material with Li2O as the effective component can be lithium carbonate, etc.

[0040] In some embodiments, the first oxide is Al2O3, B2O3, Li2O, a combination of Al2O3 and B2O3, a combination of Li2O and B2O3, or a combination of Al2O3 and P2O5.

[0041] In some embodiments, the melting process is as follows: first heating to a first set temperature, then heating to a second set temperature, and then heating to a third set temperature; the first set temperature is 350-450°C, the second set temperature is 950-1050°C, and the third set temperature is 1450-1550°C.

[0042] In one or more embodiments, the heating rate to the second set temperature is higher than the heating rate to the first set temperature and the heating rate to the third set temperature. This method is beneficial for improving the mixing uniformity of the components and enhancing the fluorescence performance of the fluorescent glass.

[0043] In one or more embodiments, the heating rate to the first set temperature is 4.6–5.4 °C / min, the heating rate to the second set temperature is 5.6–6.4 °C / min, and the heating rate to the third set temperature is 4.6–5.4 °C / min.

[0044] In some embodiments, the melting time at 1450–1550°C is 0.5–1.5 hours.

[0045] In some embodiments, the molten glass is added to a preheated mold and cooled to solidify at room temperature. This avoids a large temperature difference between the mold and the molten glass, which could cause the glass to crack.

[0046] In some embodiments, the annealing process takes 1 to 3 hours.

[0047] Another embodiment of the present invention provides an application of the above-mentioned terbium-doped fluorescent glass in LED light-emitting devices, artistic decorations, color displays, X-ray imaging, scintillation materials, or nuclear technology.

[0048] A third embodiment of the present invention provides a method for controlling the intensity of the violet emission band of a terbium-doped fluorescent glass, comprising the following steps:

[0049] The raw materials are mixed evenly according to the molar ratio of the effective components, and the composition of the first oxide, the second oxide and the fluoride in the effective components are adjusted to obtain the glass batch material.

[0050] The glass batch is heated to 1450-1550°C and melted to obtain molten glass.

[0051] The molten glass is cooled and shaped, and then annealed at 420-500°C to obtain the final product.

[0052] The raw materials, based on the effective components, have a molar ratio of SiO2, the first oxide, the second oxide, ZnO, fluoride, and Tb4O7 of 45–55:8–16:10–20:5–12:10–20:0.05–0.1; the first oxide is selected from one or more combinations of Al2O3, B2O3, P2O5, and Li2O; the second oxide is selected from one or two combinations of CaO and Na2O; and the fluoride is selected from one or two combinations of CaF2 and NaF.

[0053] In some embodiments, the first oxide modulating composition includes Al2O3, B2O3, Li2O, a combination of Al2O3 and B2O3, a combination of Li2O and B2O3, or a combination of Al2O3 and P2O5.

[0054] In some embodiments, the melting process is as follows: first heating to a first set temperature, then heating to a second set temperature, and then heating to a third set temperature; the first set temperature is 350-450°C, the second set temperature is 950-1050°C, and the third set temperature is 1450-1550°C.

[0055] In one or more embodiments, the heating rate to the second set temperature is higher than the heating rate to the first set temperature and the heating rate to the third set temperature. This method is beneficial for improving the mixing uniformity of the components and enhancing the fluorescence modulation effect of the fluorescent glass.

[0056] In one or more embodiments, the heating rate to the first set temperature is 4.6–5.4 °C / min, the heating rate to the second set temperature is 5.6–6.4 °C / min, and the heating rate to the third set temperature is 4.6–5.4 °C / min.

[0057] In some embodiments, the melting time at 1450–1550°C is 0.5–1.5 hours.

[0058] In some embodiments, the molten glass is added to a preheated mold and cooled to solidify at room temperature. This avoids a large temperature difference between the mold and the molten glass, which could cause the glass to crack.

[0059] In some embodiments, the annealing process takes 1 to 3 hours.

[0060] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0061] Example 1

[0062] A Tb-doped fluorescent glass, the raw materials of which include the following molar proportions of effective components: SiO2: 50 parts, Al2O3: 12 parts, ZnO: 8 parts, NaF: 15 parts, CaO: 15 parts, Tb4O7: 0.075 parts.

[0063] Its preparation method includes the following steps:

[0064] (1) According to the above glass composition, accurately weigh 13.6546g of silicon dioxide, 5.5615g of aluminum oxide, 2.9596g of zinc oxide, 6.8243g of calcium carbonate, 2.8630g of sodium fluoride and 0.2549g of terbium oxide, and grind and mix these raw materials thoroughly to obtain glass batching material.

[0065] (2) Melting: Pour the glass batch into a corundum crucible, heat it from room temperature to 400°C at a heating rate of 5°C / min, then heat it to 1000°C at a heating rate of 6°C / min, and then heat it to 1500°C at a heating rate of 5°C / min. Melt it at this temperature for 1 hour to obtain glass melt.

[0066] (3) Pour the glass liquid obtained in step (2) into a copper mold that has been preheated to 470°C and cool it at room temperature to form the glass; anneal it at 470°C for 2 hours to obtain the glass.

[0067] The emission spectrum of the sample prepared in this embodiment under 378nm wavelength excitation is as follows: Figure 1 As shown, multiple emission bands originating from Tb are displayed. 3+ ion 5 D3 and 5 Electron transition from the D4 excited state to the ground state. The emission band peak is located at 415 nm ( 5 D3→ 7 F5), 437nm 5 D3→ 7 F4), 488nm 5 D4→ 7 F6), 543nm 5 D4→ 7 F5), 585nm 5 D4→ 7 F4), 623nm 5 D4→ 7 F3).

[0068] Example 2

[0069] A Tb-doped fluorescent glass, the raw materials of which include the following molar proportions of effective components: SiO2: 50 parts, Al2O3: 3 parts, B2O3: 9 parts, CaO: 15 parts, NaF: 15 parts, ZnO: 8 parts, Tb4O7: 0.075 parts.

[0070] Its preparation method includes the following steps:

[0071] (1) According to the above glass composition, accurately weigh 13.3511g of silicon dioxide, 1.3595g of aluminum oxide, 4.9464g of boric acid, 6.6727g of calcium carbonate, 2.7993g of sodium fluoride, 2.8939g of zinc oxide and 0.2492g of terbium oxide, and grind and mix these raw materials thoroughly to obtain glass batch material.

[0072] (2) Melting: Pour the glass batch into a corundum crucible, heat it from room temperature to 400°C at a heating rate of 5°C / min, then heat it to 1000°C at a heating rate of 6°C / min, and then heat it to 1500°C at a heating rate of 5°C / min. Melt it at this temperature for 1 hour to obtain glass melt.

[0073] (3) Pour the glass liquid obtained in step (2) into a copper mold that has been preheated to 470°C and cool it at room temperature to form the glass; anneal it at 470°C for 2 hours to obtain the glass.

[0074] The emission spectrum of the sample prepared in this embodiment under 378nm wavelength excitation is as follows: Figure 1 As shown, the data originates from Tb. 3+ Multiple launch belts.

[0075] Example 3

[0076] A Tb-doped fluorescent glass, the raw materials of which include the following molar proportions of effective components: SiO2: 50 parts, B2O3: 12 parts, CaO: 15 parts, NaF: 15 parts, ZnO: 8 parts, Tb4O7: 0.075 parts.

[0077] Its preparation method includes the following steps:

[0078] (1) According to the above glass composition, accurately weigh 13.3511g of silicon dioxide, 6.5952g of boric acid, 6.6727g of calcium carbonate, 2.7993g of sodium fluoride, 2.8939g of zinc oxide and 0.2492g of terbium oxide, and grind and mix these raw materials thoroughly to obtain glass batching material.

[0079] (2) Melting: Pour the glass batch into a corundum crucible, heat it from room temperature to 400°C at a heating rate of 5°C / min, then heat it to 1000°C at a heating rate of 6°C / min, and then heat it to 1500°C at a heating rate of 5°C / min. Melt it at this temperature for 1 hour to obtain glass melt.

[0080] (3) Pour the glass liquid obtained in step (2) into a copper mold that has been preheated to 470°C and cool it at room temperature to form the glass; anneal it at 470°C for 2 hours to obtain the glass.

[0081] The emission spectrum of the sample prepared in this embodiment under 378nm wavelength excitation is as follows: Figure 1 As shown, the data originates from Tb. 3+ Multiple launch belts. From Figure 1 It can be seen that the peak values ​​are located at 415nm ( 5 D3→ 7 F5), 437nm 5 D3→ 7The emission band intensity of F4 gradually decreased in the order of Examples 1, 2, and 3. This indicates that replacing Al2O3 with B2O3 in the glass matrix composition can suppress Tb. 3+5 The electronic transition from the D3 excited state to the ground state modulates Tb 3+ Intensity of the violet emission band of doped fluorescent glass.

[0082] Example 4

[0083] A Tb-doped fluorescent glass comprises the following molar components: SiO2: 50 parts, Li2O: 12 parts, CaO: 15 parts, NaF: 15 parts, ZnO: 8 parts, and Tb4O7: 0.075 parts.

[0084] Its preparation method includes the following steps:

[0085] (1) According to the above glass composition, accurately weigh 14.3048g of silicon dioxide, 4.2222g of lithium carbonate, 7.1493g of calcium carbonate, 2.9993g of sodium fluoride, 3.1006g of zinc oxide and 0.2670g of terbium oxide, and grind and mix these raw materials thoroughly to obtain glass batching material.

[0086] (2) Melting: Pour the glass batch into a corundum crucible, heat it from room temperature to 400°C at a heating rate of 5°C / min, then heat it to 1000°C at a heating rate of 6°C / min, and then heat it to 1500°C at a heating rate of 5°C / min. Melt it at this temperature for 1 hour to obtain glass melt.

[0087] (3) Pour the glass liquid obtained in step (2) into a copper mold that has been preheated to 470°C and cool it at room temperature to form the glass; anneal it at 470°C for 2 hours to obtain the glass.

[0088] Example 5

[0089] A Tb ion-doped fluorescent glass, the raw materials of which include the following molar proportions of effective components: SiO2: 50 parts, B2O3: 9 parts, Li2O: 3 parts, CaO: 15 parts, NaF: 15 parts, ZnO: 8 parts, Tb4O7: 0.075 parts.

[0090] Its preparation method includes the following steps:

[0091] (1) According to the above glass composition, accurately weigh 13.3511g of silicon dioxide, 4.9464g of boric acid, 0.9852g of lithium carbonate, 6.6727g of calcium carbonate, 2.7993g of sodium fluoride, 2.8939g of zinc oxide and 0.2492g of terbium oxide, and grind and mix these raw materials thoroughly to obtain glass batch material.

[0092] (2) Melting: Pour the glass batch into a corundum crucible, heat it from room temperature to 400°C at a heating rate of 5°C / min, then heat it to 1000°C at a heating rate of 6°C / min, and then heat it to 1500°C at a heating rate of 5°C / min. Melt it at this temperature for 1 hour to obtain glass melt.

[0093] (3) Pour the glass liquid obtained in step (2) into a copper mold that has been preheated to 470°C and cool it at room temperature to form the glass; anneal it at 470°C for 2 hours to obtain the glass.

[0094] The emission spectra of the fluorescent glasses prepared in Examples 4 and 5 under 378 nm excitation are as follows: Figure 2 As shown in the figure, it can be seen that with the increase of Li2O content in the matrix glass composition, the amount of Tb-derived components increases. 3+ ion 5 D3→ 7 F5 and 5 D3→ 7 The emission band intensity of F4 is enhanced, specifically the intensity of the violet emission band with peak values ​​at 415nm and 437nm.

[0095] Example 6

[0096] A Tb-doped fluorescent glass, the raw materials of which include the following molar proportions of effective components: SiO2: 50 parts, Al2O3: 12 parts, CaO: 15 parts, CaF2: 15 parts, ZnO: 8 parts, Tb4O7: 0.075 parts.

[0097] Its preparation method includes the following steps:

[0098] (1) According to the above glass composition, accurately weigh 12.6218g of silicon dioxide, 5.1408g of aluminum oxide, 6.3082g of calcium carbonate, 4.9204g of calcium fluoride, 2.7358g of zinc oxide and 0.2356g of terbium oxide, and grind and mix these raw materials thoroughly to obtain glass batching material.

[0099] (2) Melting: Pour the glass batch into a corundum crucible, heat it from room temperature to 400°C at a heating rate of 5°C / min, then heat it to 1000°C at a heating rate of 6°C / min, and then heat it to 1500°C at a heating rate of 5°C / min. Melt it at this temperature for 1 hour to obtain glass melt.

[0100] (3) Pour the glass liquid obtained in step (2) into a copper mold that has been preheated to 470°C and cool it at room temperature to form the glass; anneal it at 470°C for 2 hours to obtain the glass.

[0101] The emission spectrum of the fluorescent glass prepared in this embodiment under 378nm wavelength excitation is as follows: Figure 3As shown. For ease of comparison, the emission spectrum of Example 1 is also listed below. Figure 3 Example 6 is from Tb. 3+5 D3→ 7 F5 and 5 D3→ 7 The emission band strength of F4 is enhanced compared to Example 1, indicating that replacing NaF with CaF2 in the glass matrix can enhance the emission band strength derived from Tb. 3+5 The electronic transition from the D3 excited state to the ground state results in an enhanced intensity of the violet emission bands with peak values ​​at 415 nm and 437 nm, respectively.

[0102] Example 7

[0103] A Tb-doped fluorescent glass, the raw materials of which include the following molar proportions of effective components: SiO2: 50 parts, Al2O3: 12 parts, Na2O: 15 parts, CaF2: 15 parts, ZnO: 8 parts, Tb4O7: 0.075 parts.

[0104] Its preparation method includes the following steps:

[0105] (1) According to the above glass composition, accurately weigh 12.5167g of silicon dioxide, 5.0980g of aluminum oxide, 6.6244g of sodium carbonate, 4.8794g of calcium fluoride, 2.7130g of zinc oxide and 0.2337g of terbium oxide, and grind and mix these raw materials thoroughly to obtain glass batching material.

[0106] (2) Melting: Pour the glass batch into a corundum crucible, heat it from room temperature to 400°C at a heating rate of 5°C / min, then heat it to 1000°C at a heating rate of 6°C / min, and then heat it to 1500°C at a heating rate of 5°C / min. Melt it at this temperature for 1 hour to obtain glass melt.

[0107] (3) Pour the glass liquid obtained in step (2) into a copper mold that has been preheated to 470°C and cool it at room temperature to form the glass; anneal it at 470°C for 2 hours to obtain the glass.

[0108] The emission spectrum of the fluorescent glass prepared in this embodiment under 378nm wavelength excitation is as follows: Figure 4 As shown. For ease of comparison, the emission spectrum of Example 6 is also listed below. Figure 4 As can be seen from the figure, Example 7 is derived from Tb. 3+5 D3→ 7 F5 and 5 D3→ 7 The emission band intensity of F4 was reduced compared to Example 6, indicating that replacing CaO with NaO in the glass matrix can reduce the amount of Tb-derived radiation. 3+5 Electronic transition from the D3 excited state to the ground state.

[0109] The X-ray diffraction patterns of the samples prepared in Examples 6 and 7 are as follows: Figure 5 As shown.

[0110] The X-ray diffraction pattern of Example 6 showed no diffraction peaks, indicating that the material prepared in this example was in a glassy state. However, the material prepared in Example 7 exhibited obvious diffraction peaks, corresponding to CaF2 crystals (PDF 35-0816). Generally, crystallization in glass requires microcrystallization heat treatment. The X-ray diffraction results of Example 7 show that by precisely designing the composition of the glass matrix, crystal precipitation during the cooling process of the glass melt can be achieved. Figure 4 The emission spectrum shows that the precipitation of the crystal in Example 7 altered Tb. 3+ The local environment suppressed the source of Tb 3+5 D3→ 7 F5 and 5 D3→ 7 The electron transition of F4 reduces the intensity of the corresponding emission band.

[0111] Example 8

[0112] A Tb-doped fluorescent glass, the raw materials of which include the following molar proportions of effective components: SiO2: 50 parts, Al2O3: 6 parts, P2O5: 6 parts, CaO: 15 parts, ZnO: 8 parts, NaF: 15 parts, Tb4O7: 0.075 parts.

[0113] Its preparation method includes the following steps:

[0114] (1) According to the above glass composition, accurately weigh 11.7804g of silicon dioxide, 2.3991g of aluminum oxide, 5.4127g of ammonium dihydrogen phosphate, 5.8876g of calcium carbonate, 2.4700g of sodium fluoride, 2.5534g of zinc oxide and 0.2199g of terbium oxide, and grind and mix these raw materials thoroughly to obtain glass batching material.

[0115] (2) Melting: Pour the glass batch into a corundum crucible, heat it from room temperature to 400°C at a heating rate of 5°C / min, then heat it to 1000°C at a heating rate of 6°C / min, and then heat it to 1500°C at a heating rate of 5°C / min. Melt it at this temperature for 1 hour to obtain glass melt.

[0116] (3) Pour the glass liquid obtained in step (2) into a copper mold that has been preheated to 470°C and cool it at room temperature to form the glass; anneal it at 470°C for 2 hours to obtain the glass.

[0117] The emission spectrum of the fluorescent glass prepared in this embodiment under 378nm wavelength excitation is as follows: Figure 6As shown. For ease of comparison, the emission spectrum of Example 1 is also listed below. Figure 6 From. Figure 6 It can be seen that Example 8 is derived from Tb 3+5 D3→ 7 F5 and 5 D3→ 7 The emission band intensity of F4 was reduced compared to Example 1, indicating that replacing Al2O3 with P2O5 in the glass matrix can reduce the emission band intensity from Tb. 3+ 5 Electronic transition from the D3 excited state to the ground state.

[0118] The X-ray diffraction patterns of the samples prepared in Examples 1 and 8 are as follows: Figure 7 As shown.

[0119] The X-ray diffraction pattern of Example 1 showed no diffraction peaks, indicating that the material prepared in this example was in a glassy state. However, the material prepared in Example 8 showed obvious diffraction peaks, corresponding to Ca5(PO4)3F crystals (PDF 15-0876). Generally, crystallization in glass requires microcrystallization heat treatment. The X-ray diffraction results of Example 8 show that by precisely designing the composition of the glass matrix, crystal precipitation during the cooling process of the glass melt can be achieved. Figure 6 The emission spectrum shows that the precipitation of the crystal in Example 8 altered Tb. 3+ The local environment suppressed the source of Tb 3+5 D3→ 7 F5 and 5 D3→ 7 The electron transition of F4 reduces the intensity of the corresponding emission band.

[0120] Comprehensive analysis shows that by precisely designing the matrix glass composition, especially by altering the contents of B2O3, P2O5, CaF2, NaF, CaO, and Na2O in the glass matrix, Tb can be achieved. 3+ ion 5 Electronic transitions from the D3 excited state to the ground state are modulated to adjust Tb. 3+ By controlling the intensity of the violet light emission band, the luminescence properties of the material can be regulated.

[0121] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A terbium-doped fluorescent glass, characterized in that, Based on the molar parts of the effective components, it includes: 45-55 parts of SiO2, 8-16 parts of the first oxide, 10-20 parts of the second oxide, 5-12 parts of ZnO, 10-20 parts of fluoride, and 0.05-0.1 parts of Tb4O7; Wherein, the first oxide is Al2O3; the second oxide is Na2O; and the fluoride is CaF2; Alternatively, the first oxide is Al2O3 and P2O5; the second oxide is CaO; and the fluoride is NaF. Its preparation method includes the following steps: Mix all raw materials evenly according to the molar ratio of the effective components to obtain glass batch material; The glass batch is heated to 1450~1550℃ and melted to obtain molten glass; The molten glass is cooled and shaped, and then annealed at 420~500℃ to obtain the final product.

2. The terbium-doped fluorescent glass as described in claim 1, characterized in that, The melting process is as follows: first heat to the first set temperature, then heat to the second set temperature, and then heat to the third set temperature; the first set temperature is 350~450 ℃, the second set temperature is 950~1050 ℃, and the third set temperature is 1450~1550 ℃.

3. The terbium-doped fluorescent glass as described in claim 2, characterized in that, The heating rate to the second set temperature is higher than the heating rate to the first set temperature and the heating rate to the third set temperature.

4. The terbium-doped fluorescent glass as described in claim 3, characterized in that, The heating rate to the first set temperature is 4.6~5.4 ℃ / min, the heating rate to the second set temperature is 5.6~6.4 ℃ / min, and the heating rate to the third set temperature is 4.6~5.4 ℃ / min.

5. The application of the terbium-doped fluorescent glass according to any one of claims 1 to 4 in LED light-emitting devices, artistic decorations, color displays, X-ray imaging, scintillation materials, or nuclear technology.

6. A method for controlling the intensity of the violet emission band of a terbium-doped fluorescent glass, characterized in that, Includes the following steps: The raw materials are mixed evenly according to the molar ratio of the effective components, and the composition of the first oxide, the second oxide and the fluoride in the effective components are adjusted to obtain the glass batch material. The glass batch is heated to 1450~1550℃ and melted to obtain molten glass; The molten glass is cooled and shaped, and then annealed at 420~500℃ to obtain the final product. The molar ratio of SiO2, primary oxide, secondary oxide, ZnO, fluoride, and Tb4O7 in the raw materials, based on the effective components, is 45~55: 8~16: 10~20: 5~12: 10~20: 0.05~0.

1. The first oxide is Al2O3; the second oxide is Na2O; the fluoride is CaF2; Alternatively, the first oxide is Al2O3 and P2O5; the second oxide is CaO; and the fluoride is NaF.

7. The method for controlling the intensity of the violet emission band of terbium-doped fluorescent glass as described in claim 6, characterized in that, The melting process is as follows: first heat to the first set temperature, then heat to the second set temperature, and then heat to the third set temperature; the first set temperature is 350~450 ℃, the second temperature is 950~1050 ℃, and the third set temperature is 1450~1550 ℃.

8. The method for controlling the intensity of the violet emission band of terbium-doped fluorescent glass as described in claim 7, characterized in that, The heating rate to the second set temperature is higher than the heating rate to the first set temperature and the heating rate to the third set temperature.

9. The method for controlling the intensity of the violet emission band of terbium-doped fluorescent glass as described in claim 7, characterized in that, The heating rate to the first set temperature is 4.6~5.4 ℃ / min, the heating rate to the second set temperature is 5.6~6.4 ℃ / min, and the heating rate to the third set temperature is 4.6~5.4 ℃ / min.

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