Tb < 3 + >-doped borosilicate glass with thermoluminescence as well as preparation method and application of Tb < 3 + >-doped borosilicate glass

Abstract

The invention relates to the technical field of glass preparation, in particular to Tb < 3 + > doped borosilicate glass with thermoluminescence as well as a preparation method and application thereof, and the Tb < 3 + > doped borosilicate glass comprises the following raw materials in molar percentage: 25-35% of SiO2, 35-42% of B2O3, 18-22% of Na2CO3, 8-12% of Al2O3 and 0.25% of Tb4O7. The glass prepared in the invention has excellent transparency stability, and shows a strong thermoluminescence phenomenon in a heat treatment process after being irradiated by X-rays for 20 minutes, and the luminous intensity of the glass is increased along with the increase of temperature. Compared with a crystal material, the process is simple and environment-friendly, and has stronger thermoluminescence, so that the glass is expected to be practically applied in the fields of temperature sensing, safety detection, thermal imaging and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of glass preparation, and particularly relates to a Tb-doped borosilicate glass with thermoluminescence, 3+ its preparation method and application. Background Art

[0002] Thermoluminescent glass refers to glass that exhibits obvious thermoluminescence under heat treatment. Such materials are usually related to defects generated inside the glass. There are free carriers in the glass whose energy can be collected and emitted, and their energy levels are close to those of free electrons, also known as active centers. When the glass is heated, its temperature rises, and the free carriers are excited and enter the excited state of high energy. At this time, they have enough energy to transition to the low energy state, and luminescence occurs during the radiative transition process. Currently, thermoluminescent materials show great application prospects in fields such as medical diagnosis, thermal sensors, and energy conversion. For example, they emit bright light when the temperature rises, thus preventing the occurrence of dangerous accidents such as fires and explosions. However, current thermoluminescent materials are mainly in crystalline materials, and such materials are prone to defects. There is little research on amorphous thermoluminescent glass. Glass has excellent transparency, corrosion resistance, high-temperature stability, and is economical, environmentally friendly. Therefore, a Tb-doped borosilicate glass with thermoluminescence is prepared. 3+ This technology solves the key problem of weak thermoluminescence of amorphous glass through defect engineering, providing a new glass material for thermal sensing technology.

[0003] The existing Chinese patent document CN202011106355.0 discloses a rare earth element Tb-doped fluorosilicate luminescent glass and its preparation method. The raw materials of the luminescent glass are composed of SiO2, CaF2, SrCO3, BaCO3, and ZnO, where SiO2 is 40-60%, CaF2 is 10-20%, SrCO3 is 5-20%, BaCO3 is 5-20%, and ZnO is 5-20%; the rare earth oxide is Tb4O7, with a mass percentage of 0.1-10%; the raw material ratio is weighed and ground evenly; by the melt quenching method, the premixed material is heated to 1200°C and kept warm for 1-5 h to obtain a molten glass material; it is poured into a mold at 300-500°C and kept at this temperature for 2-10 h, and then cooled to room temperature to obtain the luminescent glass;

[0004] The existing Chinese patent document CN201810571134.7 discloses a thermochromic aluminosilicate glass and its preparation method, which is made from the following raw materials by weight percentage: SiO2 55% - 72%, Al2O3 15% - 24%, B2O3 0% - 7%, K2O 0 - 8%, MgO 0 - 4%, CaO 0 - 1%, Na2O 2 - 15%, VO2 0.8% - 8%; (1) batching; (2) mixing and ball milling for 0.25 - 0.5 h to make the raw materials evenly mixed; (3) melting: melting in a furnace, heating to 1000 °C at a rate of 5 - 10 °C / min, then heating to the melting temperature at a rate of 3 - 5 °C / min, the melting temperature is 1300 - 1600 °C, and keeping warm for 2 - 5 h to obtain glass liquid; (4) forming: quickly pouring the glass liquid into a stainless steel plate mold for forming; (5) annealing: keeping warm at 650 °C for 3 - 6 h, and the glass sample is cooled to room temperature with the furnace.

[0005] The existing Chinese patent document CN202011106355.01 is a fluorosilicate system, which mentions the luminescence characteristics of Tb. The existing Chinese patent document CN201810571134.7 is an aluminosilicate system, which mentions that the glass has a thermochromic effect; while the present technical solution is a borosilicate system, which discloses Tb 3+ After X-ray irradiation of the Tb-doped borosilicate glass, by using the energy matching relationship between the defect state and the Tb 3+ luminescence center, bright thermoluminescence in the glass is realized, and the application of thermoluminescent glass in temperature sensing is expanded. Summary of the Invention

[0006] The purpose of the present invention is to provide a Tb 3+ -doped borosilicate glass with thermoluminescence, its preparation method and application. The glass prepared in the present invention has excellent transparency stability. After 20 minutes of X-ray irradiation, the glass shows strong thermoluminescence during the heat treatment process, and its luminescence intensity increases with the increase of temperature. Compared with crystal materials, this process is simple, environmentally friendly, and has stronger thermoluminescence. Therefore, this glass is expected to be practically applied in the fields of temperature sensing, safety detection, thermal imaging, etc.

[0007] To achieve the above technical purposes and reach the above technical effects, the present invention is realized through the following technical solutions:

[0008] A Tb 3+ -doped borosilicate glass with thermoluminescence, comprising raw materials in the following molar percentages: SiO2: 25 - 35%, B2O3: 35 - 42%, Na2CO3: 18 - 22%, Al2O3: 8 - 12%, Tb4O7: 0.25%.

[0009] On the other hand, the present invention provides a method for preparing the above-mentioned glass, comprising the following steps:

[0010] S1: Weigh the above raw materials according to molar percentages, grind them in air for 10 minutes, and load the uniformly mixed raw materials into a ceramic crucible;

[0011] S2: Transfer the raw materials loaded in the ceramic crucible to a box furnace at 1350 °C and sinter for 40 minutes. Pour the glass melt onto a preheated copper plate to obtain a precursor glass;

[0012] S3: Heat the glass prepared in S2 to 400 °C and hold for 5 hours to remove the residual stress in the glass and improve the mechanical strength of the glass;

[0013] S4: Grind and polish the glass prepared in S3, and then irradiate the glass with X-rays for 20 minutes to obtain a Tb 3+ -doped glass with thermoluminescence;

[0014] Further, the glass in S4 is irradiated with X-rays at a dose of 7.51 μGy S -1 .

[0015] On the other hand, the present invention provides an application of the above-mentioned glass in thermoluminescent materials.

[0016] On the other hand, the present invention provides an application of the above-mentioned glass in temperature sensing.

[0017] Advantages of the present invention:

[0018] By introducing controllable defects into the glass network through X-ray irradiation and combining with the characteristic transitions of Tb 3+ ions, the present invention constructs a unique energy storage-release system. In a specific implementation, X-ray irradiation causes the oxygen bonds in the borosilicate network to break, forming oxygen vacancy defects and electron trap centers. At the same time, Tb 3+ acts as an activator ion, and its unfilled 4f electron layer forms metastable states by capturing carriers. During subsequent heat treatment, thermal excitation causes the electrons in the defect energy levels to de-trap and migrate through the conduction band to the excited state of Tb 3+ , and finally green visible light is emitted through the 5D4→7F5 transition. The amorphous nature of the glass matrix makes the defect distribution more uniform, while the localized 4f orbitals of Tb 3+ reduce the non-radiative recombination probability. The synergistic effect of the two significantly improves the luminescence efficiency. Figure 2-4 The gradient change of the luminescence intensity at different temperatures verifies the dynamic matching characteristics of the defect concentration and the thermal activation energy, realizing temperature-responsive luminescence regulation. It not only solves the key problem of weak thermoluminescence of amorphous glass but also provides a new idea for the design of high-efficiency photothermal conversion materials.

[0019] The present invention adopts a ternary system of SiO2 - B2O3 - Al2O3 with a specific ratio to form a mixed network structure with a high degree of polymerization. SiO2 provides a rigid skeleton, B2O3 adjusts the network connectivity through [BO3] and [BO4] units, and Al2O3 acts as a network intermediate to enhance the structural density. This design endows the glass with excellent high - temperature stability, while reducing the phonon energy of the matrix and suppressing the non - radiative loss of the excited - state energy of Tb 3+ By introducing Na2O to adjust the optical basicity, the coordination field environment of Tb 3+ is optimized, resulting in a significant increase in the 4f - 4f transition probability. The high transparency and low scattering characteristics of the glass ensure the efficient output of the luminescence signal, providing a basis for optical detection in practical applications. This structural stability and optical optimization design enable the glass material to be not only suitable for high - temperature environments but also capable of achieving efficient optical signal transmission in optical devices.

[0020] The present invention optimizes the energy - level difference between the internal defect energy levels of the glass and the excited state of Tb 3+ to enable the material to exhibit temperature - dependent carrier - release kinetics. During low - temperature heat treatment, electrons in the shallow trap energy levels are preferentially de - trapped, resulting in weak luminescence; as the temperature increases, the deep trap energy levels are gradually activated, and the electron - hole recombination channels increase, and the luminescence intensity increases exponentially. This characteristic enables the material to accurately reflect the ambient temperature fluctuations through the change in luminescence intensity and maintain stable performance during multiple thermal cycles. For example, no intensity attenuation occurred during repeated high - temperature treatment in Example 3. Compared with the inhomogeneous luminescence affected by grain boundaries in crystalline materials, the continuous defect distribution of the amorphous glass enables a linear response over a wider temperature range, providing a new idea for high - precision thermal sensing. This dynamic luminescence characteristic with temperature - gradient response makes the glass material of the present invention show broad application prospects in the fields of temperature sensing, safety monitoring, etc.

[0021] The present invention adopts a conventional glass melting - quenching process, which has low raw material costs and strong process compatibility. The melting temperature of 1350 °C matches the industrial float production line, and the annealing process effectively eliminates internal stress to ensure the mechanical strength of the material; the X - ray post - treatment can be flexibly implemented after forming, and the defect density is controlled by adjusting the irradiation parameters. The obtained glass combines the easy - processing property of bulk materials with functional characteristics, breaking through the technical bottleneck of difficult forming of crystalline materials. Based on its thermoluminescence characteristics, this material can be made into a thin - film sensor for real - time monitoring of high - temperature equipment, or used as a safety sign to give a luminescence warning in fire alarms; combined with the transparent characteristics, it can also be integrated into an intelligent window system to achieve temperature visualization monitoring. In addition, its thermoluminescence characteristics make it have potential application value in the field of radiation dose detection, reflecting the design advantage of "one material with multiple uses".

[0022] Of course, it is not necessary for any product implementing the present invention to simultaneously achieve all the above - mentioned advantages. Brief Description of the Drawings

[0023] To more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0024] Figure 1 is the transmission spectrum of the glass obtained in Embodiment 1 of the present invention and a photo of the glass;

[0025] Figure 2 is the thermoluminescence spectrum of the glass in Embodiment 1 of the present invention during heat treatment at 300 °C and a photo of the glass emitting light;

[0026] Figure 3 is the thermoluminescence spectrum of the glass in Embodiment 2 of the present invention during heat treatment at 400 °C and a photo of the glass emitting light;

[0027] Figure 4 is the thermoluminescence spectrum of the glass in Embodiment 3 of the present invention during heat treatment at 500 °C and a photo of the glass emitting light.

[0028] Figure 5 is the thermoluminescence glow curve of the glass in Embodiment 3 of the present invention after X-ray irradiation. Detailed Description of the Embodiments

[0029] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, rather than all, embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0030] Embodiment 1

[0031] A method for preparing a Tb 3+ -doped borosilicate glass with thermoluminescence includes the following steps:

[0032] S1: Weigh SiO2: 25%, B2O3: 42%, Na2CO3: 22%, Al2O3: 10.75%, and Tb4O7: 0.25% according to molar percentages, grind them in air for 10 minutes, and put the uniformly mixed raw materials into a ceramic crucible;

[0033] S2: Transfer the raw materials in the ceramic crucible to a box furnace at 1350 °C and sinter for 40 minutes, then pour the glass liquid onto a preheated copper plate to obtain a precursor glass;

[0034] S3: Heat the glass prepared in step S2 to 400 °C and hold for 5 hours to remove the residual stress in the glass and improve the mechanical strength of the glass;

[0035] S4: Grind and polish the glass obtained in step S3, and then irradiate the glass with X-rays for 20 minutes to obtain a Tb-doped glass with thermoluminescence; 3+ doped glass;

[0036] S5: Characterize the transparency of the glass and conduct heat treatment at 300 °C to explore its thermoluminescence phenomenon.

[0037] It can be seen through Figure 1 that the glass in Example 1 exhibits high transparency. In addition, the glass exhibits obvious thermoluminescence during the heat treatment at 300 °C. As Figure 2 shown, the Tb-doped borosilicate glass exhibits green thermoluminescence. 3+ doped borosilicate glass exhibits green thermoluminescence.

[0038] Example 2

[0039] A method for preparing a Tb-doped borosilicate glass with thermoluminescence according to this example includes the following steps: 3+ doped borosilicate glass includes the following steps:

[0040] S1: Weigh SiO2: 35%, B2O3: 35%, Na2CO3: 18%, Al2O3: 11.75%, and Tb4O7: 0.25% according to the molar percentage, grind in air for 10 minutes, and load the uniformly mixed raw materials into a ceramic crucible;

[0041] S2: Transfer the raw materials loaded in the ceramic crucible to a box furnace at 1350 °C and sinter for 40 minutes. Pour the glass melt onto a preheated copper plate to obtain a precursor glass;

[0042] S3: Heat the glass prepared in step S2 to 400 °C and hold for 5 hours to remove the residual stress in the glass and improve the mechanical strength of the glass;

[0043] S4: Grind and polish the glass obtained in step S3, and then irradiate the glass with X-rays for 20 minutes to obtain a Tb-doped glass with thermoluminescence; 3+ doped glass;

[0044] S5: Conduct heat treatment on the glass at a higher temperature, i.e., 400 °C, to explore its thermoluminescence phenomenon.

[0045] The glass in this Example 2 exhibits stronger thermoluminescence than that in Example 1. As Figure 3As shown, this may be related to the concentrated release of electrons. Therefore, it also shows a trend of increasing luminescence intensity with increasing temperature, further elaborating on the application of the Tb-doped glass with thermoluminescence in fields such as temperature sensing. 3+

[0046] Example 3

[0047] A preparation method of a Tb-doped borosilicate glass with thermoluminescence according to this example includes the following steps: 3+

[0048] S1: Weigh SiO2: 35%, B2O3: 34.75%, Na2CO3: 22%, Al2O3: 8%, and Tb4O7: 0.25% according to molar percentages, grind them in air for 10 minutes, and put the evenly mixed raw materials into a ceramic crucible.

[0049] S2: Transfer the raw materials in the ceramic crucible to a box furnace at 1350 °C and sinter for 40 minutes, then pour the glass melt onto a preheated copper plate to obtain a precursor glass.

[0050] S3: Heat the glass prepared in step S2 to 400 °C and keep it warm for 5 hours to remove the residual stress in the glass and improve the mechanical strength of the glass.

[0051] S4: Grind and polish the glass prepared in step S3, and then irradiate the glass with X-rays for 20 minutes to obtain a Tb-doped borosilicate glass with thermoluminescence. 3+

[0052] S5: Characterize the transparency of the glass, test the thermoluminescence curve after irradiation, and conduct heat treatment at 500 °C to explore its thermoluminescence phenomenon.

[0053] Compared with Examples 1-2, the glass in this Example 3 shows a stronger thermally induced green luminescence phenomenon during heat treatment at 500 °C, as Figure 4 shown, further showing a trend of increasing luminescence intensity with increasing temperature. As Figure 5 shown, after irradiation, the thermoluminescence curve of the glass was tested, showing a very strong peak, which benefits from a large number of defects generated in the glass. At the same time, it also indicates that the glass is an excellent thermoluminescence material. Through thermoluminescence, this glass also shows great application prospects in fields such as temperature sensing, thermal imaging, and security detection.

[0054] In summary, a Tb-doped borosilicate glass with thermoluminescence of this application 3+ ​Doped borosilicate glass, utilizing the thermoluminescence phenomenon caused by defect engineering after X-ray irradiation of the glass, can be applied to fields such as temperature sensing, safety monitoring, and thermal imaging. The amorphous glass exhibits excellent transparency and stability. Compared with current thermosensitive materials, the Tb 3+ -doped glass prepared in this invention has higher photothermal conversion efficiency and luminescence efficiency.

[0055] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific embodiments described. Obviously, many modifications and changes can be made according to the content of this specification. These embodiments are selected and specifically described in this specification to better explain the principle and practical application of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A Tb with thermoluminescence 3+ Doped borosilicate glass, characterized in that The invention comprises raw materials in the following molar percentages: SiO2: 25-35%, B2O3: 35-42%, Na2CO3: 18-22%, Al2O3: 8-12%, and Tb4O7: 0.25%.

2. The Tb with thermoluminescence as claimed in claim 1 3+ The method for preparing doped borosilicate glass is characterized by: The following steps are involved: S1: weigh the above raw materials according to molar percentage, grind them in air for 10 minutes, and put the mixed raw materials into a ceramic crucible; S2: Load the raw materials into a ceramic crucible and move them into a box furnace at 1350°C for sintering for 40 minutes, pour the glass liquid onto a preheated copper plate to obtain a precursor glass; S3: The glass prepared in S2 is heated to 400° C. and kept warm for 5 hours to remove residual stress in the glass and improve the mechanical strength of the glass; S4: The glass prepared in S3 was polished and then irradiated with X-rays for 20 minutes to obtain Tb with thermoluminescence. 3+ Doped glass.

3. The preparation method according to claim 2, characterized in that: The glass in S4 was exposed to a dose of 7.51 μGy S -1 of X-ray irradiation.

4. Use of the glass as claimed in claim 1 in thermoluminescent materials.

5. Use of the glass as claimed in claim 1 in temperature sensing.

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