A method for preparing silver-doped silicon phosphate glass sheets and applications thereof

Abstract

The present application relates to the technical field of radiation dose, and specifically discloses a preparation method and application of silver-doped silicon phosphate glass sheet, aiming at solving the problems of easy cracking, easy hydrolysis of glass and unstable radiation photoluminescence performance in the prior art, the method comprising: mixing component raw materials, degassing, high-temperature melting, pouring the molten glass liquid into a preheated graphite crucible for shaping, and then performing constant-temperature annealing, polishing, polishing and cutting to obtain an X-ray radiation dosimeter. The present application effectively adjusts the material microstructure and the formation process of the radiation photoluminescence center by adding precisely regulated phosphate glass components and optimizing the annealing process, and prepares an X-ray radiation dosimeter with stable structure, good thermal stability and low hydrolysis resistance. The medium performs excellently in radiation photoluminescence intensity, signal retention capacity, response stability and chemical stability, and can be widely applied in the fields of X-ray imaging, medical diagnosis, non-destructive detection and precise structure analysis.

Description

Technical Field

[0001] This invention relates to the field of radiation dosimeter technology, and more specifically, to a method for preparing and applying a silver-doped silicon phosphate glass slide. Background Technology

[0002] To further improve the thermal and physicochemical stability of Ag-doped phosphate glasses, this study employed a high-temperature melt-quench method to synthesize the glass, while simultaneously introducing [a specific ingredient] into the glass system. Under conventional preparation conditions, Ag-doped phosphate glasses primarily consist of POP chain or ring structures with low network connectivity. This makes them prone to structural relaxation or partial depolymerization at high temperatures. Furthermore, they are sensitive to moisture and chemical media, exhibiting hygroscopicity, dissolution, and chemical degradation, thus affecting the long-term stability and retention of photoluminescence properties. These defects lead to existing phosphate glass materials being prone to cracking and hydrolysis in applications, and exhibiting unstable photoluminescence properties, making it difficult to meet the practical requirements of high-precision radiation dose detection.

[0003] To overcome the aforementioned shortcomings, this invention introduces Si into the glass melt. Si can form synergistic crosslinks with the phosphate network, enhancing the overall density and rigidity of the glass network through Si-OP bonds, effectively improving the material's thermal stability and chemical durability. Simultaneously, this modification method maintains the material's excellent radiation response performance without interfering with the formation of photoluminescent centers by silver ions. Based on this, this invention proposes a method for preparing silver-doped silicon phosphate glass and its application. By adjusting the P / Si ratio and annealing process parameters, the microstructure of the material and the formation process of photoluminescent centers can be effectively controlled. Summary of the Invention

[0004] The purpose of this invention is to solve the technical problems mentioned in the background art above, and to provide a method for preparing silver-doped silicon phosphate glass and its application. The X-ray information storage medium prepared by this method can be applied to high spatial resolution X-ray imaging.

[0005] The above-mentioned objective of the present invention is achieved as follows: One aspect of the present invention provides a method for preparing a silver-doped silicon phosphate glass slide, the method comprising the following steps: After the raw materials are mixed evenly, they are heated to remove gas. The degassed raw material powder is then placed in a lifting furnace and fully melted under high temperature conditions to obtain glass melt; The graphite crucible is preheated to a preset temperature, and after the crucible reaches the required temperature, the resulting glass melt is poured into the preheated graphite crucible to form a glass preform. The glass blank is then transferred to a muffle furnace for isothermal annealing; after annealing, it is precisely ground, polished and cut to obtain an X-ray radiation dosimeter.

[0006] Furthermore, the method specifically includes the following steps: S1. Silver ion-doped phosphate glass was prepared on the surface of a pretreated graphite crucible using a melt-cool process. S2. Place the obtained silver-doped silicon phosphate glass into a muffle furnace and perform constant temperature holding and annealing treatment at a set temperature. S3. After annealing, the glass sample is cleaned with anhydrous ethanol to remove residual graphite impurities on the surface, and the sample is cut to size using a wire cutting device. S4. The cut glass blanks are successively ground and polished to obtain a product with a smooth surface.

[0007] Furthermore, the method for preparing silver-doped silica phosphate glass on a graphite crucible using the melt-quench method in step S1 specifically includes: S1-1. Weigh out sodium metaphosphate, aluminum phosphate, silicon dioxide and silver chloride according to the stoichiometric ratio, and mix the raw materials thoroughly and evenly. S1-2. The mixed raw material powder is loaded into a corundum crucible and placed in a muffle furnace for degassing. S1-3. Place the graphite crucible into a muffle furnace with the preheating temperature set for preheating; S1-4. Transfer the degassed corundum crucible containing the raw material powder to the lifting furnace to clarify and homogenize the glass melt at high temperature. S1-5. After the raw materials have completely melted into a clear glass liquid, the preheated graphite crucible is removed and the glass liquid is poured onto the surface of the graphite crucible to form a glass preform.

[0008] Furthermore, the temperature range for degassing in step S1-2 is 350–800℃, and the treatment time is 0.5–3 hours. In steps S1-3, the preheating temperature of the graphite crucible is 400-750℃, and the preheating time is 0.5-6h. In steps S1-4, the melting temperature of the raw materials in the lifting furnace is 1000-1600℃, and the melting duration is 0.4-4h.

[0009] The response mechanism of the silver-doped phosphate glass obtained in step S1 after X-ray irradiation is carried out through the following reaction equation: (1) ; (2) (Electronic trap); (3) (The Hole Trap).

[0010] Furthermore, the method for heat-annealing the silver-doped phosphate glass in step S2 to eliminate internal residual stress includes the following steps: S2-1. Remove the graphite crucible from the muffle furnace; S2-2. Pour the molten glass onto a graphite crucible and cool it in air for 2-4 minutes. S2-3. Place the slightly cooled and shaped glass into a muffle furnace for heat preservation and annealing.

[0011] Furthermore, in steps S2-3, the heat treatment temperature is 200-600℃, the heat treatment time is 300-1200 min, the annealing temperature is 300-500℃, and the annealing time is 300-1200 min.

[0012] Furthermore, in step S4, 200-grit, 600-grit, 2500-grit, 4000-grit, 8000-grit, and 10000-grit sandpapers are selected, and then the samples are polished respectively.

[0013] Another aspect of the present invention provides an X-ray radiation dosimeter made of silver-doped silicon phosphate glass, which is prepared by the preparation method described above.

[0014] Another aspect of the present invention provides an application of an X-ray radiation dosimeter in the preparation of radiation detection, non-destructive testing, or environmental monitoring products.

[0015] Compared with the prior art, the present invention has the following beneficial effects: 1. This invention obtains an X-ray radiation dosimeter with superior luminescence performance, large size, and adjustable diameter and thickness by adjusting the P / Si ratio and the precise control of the annealing temperature. Among them, the introduction of SiO2 enables the glass network to form Si-OP bonds, which enhances the overall network density and rigidity, and effectively improves the defects of Ag-doped phosphate glass under conventional preparation conditions, such as low network connectivity and easy structural relaxation or partial depolymerization.

[0016] 2. The X-ray radiation dosimeter prepared by this invention has stable composition, uniform thickness, no cracks, and excellent radiation photoluminescence performance, which has important application value in ultra-high spatial resolution X-ray imaging. At the same time, this material overcomes the problems of existing phosphate glass being sensitive to moisture and chemical media, easily absorbing moisture and dissolving, and chemically degrading, and exhibits excellent chemical stability and long-term stability, which can significantly reduce the fragile and hydrolytic characteristics of Ag-doped phosphate glass itself.

[0017] 3. The preparation method of this invention is simple, reliable, and highly repeatable. The prepared material has stable components, is not prone to cracking, has strong processing adaptability, high sensitivity, and good recyclability. It can be widely used in X-ray imaging, medical diagnosis, non-destructive testing, and precision structural analysis, and has significant application value and huge potential economic benefits. Attached Figure Description

[0018] Figure 1 The images show the emission spectra of an X-ray radiation dosimeter before and after irradiation. Figure 2 The excitation spectrum of the X-ray radiation dosimeter at the emission peak at 650 nm; Figure 3 The fluorescence decay lifetime curves of the X-ray radiation dosimeter at 450 nm and 650 nm are shown (a is 450 nm; b is 650 nm). Figure 4 An emission spectrum of an X-ray radiation dosimeter showing how its intensity changes with radiation dose; Figure 5 These are photographs of an X-ray radiation dosimeter before and after irradiation under a 365nm ultraviolet lamp (left image is before irradiation, right image is after irradiation). Figure 6 Photoluminescence intensity curves of silver-doped silicon phosphate glasses with different P:Si ratios; Figure 7 This is a linear relationship curve between irradiation dose and irradiation intensity. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of this invention clearer, the following description is provided in conjunction with the appendix. Figure 1-7 The present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0020] The implementation of the present invention will be described in detail below with reference to specific embodiments.

[0021] Example 1: This example provides a method for preparing a silver-doped silicon phosphate glass slide, the specific steps of which are as follows: (1) Weighing and mixing of raw materials: Weigh sodium metaphosphate, aluminum phosphate, silicon dioxide and silver chloride according to the stoichiometric ratio, wherein the molar ratio of sodium metaphosphate, aluminum phosphate and silicon dioxide is 35:45:20 and the doping amount of silver chloride is 0.5 mol%. Place the weighed raw materials in an agate mortar and grind and mix them thoroughly for 30 min to ensure that each component is evenly distributed.

[0022] (2) Degassing treatment: The uniformly mixed raw material powder is placed into an alumina crucible and then placed in a muffle furnace for degassing treatment. The degassing treatment temperature is 550℃ and the treatment time is 1.5h to remove volatiles and adsorbed gases from the raw material.

[0023] (3) Preheating of graphite crucible: Place the finely polished graphite crucible into another muffle furnace for preheating. The preheating temperature is 600℃ and the preheating time is 2h to ensure uniform crucible temperature.

[0024] (4) High-temperature melting: After degassing, the corundum crucible is transferred to the lifting furnace and heated to 1200°C at a heating rate of 5°C / min. The crucible is then kept at 1200°C for 2 hours to fully clarify and homogenize the glass melt, resulting in a uniform glass melt.

[0025] (5) Forming: After the raw materials have completely melted into clear glass liquid, quickly remove the preheated graphite crucible and pour the glass melt onto the surface of the graphite crucible at a uniform speed to form a glass preform. Avoid generating air bubbles during the pouring process.

[0026] (6) Cooling and Annealing: Cool the graphite crucible containing molten glass in air for 3 minutes. After the glass has slightly solidified, transfer it to a muffle furnace for heat treatment and annealing. Set the heat treatment temperature to 400℃ and the heat treatment time to 600 minutes; set the annealing temperature to 400℃ and the annealing time to 600 minutes. After annealing, cool the furnace to room temperature.

[0027] (7) Cleaning: After annealing, take out the glass sample and ultrasonically clean it with anhydrous ethanol for 10 minutes to remove the residual graphite impurities on the surface.

[0028] (8) Cutting: Use wire cutting equipment to cut the glass into glass sheets with a size of 20×20×2mm.

[0029] (9) Grinding and polishing: Grind and polish the cut glass sheet with sandpaper of 200 grit, 600 grit, 2500 grit, 4000 grit, 8000 grit and 10000 grit in sequence. Each grit is ground for 5 minutes to finally obtain a smooth and scratch-free silver-doped silicon phosphate glass sheet.

[0030] Example 2: This example provides a method for preparing a silver-doped silicon phosphate glass sheet, which is basically the same as that in Example 1, except that the raw material ratio in step (1) is different. In this example, the molar ratio of sodium metaphosphate, aluminum phosphate, and silicon dioxide is 30:40:30, and the doping amount of silver chloride is still 0.5 mol%. By increasing the proportion of SiO2, the density of the glass network is further enhanced.

[0031] Example 3: This example provides a method for preparing a silver-doped silicon phosphate glass sheet, which is basically the same as that in Example 1, except that the raw material ratio in step (1) is different. In this example, the raw materials are mixed in a ratio of P:Si = 10:1, and the atomic percentages of each component are as follows: Na is 12.57 mol%, Al is 3.14 mol%, P is 19.98 mol%, O is 62.27%, Ag is 0.04%, and Si is 2.01%. After the raw materials are thoroughly mixed, the process is carried out according to the steps of Example 1: degassing, melting, forming, annealing, cutting, and polishing to finally obtain a silver-doped silicon phosphate glass sheet with a smooth surface.

[0032] Example 4: This example provides a method for preparing silver-doped silicon phosphate glass sheets, which is basically the same as that in Example 1, except that the annealing process parameters in step (6) are different. In this example, the heat treatment temperature is 500℃ and the heat treatment time is 480 min; the annealing temperature is 450℃ and the annealing time is 720 min. By adjusting the annealing temperature, silver-doped silicon phosphate glasses with different Na / Al ratios can be obtained, and the internal stress relief effect can be optimized.

[0033] Example 5: This example provides a method for preparing silver-doped silica phosphate glass sheets, which is basically the same as that in Example 1, except that the melting temperature in step (4) is different. In this example, the melting temperature is 1400℃ and the melting holding time is 1.5h. A higher melting temperature helps the glass melt to be better clarified and homogenized.

[0034] Comparative Example 1: This comparative example provides a method for preparing a silver-doped phosphate glass slide without the addition of SiO2, which is basically the same as Example 1, except that silicon dioxide is not added in step (1), the molar ratio of sodium metaphosphate to aluminum phosphate is 40:60, and the amount of silver chloride doping is the same.

[0035] Example 6: X-ray radiation photoluminescence performance and physicochemical properties of the silver-doped silicon phosphate glass slides prepared in Examples 1-5 and Comparative Example 1 were tested, as follows.

[0036] 1. Radiation-induced photoluminescence performance test: The glass sample was irradiated with an X-ray source at a dose rate of 10 Gy / min for 10 min. The emission and excitation spectra of the sample were recorded using a fluorescence spectrometer.

[0037] Figure 1The images show the emission spectra of the X-ray radiation dosimeter of this invention before and after irradiation. As can be seen from the images, the sample showed no obvious emission peak in the visible light region before irradiation; after irradiation, two distinct emission peaks appeared at 450 nm and 650 nm, indicating that X-ray irradiation induced the formation of radioluminescent centers in the material, demonstrating the excellent radioluminescent properties of silver-doped silica phosphate glass. The orange light emission intensity at 650 nm was relatively high and was the dominant radioluminescent signal. These results demonstrate that this invention, by introducing SiO2 to form a PO-Si glass structure network, significantly enhances the radiation response performance of the material without altering the internal coordination environment of Ag ions.

[0038] Figure 2 The figure shows the excitation spectrum of the emission peak at 650 nm of the X-ray radiation dosimeter of this invention. As can be seen from the figure, there is an excitation peak around 328 nm, indicating that the optimal excitation wavelength of this emission peak is in the ultraviolet region, and it can be used for ultraviolet-excited radiation dose detection.

[0039] Figure 3 (a) and (b) in the figure show the fluorescence decay lifetime curves of the X-ray radiation dosimeter at 450 nm and 650 nm, respectively. Figure 3 As can be seen, the decay times are all within the microsecond range, indicating that the radiative recombination time is also within the microsecond range, demonstrating good radiative recombination capability. Through fitting calculations, the fluorescence lifetimes of the 450nm and 650nm emission peaks are 2.5μs and 1.8μs, respectively, indicating that the material has excellent fluorescence lifetime characteristics, which is beneficial for stable signal reading.

[0040] Figure 4 This is a graph showing the change in emission spectral intensity of the X-ray radiation dosimeter of this invention as the radiation dose increases. From... Figure 4 As can be seen, the intensity of the emission peak at 650 nm gradually increases with the X-ray irradiation dose from 0, indicating that the material can be used to read the cumulative radiation dose. Figure 6 As shown, when P:Si = 10:1, under the same irradiation dose conditions, silver-doped silicon phosphate glass exhibits the strongest photoluminescence intensity; for example... Figure 7 As shown, this is the linear relationship curve between irradiation dose and irradiation intensity (Rd). 2 =0.995), with a minimum response dose of 0.1 Gy. Within the dose range of 0-60 Gy, the irradiation dose of silver-doped silicon phosphate glass exhibits a linear response to the irradiation intensity, indicating that this material can be used for precise detection of radiation dose.

[0041] 2. Radiation imaging performance test: The glass slides prepared in Examples 1-5 were compared and observed before and after X-ray irradiation. Figure 5These are photographs of the X-ray radiation dosimeter of this invention before and after irradiation under a 365nm ultraviolet lamp. Figure 5 As can be seen from the image, before irradiation (left image), the glass slide is colorless and transparent, and does not emit light under a 365nm ultraviolet lamp; after X-ray irradiation (right image), when excited under a 365nm ultraviolet lamp, the glass slide emits uniform orange light, indicating that the photoluminescence centers are uniformly distributed in the glass matrix. This result demonstrates that the silver-doped silicon phosphate glass slide prepared in this invention has the potential for radiation imaging and can be applied to the field of high spatial resolution X-ray imaging.

[0042] 3. Performance comparison of different embodiments: The performance of the glass slides prepared in Examples 1-5 was tested, and the results are shown in Table 1.

[0043] Table 1 As shown in Table 1, the photoluminescence intensity of Examples 1-5 is superior to that of Comparative Example 1, indicating that the introduction of SiO2 significantly enhances the radiation response performance of the material. Example 3 (P:Si = 10:1), with its moderate SiO2 ratio, forms the optimal PO-Si glass structure network, exhibiting the highest luminescence intensity, best flexural strength, and lowest hydrolysis weight loss rate. It also has the highest glass transition temperature, indicating the best thermal stability. Example 2, with its higher SiO2 ratio, has a denser glass network and good overall performance. Example 4 further optimizes the internal stress relief effect by adjusting the annealing process. Example 5, by increasing the melting temperature, achieves better glass clarification and slightly improves performance. Comparative Example 1, lacking SiO2, has a glass network mainly composed of POP structures with low network connectivity, resulting in lower luminescence intensity, poor mechanical strength, easy hydrolysis, and poor thermal stability.

[0044] 4. Chemical stability test: The glass slides of Example 3 and Comparative Example 1 were immersed in deionized water for 48 hours, and their hydrolysis weight loss rate was tested. The results showed that the hydrolysis weight loss rate of Example 3 was 0.06%, while that of Comparative Example 1 was 0.35%. This indicates that the present invention significantly enhances the chemical stability of the glass by introducing PO-Si bonds formed by SiO2, effectively inhibiting the occurrence of hydrolysis reaction and changing the original POP network structure's tendency to hydrolyze.

[0045] 5. Thermal Stability Test: The thermal stability of the glass samples from Examples 1-5 and Comparative Example 1 was tested using a differential scanning calorimeter. The results showed that the glass transition temperature (Tg) of Examples 1-5 was higher than 485℃, while the Tg of Example 3 reached 518℃, and the Tg of Comparative Example 1 was only 425℃. The results indicate that the introduction of SiO2 significantly improved the thermal stability of the glass, which is beneficial for the application of the material in high-temperature environments.

[0046] 6. Cyclic Reuse Performance Test: The glass slide of Example 3 was subjected to multiple irradiation-reading-annealing cycle tests. The luminescence intensity was read after each irradiation, followed by thermal annealing at 300°C for 30 minutes to eliminate the radiation signal. After 10 cycles, the luminescence intensity remained above 98% of its initial value, indicating that the material has good cyclic reuse performance.

[0047] 7. Structural Stability Analysis: The glass structures of Example 3 and Comparative Example 1 were analyzed using infrared and Raman spectroscopy. The results showed that significant Si-OP bonds were formed in the glass network of Example 3, while the strength of POP bonds was relatively weakened. This indicates that the introduction of SiO2 and the phosphate network formed a synergistic crosslinking, enhancing the overall density and rigidity of the glass network, thereby improving the structural stability of the material. Simultaneously, the coordination environment of Ag ions did not change significantly, ensuring the excellent radioluminescence properties of the material.

[0048] In summary, through the above embodiments of the present invention, by introducing SiO2 to precisely control the composition of the phosphate glass and combining it with an optimized annealing process, a silver-doped silicon phosphate glass sheet with stable structure, good thermal stability, and resistance to hydrolysis was successfully prepared. This material exhibits excellent radiation photoluminescence properties, chemical stability, and mechanical properties, possesses high sensitivity and good recyclability, and emits uniform orange light after X-ray irradiation. It is suitable for X-ray imaging, medical diagnosis, non-destructive testing, and other fields, and has significant potential for widespread application.

[0049] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a silver-doped silicon phosphate glass slide, characterized in that, The method includes the following steps: After the raw materials are mixed evenly, they are heated to remove gas. The degassed raw material powder is then placed in a lifting furnace and fully melted under high temperature conditions to obtain glass melt; The graphite crucible is preheated to a preset temperature, and after the crucible reaches the required temperature, the resulting glass melt is poured into the preheated graphite crucible to form a glass preform. The glass blank is then transferred to a muffle furnace for isothermal annealing; after annealing, it is precisely ground, polished and cut to obtain an X-ray radiation dosimeter.

2. The method for preparing a silver-doped silicon phosphate glass sheet according to claim 1, characterized in that, The method specifically includes the following steps: S1. Silver ion-doped phosphate glass was prepared on the surface of a pretreated graphite crucible using a melt-cool process. S2. Place the obtained silver-doped silicon phosphate glass into a muffle furnace and perform constant temperature holding and annealing treatment at a set temperature. S3. After annealing, the glass sample is cleaned with anhydrous ethanol to remove residual graphite impurities on the surface, and the sample is cut to size using a wire cutting device. S4. The cut glass blanks are successively ground and polished to obtain a product with a smooth surface.

3. The method for preparing a silver-doped silicon phosphate glass sheet according to claim 2, characterized in that, The method for preparing silver-doped silica phosphate glass on a graphite crucible using the melt-quench method in step S1 specifically includes: S1-1. Weigh out sodium metaphosphate, aluminum phosphate, silicon dioxide and silver chloride according to the stoichiometric ratio, and mix the raw materials thoroughly and evenly. S1-2. The mixed raw material powder is loaded into a corundum crucible and placed in a muffle furnace for degassing. S1-3. Place the graphite crucible into a muffle furnace with the preheating temperature set for preheating; S1-4. Transfer the degassed corundum crucible containing the raw material powder to the lifting furnace to clarify and homogenize the glass melt at high temperature. S1-5. After the raw materials have completely melted into a clear glass liquid, the preheated graphite crucible is removed and the glass liquid is poured onto the surface of the graphite crucible to form a glass preform.

4. The method for preparing a silver-doped silicon phosphate glass sheet according to claim 3, characterized in that, The temperature range for degassing in step S1-2 is 350–800℃, and the treatment time is 0.5–3 hours. In steps S1-3, the preheating temperature of the graphite crucible is 400-750℃, and the preheating time is 0.5-6h. In steps S1-4, the melting temperature of the raw material in the lifting furnace is 1000-1600℃, and the melting duration is 0.4-4h.

5. The method for preparing a silver-doped silicon phosphate glass sheet according to claim 4, characterized in that, The method for annealing silver-doped phosphate glass at a specific temperature in step S2 to eliminate internal residual stress includes the following steps: S2-1. Remove the graphite crucible from the muffle furnace; S2-2. Pour the molten glass onto a graphite crucible and cool it in air for 2-4 minutes. S2-3. Place the slightly cooled and shaped glass into a muffle furnace for heat preservation and annealing.

6. The method for preparing a silver-doped silicon phosphate glass sheet according to claim 5, characterized in that, In steps S2-3, the heat treatment temperature is 200-600℃ and the heat treatment time is 300-1200 min, the annealing temperature is 300-500℃ and the annealing time is 300-1200 min.

7. The method for preparing a silver-doped silicon phosphate glass sheet according to claim 2, characterized in that, In step S4, select sandpaper of 200 grit, 600 grit, 2500 grit, 4000 grit, 8000 grit and 10000 grit, and then polish the sample respectively.

8. An X-ray radiation dosimeter using a silver-doped silicon phosphate glass slide, characterized in that, It is prepared by the preparation method according to any one of claims 1-7.

9. The application of the X-ray radiation dosimeter as described in claim 8 in the preparation of radiation detection, non-destructive testing, or environmental monitoring products.

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