A rare earth element-doped radiation photoluminescent glass, a preparation method and application thereof

Abstract

The application provides a rare earth element doped radiation photoluminescence glass, a preparation method and application thereof, and solves the technical problem that the upper limit of a conventional radiation photoluminescence dosimeter is still insufficient for a high dose field. A glass component molar fraction expression of the rare earth element doped sodium aluminum phosphate silver glass is (1-x)[15.2%Al2O3-26.52%Na2O-58.06%P2O5-0.22%Ag2O]-xZ2O3, wherein Z is a rare earth element Lu or La, x is a molar fraction of Z2O3 in the rare earth element doped sodium aluminum phosphate silver glass, and 20%≤x≤40%. The rare earth oxide Lu2O3 or La2O3 is added into the sodium aluminum phosphate silver glass as a glass additive, the density of the glass is increased, more light emitting centers are formed, the glass has stronger ray blocking capacity, higher radiation detection efficiency, and better radiation dose-photoluminescence linearity, and the like; and the upper limit of a radiation dosimeter using the glass as a radiation photoluminescence material is improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of phosphate luminescent glass, and particularly relates to a rare earth element doped radiation photoluminescent glass as well as a preparation method and application thereof. BACKGROUND

[0002] In recent years, with the development and progress of nuclear energy and nuclear radiation technology in China, ionizing radiation technology is gradually widely applied in the fields of nuclear industry, aerospace technology, nuclear radiation medical technology and the like. At the same time, due to the harm of radiation to the human body, the demand for dosimeters for radiation dose monitoring is increasing day by day, and therefore, it is imperative to develop radiation sensitive detection materials with excellent performance.

[0003] Radio-photoluminescence (RPL) is a phenomenon that new luminescent centers are formed in the material through the interaction of ionizing radiation and medium, and visible light is emitted under ultraviolet excitation. In 1951, Schulman et al. first proposed to apply this luminescence phenomenon to a radiation photoluminescence glass dosimeter, and the component thereof is Ag-doped phosphate glass (Ag-PG); thereafter, Yokota et al. of Toshiba Company in Japan optimized the chemical components of the glass to improve the irradiation sensitivity, energy dependence and stability of the glass. With the further development of RPL technology, Chiyoda Technol Company first used Ag-doped phosphate glass as a personal dosimeter and put it into use in 2006.

[0004] RPL materials have the characteristics of small energy dependence, high sensitivity, repeatable reading, almost no signal decay, good dose linearity and the like. Among them, compared with optically stimulated luminescence (OSL) and thermally stimulated luminescence (TSL) materials, the most significant advantage of RPL materials as a radiation dosimeter is that the luminescent center is stable, and the RPL luminescent center will not disappear after being excited by ultraviolet light, and therefore, it has repeatable reading. In view of the above characteristics, the radiation photoluminescence glass dosimeter has received extensive attention in the field of radiation dose detection.

[0005] Previously, researchers have explored and improved phosphate radiation photoluminescence glass. Chinese patent CN102206042B aims at the problem that the structure of sodium aluminum phosphate glass is not compact, and simultaneously The chemical stability of the glass is poor due to the reaction with water. A Ag-doped lithium-sodium-aluminum phosphate glass is provided to improve the chemical stability of the radiation photoluminescence glass. A Ag and Nd co-doped lithium-aluminum glass is provided in Chinese Patent CN114180836B to improve the accuracy of the measurement by jointly calibrating the intensity of two luminescence peaks under ultraviolet light excitation.

[0006] However, according to the current research on phosphate glass in radiation dosimeter, the detection limit of radiation is rarely explored. The detection limit of the traditional Ag-doped phosphate glass radiation photoluminescence dosimeter is 10 muGy~1kGy, which is low enough, but the maximum radiation dose detection limit is still insufficient for high dose field, so it is necessary to improve the detection upper limit of the Ag-doped phosphate glass radiation photoluminescence dosimeter. SUMMARY

[0007] The purpose of the present application is to solve the technical problem that the detection upper limit of the traditional radiation photoluminescence dosimeter is still insufficient for high dose field, and to provide a rare earth element-doped radiation photoluminescence glass, its preparation method and application, to improve the luminescence efficiency of the glass and improve the radiation dose detection limit of the radiation photoluminescence material.

[0008] To achieve the above purpose, the technical solution provided by the present application is:

[0009] A rare earth element-doped aluminum sodium silver phosphate glass, characterized in that: the glass component mole fraction expression is (1-x) [15.2% Al2O3-26.52% Na2O-58.06% P2O5-0.22% Ag2O]-xZ2O3, wherein Z is a rare earth element Lu or La, 20%≤x≤40%, x is the mole fraction of Z2O3 in the rare earth element-doped aluminum sodium silver phosphate glass, and it is a luminescent glass.

[0010] The present application also provides a preparation method of the above-mentioned rare earth element-doped aluminum sodium silver phosphate glass, which is characterized by comprising the following steps:

[0011] 1) Raw material weighing

[0012] According to the components and mole percentages in the above general formula, the raw material formula is calculated, and the high-purity sodium phosphate (Na3PO4), sodium metaphosphate (NaPO3), aluminum metaphosphate (Al(PO3)3), silver oxide (Ag2O), and lutetium oxide (Lu2O3) or lanthanum oxide (La2O3) are weighed according to the formula to obtain the glass batch;

[0013] 2) Preparation of glass premix

[0014] The raw materials weighed in step 1) are blended with anhydrous ethanol (since some of the raw materials are soluble in water, anhydrous ethanol is selected as the grinding solvent when wet grinding) after ball milling, and then dried and ground to obtain a uniformly mixed glass premix; in order to further ensure the uniformity of the glass premix particles used in the subsequent steps, the glass premix can be sieved after grinding to obtain a glass premix;

[0015] 3) High-temperature melting glass

[0016] The glass premix obtained in step 2) is heated to complete melting to obtain a uniformly clear glass liquid;

[0017] 4) Glass forming

[0018] The glass liquid obtained in step 3) is poured into a preheated mold, and after the glass is cooled and formed, annealing treatment is performed, and the cooling is performed to room temperature to obtain a rare earth element-doped sodium aluminum phosphate silver glass.

[0019] Further, step 2) is specifically:

[0020] 2.1) The raw materials weighed in step 1) are placed in a zirconia ball mill tank, and anhydrous ethanol is mixed into a slurry; wherein the mass ratio of raw materials: anhydrous ethanol: zirconia balls is 1:2:5;

[0021] 2.2) The zirconia ball mill tank containing the slurry in step 2.1) is placed in a planetary ball mill, and ball milling is performed at a speed of 200 rad / min for 3 hours;

[0022] 2.3) The zirconia ball mill tank is removed, and the slurry in the tank is dried and ground through a 200-mesh sieve to obtain a uniformly mixed glass premix with uniform particles.

[0023] Further, step 3) is specifically:

[0024] The glass premix obtained in step 2) is transferred to a pre-cleaned platinum crucible and placed in a muffle furnace, and heated to 1300-1450℃ at a heating rate of 5-10℃ / min (below 1200℃, the heating rate is set to 10℃ / min, and above 1200℃, in order to prevent damage to the muffle furnace, the heating rate is reduced to 5℃ / min; the temperature increases with the increase of the content of lutetium oxide or lanthanum oxide), and after the temperature reaches the target temperature, it is kept for 2-3h (the purpose of this heat preservation is to allow the raw materials to melt completely), to obtain a uniformly clear glass liquid after complete melting.

[0025] Further, step 4) is specifically:

[0026] The molten glass obtained in step 3) is poured into a stainless steel mold preheated to 400°C. After the glass cools and solidifies, it is immediately placed in a muffle furnace at 400°C (this temperature is generally selected to be several tens of degrees lower than the glass transition temperature Tg) for annealing and holding for 1-3 hours. Then, it is cooled to room temperature with the furnace to eliminate the thermal stress inside the glass, thus obtaining rare earth element doped sodium aluminum phosphate silver glass.

[0027] Meanwhile, the present invention also provides the above-mentioned rare earth element-doped sodium aluminum phosphate silver glass as a radiation photoluminescent material and its application in a radiation dosimeter.

[0028] Based on the above applications, the present invention provides a radiation dosimeter that uses rare earth element-doped sodium aluminum phosphate silver glass as a radiation photoluminescent material.

[0029] The concept and principle of this invention:

[0030] In response to the problems existing in current radiation photoluminescence dosimeters, the research team of this invention believes that by increasing the density of the glass matrix, the scattering of ionizing radiation such as X-rays inside the glass can be greatly enhanced, reducing the penetration of high-energy rays into the glass. This allows more high-energy rays entering the glass to fully act on the luminescent ions during the scattering process, forming more luminescent centers, thereby improving its luminescence efficiency and increasing the radiation dose detection limit.

[0031] Heavy metals have high densities, and introducing their oxides into existing glass matrices can significantly increase the glass's density, effectively improving its radiation blocking ability, reducing radiation energy penetration, and increasing radiation detection efficiency. Simultaneously, the high atomic numbers of heavy metals give them strong scattering capabilities, enabling them to scatter radiation energy in all directions, creating more luminescent centers within the glass. This results in photoluminescent glass exhibiting excellent photoluminescence performance, improving the detection limit of the radiation dosimeter. However, given the large number of heavy metals, deciding which type of heavy metal oxide to add is another challenge for the research team. Considering that the root cause of current problems with photoluminescent dosimeters lies in increasing the luminescence of the glass itself, rather than introducing luminescence from other substances, the research team selected the non-luminescent rare earth elements lutetium and lanthanum from among the many heavy metal elements. Because trivalent ions have closed shells, the energy required for transitions from the ground state to the excited state is high, and they have no absorption in the 200-1000 nm range, thus not emitting light and fully meeting the aforementioned requirements.

[0032] Therefore, the application uses phosphate as a glass matrix, prepares a luminescent glass by using a high-temperature melting method, selects rare earth oxide Lu2O3 or La2O3 as a glass additive, increases the density of the glass by adjusting the content of Lu or La, enhances the absorption of ionizing radiation such as X-rays by the radiation photoluminescent glass, and due to the strong scattering ability of the rare earth element, more radiation energy can be applied to the formation of more and luminescent centers. The increase of the luminescent centers makes the glass have better radiation photoluminescent performance under the excitation of ultraviolet light, and improves the radiation detection limit of the glass radiation dosimeter.

[0033] The application has the following advantages:

[0034] 1. The rare earth oxide Lu2O3 or La2O3 is added into the sodium aluminum silver phosphate glass as a glass additive, the density of the glass is increased, more luminescent centers are formed, and compared with the traditional Ag-PG, the glass has stronger ray blocking ability, higher radiation detection efficiency, and better radiation dose-photoluminescent linear relationship.

[0035] 2. The glass prepared by the application has good ultraviolet-visible light transmittance, and the absorption peak of the glass does not change obviously before and after irradiation, which indicates that the absorption of the material does not affect the detection effect of PL (photoluminescence) and RPL (radiation photoluminescence).

[0036] 3. The process method for synthesizing the glass is simple, the yield is high, the radiation photoluminescent glass doped with the rare earth elements lutetium or lanthanum prepared by the application has good irradiation stability, can realize automation and large-scale industrialization, and has wide application prospects.

[0037] 4. The glass prepared by the application as a radiation dosimeter of a radiation photoluminescent material has improved upper detection limit; and due to the luminescence mechanism of the radiation photoluminescent material, the radiation dosimeter has the advantages of non-destructive data reading and repeated use below 400 DEG C. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 The XRD patterns of the glasses obtained in Examples 1-5 and Comparative Example 1 of the application.

[0039] Figure 2 The ultraviolet-visible transmittance spectrum of the glass obtained in Examples 2-4 of the application.

[0040] Figure 3 The ultraviolet-visible absorption spectrum of the glass obtained in Examples 2-4 of the application before irradiation.

[0041] Figure 4The UV-visible absorption spectrum of the glass obtained in Example 2-4 of the present application after irradiation.

[0042] Figure 5 The fluorescence emission spectrum of the glass obtained in Example 1-5 and Comparative Example 1 of the present application after irradiation with the same dose of X-rays under excitation of 365 nm ultraviolet light.

[0043] Figure 6 The radiation measurement comparison chart of Example 4 and Comparative Example 1 of the present application. DETAILED DESCRIPTION

[0044] The content of the present application is further described in detail below in combination with the drawings and specific examples:

[0045] Example 1

[0046] Table 1 is the specific components of the inventive glass and their mole percentages.

[0047] Table 1

[0048]

[0049] 1) Raw material weighing:

[0050] The raw material formula was calculated according to the components of the glass described in Table 1, and 1.571 g of sodium phosphate (Na3PO4), 2.1008 g of sodium metaphosphate (NaPO3), 6.9729 g of aluminum metaphosphate (Al(PO3)3), 0.0965 g of silver oxide (Ag2O), and 9.2588 g of lutetium oxide (Lu2O3) powder were weighed according to the formula to obtain the glass batch;

[0051] 2) Preparation of glass premix:

[0052] The weighed raw materials were placed in a zirconia ball mill jar and 50 ml of anhydrous ethanol was added to form a slurry; the zirconia ball mill jar containing the slurry was placed in a planetary ball mill and ball milled at a speed of 200 rad / min for 3 hours; then the zirconia ball mill jar was taken out and the slurry inside was dried and ground into powder (through a 200 mesh sieve) to obtain a uniformly mixed glass premix;

[0053] 3) High temperature melting of glass:

[0054] The obtained glass premix was transferred to a pre-cleaned platinum crucible and placed in a muffle furnace, and the temperature was raised to 1300℃ (the heating rate was set at 10 ℃ / min below 1200℃, and the heating rate was reduced to 5 ℃ / min above 1200℃ to prevent damage to the muffle furnace), and the temperature was kept at 1300℃ for 2 hours to obtain a completely melted and uniformly clarified glass liquid;

[0055] 4) Glass forming:

[0056] The completely melted glass liquid was cast into a stainless steel mold preheated to 400°C, and after the glass was cooled and formed, it was immediately placed in a 400°C muffle furnace for annealing for 1 hour, and then furnace-cooled to room temperature to eliminate the thermal stress in the glass, to obtain the target glass.

[0057] Example 2

[0058] Table 2 is the specific components of the inventive glass and their mole percentages.

[0059] Table 2

[0060]

[0061] 1) Raw material weighing:

[0062] The raw material formula was calculated according to the components of the glass described in Table 2, and 1.361 g of sodium phosphate (Na3PO4), 1.82 g of sodium metaphosphate (NaPO3), 6.04 g of aluminum metaphosphate (Al(PO3)3), 0.0836 g of silver oxide (Ag2O), and 10.6947 g of lutetium oxide (Lu2O3) powder were weighed according to the formula to obtain the glass batch;

[0063] 2) Preparation of glass premix:

[0064] The weighed raw materials were placed in a zirconia ball mill jar, and 50 ml of anhydrous ethanol was added to form a slurry; the zirconia ball mill jar containing the slurry was placed in a planetary ball mill, and ball milled at a speed of 200 rad / min for 3 hours; then the zirconia ball mill jar was taken out, and the slurry in it was dried and ground into powder (through a 200 mesh sieve) to obtain a uniformly mixed glass premix;

[0065] 3) High-temperature melting of glass:

[0066] The obtained glass premix was transferred to a pre-cleaned platinum crucible and placed in a muffle furnace, and heated to 1350°C (below 1200°C, the heating rate was set to 10 ℃ / min, and above 1200°C, to prevent damage to the muffle furnace, the heating rate was reduced to 5 ℃ / min), and after the temperature reached 1350°C, it was kept for 2 hours to obtain a completely melted and uniformly clarified glass liquid;

[0067] 4) Glass forming:

[0068] The completely melted glass liquid was cast into a stainless steel mold preheated to 400°C, and after the glass was cooled and formed, it was immediately placed in a 400°C muffle furnace for annealing for 1 hour, and then furnace-cooled to room temperature to eliminate the thermal stress in the glass, to obtain the target glass.

[0069] Example 3

[0070] Table 3 is the specific components of the inventive glass and their mole percentages.

[0071] Table 3

[0072]

[0073] 1) Raw material weighing:

[0074] The raw material formula was calculated according to the components of the glass described in Table 3, and 1.181 g of sodium phosphate (Na3PO4), 1.579 g of sodium metaphosphate (NaPO3), 5.24 g of aluminum metaphosphate (Al(PO3)3), 0.0725 g of silver oxide (Ag2O), and 11.928 g of lutetium oxide (Lu2O3) powder were weighed according to the formula to obtain the glass batch;

[0075] 2) Preparation of glass premix:

[0076] The weighed raw materials were placed in a zirconia ball mill jar and 50 ml of anhydrous ethanol was added to form a slurry; the zirconia ball mill jar containing the slurry was placed in a planetary ball mill and ball milled at a speed of 200 rad / min for 3 hours; then the zirconia ball mill jar was taken out and the slurry in it was dried and ground into powder (through a 200 mesh sieve) to obtain a uniformly mixed glass premix;

[0077] 3) High temperature melting of glass:

[0078] The obtained glass premix was transferred to a pre-cleaned platinum crucible and placed in a muffle furnace, and the temperature was raised to 1350℃ (the heating rate was set at 10 ℃ / min below 1200℃, and the heating rate was reduced to 5 ℃ / min above 1200℃ to prevent damage to the muffle furnace), and the temperature was kept at 1350℃ for 2.5 hours to obtain a completely melted and uniformly clarified glass liquid;

[0079] 4) Glass forming:

[0080] The completely melted glass liquid was poured into a stainless steel mold preheated to 400℃, and after the glass was cooled and formed, it was immediately placed in a 400℃ muffle furnace for annealing for 2 hours, and then cooled to room temperature in the furnace to eliminate the thermal stress in the glass, to obtain the target glass.

[0081] Example 4

[0082] Table 4 is the specific components of the inventive glass and their mole percentages.

[0083] Table 4

[0084]

[0085] 1) Raw material weighing:

[0086] According to the raw material formula calculated according to the components of the glass described in Table 4, 1.024 g of sodium phosphate (Na3PO4), 1.369 g of sodium metaphosphate (NaPO3), 4.545 g of aluminum metaphosphate (Al(PO3)3), 0.0629 g of silver oxide (Ag2O) and 12.9986 g of lutetium oxide (Lu2O3) powder were weighed according to the formula to obtain a mixed batch;

[0087] 2) Preparation of glass premix:

[0088] The weighed raw materials were placed in a zirconia ball mill jar, and 50 ml of anhydrous ethanol was added to form a slurry; the zirconia ball mill jar containing the slurry was placed in a planetary ball mill, and the slurry was ball milled at a speed of 200 rad / min for 3 hours; then the zirconia ball mill jar was taken out, and the slurry in it was dried and ground into powder (through a 200 mesh sieve) to obtain a mixed glass premix;

[0089] 3) High temperature melting glass:

[0090] The obtained glass premix was transferred to a pre-cleaned platinum crucible and placed in a muffle furnace, and the temperature was raised to 1400℃ (below 1200℃, the temperature rising speed was set at 10 ℃ / min, and above 1200℃, in order to prevent damage to the muffle furnace, the temperature rising speed was reduced to 5 ℃ / min), and after the temperature reached 1400℃, it was kept for 2.5 hours to obtain a completely melted and uniformly clarified glass liquid;

[0091] 4) Glass forming:

[0092] The completely melted glass liquid was poured into a stainless steel mold preheated to 400℃, and after the glass was cooled and formed, it was immediately placed in a 400℃ muffle furnace for annealing for 3 hours, and then cooled to room temperature in the furnace to eliminate the thermal stress in the glass, to obtain the target glass.

[0093] Example 5

[0094] Table 5 is the specific components and their mole percentages of the inventive glass.

[0095] Table 5

[0096]

[0097] 1) Raw material weighing:

[0098] The raw material formula was calculated according to the components of the glass described in Table 5, and 0.8868 g of sodium phosphate (Na3PO4), 1.1859 g of sodium metaphosphate (NaPO3), 3.936 g of aluminum metaphosphate (Al(PO3)3), 0.0545 g of silver oxide (Ag2O), and 13.9369 g of lutetium oxide (Lu2O3) powder were weighed according to the formula to obtain the glass batch;

[0099] 2) Preparation of glass premix:

[0100] The weighed raw materials were placed in a zirconia ball mill jar, and 50 ml of anhydrous ethanol was added to form a slurry; the zirconia ball mill jar containing the slurry was placed in a planetary ball mill, and ball milling was carried out at a speed of 200 rad / min for 3 hours; then the zirconia ball mill jar was taken out, and the slurry in it was dried and ground into powder (through a 200 mesh sieve) to obtain a uniformly mixed glass premix;

[0101] 3) High-temperature melting of glass:

[0102] The obtained glass premix was transferred to a pre-cleaned platinum crucible and placed in a muffle furnace, and the temperature was raised to 1450°C (below 1200°C, the heating rate was set to 10 ℃ / min, and above 1200°C, the heating rate was reduced to 5 ℃ / min to prevent damage to the muffle furnace), and the temperature was kept at 1450°C for 3 hours to obtain a completely melted and uniformly clarified glass liquid;

[0103] 4) Glass forming:

[0104] The completely melted glass liquid was poured into a stainless steel mold preheated to 400°C, and after the glass was cooled and formed, it was immediately placed in a 400°C muffle furnace for annealing for 3 hours, and then cooled to room temperature in the furnace to eliminate the thermal stress in the glass, thereby obtaining the target glass.

[0105] Example 6

[0106] Table 6 shows the specific components and their mole percentages of the inventive glass.

[0107] Table 6

[0108]

[0109] 1) Raw material weighing:

[0110] The raw material formula was calculated according to the components of the glass described in Table 6, and 1.7149 g of sodium phosphate (Na3PO4), 2.2932 g of sodium metaphosphate (NaPO3), 7.6116 g of aluminum metaphosphate (Al(PO3)3), 0.1053 g of silver oxide (Ag2O), and 8.275 g of lanthanum oxide (La2O3) powder were weighed according to the formula to obtain the glass batch;

[0111] 2) Preparation of glass premix:

[0112] The raw materials were weighed into a zirconium oxide ball mill jar and mixed into a slurry with 50 ml of absolute ethanol. The slurry was ball milled in a planetary ball mill at 200 rpm for 3 hours. The slurry was then removed from the zirconium oxide ball mill jar and dried, ground into a powder (through a 200 mesh screen), and a homogeneous glass premix was obtained.

[0113] 3) High temperature melting of glass:

[0114] The glass premix was transferred into a pre-cleaned platinum crucible and placed in a muffle furnace. The temperature was ramped to 1300 °C at a rate of 10 °C / min below 1200 °C and 5 °C / min above 1200 °C to prevent damage to the muffle furnace. The temperature was held at 1300 °C for 2 hours to obtain a completely melted and homogenously clarified glass liquid.

[0115] 4) Glass forming:

[0116] The completely melted glass liquid was poured into a preheated stainless steel mold at 400 °C. The glass was allowed to cool and form. The glass was then immediately placed in a muffle furnace at 400 °C for 1 hour to anneal and then furnace cooled to room temperature to relieve internal thermal stress. The target glass was obtained.

[0117] Example 7

[0118] Table 7 lists the specific components and their mole percentages for the inventive glasses.

[0119] Table 7

[0120]

[0121] 1) Raw material weighing:

[0122] The raw material formulation was calculated based on the components of the glass described in Table 7. 1.507 g of sodium phosphate (Na3P04), 2.0153 g of sodium metaphosphate (NaP03), 6.689 g of aluminum metaphosphate (Al(P03)3), 0.0926 g of silver oxide (Ag20), and 9.6961 g of lanthanum oxide (La203) powders were weighed according to the formulation to obtain the batch of the glass.

[0123] 2) Preparation of glass premix:

[0124] The raw materials in the amount are put into a zirconium oxide ball mill jar, and 50 ml of anhydrous ethanol is added to mix into a slurry; the zirconium oxide ball mill jar containing the slurry is put into a planetary ball mill, and ball milling is performed at a speed of 200 rad / min for 3 hours; then the zirconium oxide ball mill jar is taken out, and the slurry in the jar is dried and ground into powder (through a 200-mesh sieve) to obtain a uniformly mixed glass premix;

[0125] 3) High-temperature melting of glass:

[0126] The obtained glass premix is transferred to a pre-cleaned platinum crucible and placed in a muffle furnace, and the temperature is raised to 1350°C (below 1200°C, the temperature raising speed is set to 10 ℃ / min, and above 1200°C, the temperature raising speed is reduced to 5 ℃ / min to prevent damage to the muffle furnace), and after the temperature reaches 1350°C, the temperature is kept for 2 hours to obtain a completely melted and uniformly clarified glass liquid;

[0127] 4) Glass forming:

[0128] The completely melted glass liquid is poured into a stainless steel mold preheated to 400°C, and after the glass is cooled and formed, it is immediately placed in a 400°C muffle furnace for annealing for 2 hours, and then cooled to room temperature in the furnace to eliminate the thermal stress in the glass, to obtain the target glass.

[0129] Example 8

[0130] Table 8 is the specific components of the glass of the application and their mole percentages.

[0131] Table 8

[0132]

[0133] 1) Raw material weighing:

[0134] The raw material formula is calculated according to the components of the glass described in Table 8, and 1.3237 g of sodium phosphate (Na3PO4), 1.7701 g of sodium metaphosphate (NaPO3), 5.8752 g of aluminum metaphosphate (Al(PO3)3), 0.0813 g of silver oxide (Ag2O), and 10.9497 g of lanthanum oxide (La2O3) powder are weighed according to the formula to obtain the glass batch;

[0135] 2) Preparation of glass premix:

[0136] The raw materials in the amount are put into a zirconium oxide ball mill jar, and 50 ml of anhydrous ethanol is added to mix into a slurry; the zirconium oxide ball mill jar containing the slurry is put into a planetary ball mill, and ball milling is performed at a speed of 200 rad / min for 3 hours; then the zirconium oxide ball mill jar is taken out, and the slurry in the jar is dried and ground into powder (through a 200-mesh sieve) to obtain a uniformly mixed glass premix;

[0137] 3) High temperature melting of glass:

[0138] The obtained glass premix was transferred into a pre-cleaned platinum crucible and placed in a muffle furnace, and the temperature was raised to 1350°C (the temperature was raised at a rate of 10°C / min below 1200°C, and the temperature was raised at a rate of 5°C / min above 1200°C to prevent damage to the muffle furnace), and the temperature was maintained at 1350°C for 2.5 hours, and a completely melted and uniformly clarified glass liquid was obtained;

[0139] 4) Glass forming:

[0140] The completely melted glass liquid was poured into a stainless steel mold preheated to 400°C, and after the glass was cooled and formed, it was immediately placed in a 400°C muffle furnace for annealing for 2 hours, and then cooled to room temperature in the furnace to eliminate the thermal stress in the glass, and the target glass was obtained.

[0141] Example 9

[0142] Table 9 shows the specific components of the inventive glass and their mole percentages.

[0143] Table 9

[0144]

[0145] 1) Raw material weighing:

[0146] The raw material formula was calculated according to the components of the glass described in Table 9, and 1.1607 g of sodium phosphate (Na3PO4), 1.5522 g of sodium metaphosphate (NaPO3), 5.152 g of aluminum metaphosphate (Al(PO3)3), 0.0713 g of silver oxide (Ag2O), and 12.0638 g of lanthanum oxide (La2O3) powder were weighed according to the formula, and a uniformly mixed batch was obtained;

[0147] 2) Preparation of glass premix:

[0148] The weighed raw materials were placed in a zirconia ball mill jar, and 50 ml of anhydrous ethanol was added to form a slurry; the zirconia ball mill jar containing the slurry was placed in a planetary ball mill, and the slurry was ball milled at a speed of 200 rad / min for 3 hours; then the zirconia ball mill jar was taken out, and the slurry in it was dried and ground into powder (through a 200 mesh sieve) to obtain a uniformly mixed glass premix;

[0149] 3) High temperature melting of glass:

[0150] The obtained glass premix was transferred into a pre-cleaned platinum crucible and placed in a muffle furnace, and the temperature was raised to 1400°C (the temperature was raised at a rate of 10°C / min below 1200°C, and the temperature was raised at a rate of 5°C / min above 1200°C to prevent damage to the muffle furnace), and the temperature was maintained at 1400°C for 2.5 hours, and a completely melted and uniformly clarified glass liquid was obtained;

[0151] 4) Glass forming:

[0152] The completely melted glass liquid was poured into a stainless steel mold preheated to 400°C, and after the glass was cooled and formed, it was immediately placed in a 400°C muffle furnace for annealing for 3 hours, and then cooled to room temperature in the furnace to eliminate thermal stress in the glass, and the target glass was obtained.

[0153] Example 10

[0154] Table 10 shows the specific components of the inventive glass and their mole percentages.

[0155] Table 10

[0156]

[0157] 1) Raw material weighing:

[0158] The raw material formula was calculated according to the components of the glass described in Table 10, and 1.015g of sodium phosphate (Na3PO4), 1.3573g of sodium metaphosphate (NaPO3), 4.505g of aluminum metaphosphate (Al(PO3)3), 0.0623g of silver oxide (Ag2O), and 13.0604g of lanthanum oxide (La2O3) powder were weighed according to the formula, and the glass batch was obtained;

[0159] 2) Preparation of glass premix:

[0160] The weighed raw materials were placed in a zirconia ball mill jar, and 50ml of anhydrous ethanol was added to form a slurry; the zirconia ball mill jar containing the slurry was placed in a planetary ball mill, and the slurry was ball milled at a speed of 200 rad / min for 3 hours; then the zirconia ball mill jar was taken out, and the slurry in the jar was dried and ground into powder (through a 200 mesh sieve), and a uniformly mixed glass premix was obtained;

[0161] 3) High temperature melting glass:

[0162] The obtained glass premix was transferred into a pre-cleaned platinum crucible and placed in a muffle furnace, and heated to 1450°C (the heating rate was set to 10°C / min below 1200°C, and reduced to 5°C / min above 1200°C to prevent damage to the muffle furnace), and after the temperature reached 1450°C, the temperature was maintained for 3 hours, to obtain a completely melted and uniformly clarified glass liquid;

[0163] 4) Glass forming:

[0164] The completely melted glass liquid was poured into a stainless steel mold preheated to 400°C, and after the glass was cooled and formed, it was immediately placed in a 400°C muffle furnace for annealing for 3 hours, and then cooled to room temperature with the furnace, to eliminate the thermal stress in the glass, to obtain the target glass.

[0165] Comparative Example 1

[0166] Table 11 is the specific components of the inventive glass and their mole percentages.

[0167] Table 11

[0168]

[0169] 1) Raw material weighing:

[0170] The raw material formula was calculated according to the components of the glass described in Table 11, and 1.3969 g of sodium phosphate (Na3PO4), 7.2413 g of sodium metaphosphate (NaPO3), 11.2869 g of aluminum metaphosphate (Al(PO3)3), and 0.0749 g of silver oxide (Ag2O) powder were weighed according to the formula to obtain the glass batch;

[0171] 2) Preparation of glass premix:

[0172] The weighed raw materials were placed in a zirconia ball mill jar, and 50 ml of anhydrous ethanol was added to form a slurry; the zirconia ball mill jar containing the slurry was placed in a planetary ball mill, and ball milled at a speed of 200 rad / min for 3 hours; then the zirconia ball mill jar was taken out, and the slurry in it was dried and ground into powder (through a 200 mesh sieve) to obtain a uniformly mixed glass premix;

[0173] 3) High temperature melting of glass:

[0174] The obtained glass premix was transferred into a pre-cleaned platinum crucible and placed in a muffle furnace, and heated to 1450°C (the heating rate was set to 10°C / min below 1200°C, and reduced to 5°C / min above 1200°C to prevent damage to the muffle furnace), and after the temperature reached 1450°C, the temperature was maintained for 3 hours, to obtain a completely melted and uniformly clarified glass liquid;

[0175] 4) Glass forming:

[0176] The completely molten glass liquid is cast in a stainless steel mold preheated to 400 DEG C, and after the glass is cooled and shaped, it is immediately placed in a muffle furnace at 400 DEG C for annealing for 1 hour, and then furnace-cooled to room temperature to eliminate thermal stress in the glass, to obtain the target glass.

[0177] In order to verify the properties of the rare earth element lutetium-doped sodium aluminum silver phosphate glass, the following experimental tests and theoretical analyses are carried out.

[0178] 1. Table 12 is the density of the glass samples obtained in Examples 1-5 and Comparative Example 1

[0179] As can be clearly seen from Table 12, by adding rare earth oxide Lu2O3 in the glass formula, the density of the glass is significantly improved, and as the content of Lu2O3 increases, the density of the glass increases; effectively improves the radiation blocking ability of the glass, reduces the penetration of radiation energy, and further improves the radiation detection efficiency.

[0180] Table 12

[0181]

[0182] 2. Figure 1 The XRD pattern of the glass prepared in Examples 1-5 and Comparative Example 1 of the present application is shown in Figure 2. Figure 1 As can be seen from the XRD pattern of the glass prepared in Examples 1-5 and Comparative Example 1, only amorphous peaks exist, and there are no strong peaks, which can fully guarantee the amorphous nature of the glass sample.

[0183] 3. Figure 2 The ultraviolet-visible transmittance spectrum of the glass obtained in Examples 2-4 of the present application is shown in Figure 3. Figure 2 As can be seen from the ultraviolet-visible transmittance spectrum of the glass prepared in Examples 2-4, the transmittance of the glass in the visible light region is about 75%, and there is also good transmittance in the ultraviolet light region greater than 350 nm, which can ensure that the glass emits fluorescence under the excitation of ultraviolet light.

[0184] 4. Figure 3 The ultraviolet-visible absorption spectrum of the glass obtained in Examples 2-4 of the present application before irradiation is shown in Figure 4, Figure 4 The ultraviolet-visible absorption spectrum of the glass obtained in Examples 2-4 of the present application after irradiation is shown in Figure 5. Figure 3 and Figure 4 As can be seen from the comparison, the absorption of the glass prepared in Examples 2-4 in the ultraviolet region does not change much before and after irradiation, which can ensure that the glass can absorb and utilize ultraviolet rays after irradiation.

[0185] 5. Figure 5The fluorescence emission spectra of the glasses obtained in Examples 1-5 and Comparative Example 1 of the present application after 100 Gy X-ray irradiation under 365 nm ultraviolet light excitation are shown in the following table. Figure 5 It can be seen that, with the increase of the content of rare earth oxide Lu2O3, more light emitting centers are formed through the strong scattering ability of heavy metal elements, and the fluorescence emission intensity of the sample under 365 nm ultraviolet light excitation is continuously enhanced, thereby realizing the improvement of the light emitting efficiency of the glass.

[0186] 6. Figure 6 The emission spectra of the glasses obtained in Example 4 and Comparative Example 1 of the present application under different doses of X-ray irradiation are shown in the following table.

[0187] In summary, by introducing rare earth oxide Lu2O3 into the sodium aluminum phosphate silver glass, the scattering of X-ray ionizing radiation in the glass can be greatly enhanced, the penetration of high-energy rays through the glass can be reduced, more high-energy rays entering the glass interior can fully act on the light emitting ions in the scattering process, more light emitting centers can be formed, and the light emitting efficiency can be improved, thereby increasing the radiation dose detection limit and solving the problem that the upper limit of the detection of the traditional radiation photoluminescence dosimeter is still insufficient for high dose fields.

[0188] At the same time, the research team of the present application also tested the performance of the rare earth element lanthanum doped sodium aluminum phosphate silver glasses prepared in Examples 6-10 and the comparative example, and the test results were the same as the above test results, that is, the rare earth element lanthanum doped sodium aluminum phosphate silver glasses and the rare earth element lutetium doped sodium aluminum phosphate silver glasses have the same effect, and can solve the problem that the upper limit of the detection of the traditional radiation photoluminescence dosimeter is still insufficient for high dose fields.

[0189] The above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can easily think of various equivalent modifications or replacements within the technical range disclosed in the present application, and these modifications or replacements should be covered within the protection scope of the present application.

Claims

1. A rare earth element-doped sodium aluminum phosphate silver glass, characterized in that: The expression for the mole fraction of its glass composition is (1-x)[15.2%Al2O3-26.52%Na2O-58.06%P2O5-0.22%Ag2O]-xZ2O3, where Z is the rare earth element Lu or La, and x is the mole fraction of Z2O3 in the rare earth element-doped sodium aluminum phosphate silver glass, 20%≤x≤40%.

2. A method for preparing rare earth element-doped sodium aluminum phosphate silver glass, characterized in that, Includes the following steps: 1) Weighing raw materials Calculate the raw material formula according to the components and molar percentages in the glass component mole fraction expression of claim 1, and weigh high-purity sodium phosphate, sodium metaphosphate, aluminum metaphosphate, silver oxide, and lutetium oxide or lanthanum oxide according to the formula. 2) Preparation of glass premix The raw material weighed in step 1) is mixed with anhydrous ethanol, ball-milled, dried, and ground to obtain a uniformly mixed glass premix. 3) High-temperature molten glass The glass premix obtained in step 2) is heated until it is completely melted to obtain a homogeneous and clarified glass melt. 4) Glass forming The molten glass obtained in step 3) is poured into a preheated mold. After the glass cools and solidifies, it is annealed and cooled to room temperature to obtain rare earth element-doped sodium aluminum phosphate silver glass.

3. The preparation method according to claim 2, characterized in that, Step 2) specifically involves: 2.1) Place the raw material weighed in step 1) into a zirconia ball mill jar and add anhydrous ethanol to mix into a slurry; 2.2) Place the zirconia ball mill jar containing the slurry from step 2.1) into a planetary ball mill and ball mill at a speed of 200 rad / min for 3 hours; 2.3) Remove the zirconia ball mill jar, dry the slurry inside, grind it through a 200-mesh sieve, and obtain a uniformly mixed glass premix.

4. The preparation method according to claim 2 or 3, characterized in that, Step 3) specifically involves: The glass premix obtained in step 2) is transferred to a pre-cleaned platinum crucible and placed in a muffle furnace. The temperature is increased to 1300-1450℃ at a heating rate of 5-10℃ / min and held for 2-3 hours to obtain a completely melted and uniformly clarified glass melt.

5. The preparation method according to claim 4, characterized in that, Step 4) specifically involves: The molten glass obtained in step 3) is poured into a stainless steel mold preheated to 400°C. After the glass cools and solidifies, it is immediately placed in a muffle furnace at 400°C for annealing for 1-3 hours. The glass is then cooled to room temperature in the furnace to obtain rare earth element-doped sodium aluminum phosphate silver glass.

6. The application of the rare earth element-doped sodium aluminum phosphate glass of claim 1 as a radioluminescent material.

7. The application of the rare earth element-doped sodium aluminum phosphate glass of claim 1 as a radiation photoluminescent material in a radiation dosimeter.

8. A radiation dosimeter, characterized in that, The rare earth element-doped sodium aluminum phosphate glass described in claim 1 is used as a radioluminescent material.

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