Europium-doped bismuthate radiation-resistant optical glass material and preparation method thereof

Abstract

The invention discloses a europium-doped bismuthate radiation-resistant optical glass material and a preparation method thereof, 50 to 56 parts of H3BO3, 0.9 to 1.8 parts of La2O3, 1.1 to 2.8 parts of Na2CO3, 4.8 to 5.5 parts of K2CO3, 30 to 45 parts of Bi2O3, 0.5 to 3.8 parts of Eu2O3 and 1.2 to 4.5 parts of Sb2O3 are mixed and then are subjected to high-temperature melting, and obtained high-temperature glass liquid is subjected to molding and annealing treatment to obtain the europium-doped bismuthate radiation-resistant optical glass material. According to the radiation-resistant glass prepared by the invention, the novel variable valence element Eu is added, so that the formation of a color center in a microstructure after high-dose gamma radiation can be effectively inhibited. Meanwhile, the novel variable valence element Eu can practically solve the problems that the radiation-resistant glass is discolored and the initial transmittance is reduced due to the traditional variable valence element Ce. On the basis of the gamma absorption coefficient of the element, the Bi oxide in the radiation-resistant glass is used as one of network forming bodies, so that the problem of toxicity of the Pb element is avoided while the radiation resistance is ensured. The Sb element oxide is added, so that the problems that the Bi element causes glass discoloration and the initial transmittance of the glass is reduced are effectively solved.

Description

Technical Field

[0001] The present invention relates to the technical field of optical glass materials, and particularly to an europium-doped bismuthate radiation-resistant optical glass material and a preparation method thereof. Background Art

[0002] Optical glasses have many applications in the strong radiation field of the nuclear industry, such as glove box viewing windows, hot cell observation windows, and radiation-resistant cameras. However, the irradiation of high-energy rays will cause significant degradation of the optical properties of the glass, making the optical system or monitoring device unable to work properly, which will bring great risks to the safety detection and monitoring of the strong radiation environment.

[0003] At present, the varieties of radiation-resistant optical glass materials in China are single, and the optical glasses used in the strong radiation field rely on high-cost imports. In the glass system, a large increase in the lead content not only increases the melting technical difficulty of the optical glass, but also causes harm to the environment and the human body. Replacing the lead element with the bismuth element can effectively solve this problem and improve the radiation resistance of the glass. However, the high-bismuth-content glass is prone to discoloration, which has an adverse effect on the initial transmittance of the glass. As a commonly used doping element for radiation-resistant optical glasses, cerium can effectively inhibit the formation of color centers in the glass after irradiation. However, it will also introduce absorption peaks in the visible light region in the microstructure of the glass, making the glass turn yellow and thus reducing its initial transmittance.

[0004] In view of the above deficiencies, an optical glass that is environmentally friendly, harmless to the human body, has improved radiation performance, and whose initial transmittance is not affected is urgently needed in the current field. Summary of the Invention

[0005] Based on the above analysis, in order to solve the negative impacts caused by lead and cerium elements in traditional radiation-resistant optical glasses, the present invention provides an europium-doped bismuthate radiation-resistant optical glass material and a preparation method thereof. It can effectively solve the problem that the varieties of radiation-resistant optical glass materials in China are single and the optical glasses used in the strong radiation field rely on high-cost imports. To solve this technical problem, the present invention adopts the following technical solutions:

[0006] The present invention first discloses an europium-doped bismuthate radiation-resistant optical glass material, comprising raw materials in the following weight ratio:

[0007] H3BO3 50 - 56 parts, La2O3 0.9 - 1.8 parts, Na2CO3 1.1 - 2.8 parts, K2CO3 4.8 - 5.5 parts, Bi2O3 30 - 45 parts, Eu2O3 0.5 - 3.8 parts, Sb2O3 1.2 - 4.5 parts.

[0008] Further, the europium-doped bismuthate radiation-resistant optical glass material comprises:

[0009] 53 - 56 parts of H3BO3, 0.9 - 1.3 parts of La2O3, 1.1 - 2.5 parts of Na2CO3, 4.8 - 5.1 parts of K2CO3, 30 - 41 parts of Bi2O3, 1.5 - 3.8 parts of Eu2O3, 1.2 - 2.5 parts of Sb2O3.

[0010] Furthermore, the europium - doped bismuthate radiation - resistant optical glass material includes:

[0011] 53 parts of H3BO3, 1.8 parts of La2O3, 2.2 parts of Na2CO3, 5 parts of K2CO3, 33 parts of Bi2O3, 3.5 parts of Eu2O3, 1.5 parts of Sb2O3.

[0012] The present invention also discloses a preparation method of the europium - doped bismuthate radiation - resistant optical glass material according to any of the above, including:

[0013] (1) Weigh the raw materials and mix them evenly to obtain a mixture;

[0014] (2) Melt the mixture at a high temperature, keep it warm for 1 h and then raise the temperature and stir. After clarification and homogenization treatment, a high - temperature glass melt is obtained;

[0015] (3) Pour the high - temperature glass solution into a graphite crucible to form a large - size glass blank, and obtain a formed glass blank;

[0016] (4) Anneal the formed glass blank to obtain a europium - doped bismuthate radiation - resistant optical glass material.

[0017] Furthermore, in step (2), the high - temperature melting temperature is 960 °C, start stirring when the temperature is raised to 1260 °C; the clarification and homogenization treatment time is 2 - 3 h.

[0018] Furthermore, the high - temperature glass solution in step (3) is at 1260 °C.

[0019] Furthermore, the graphite crucible in step (3) needs to be pre - heated to 500 °C before use.

[0020] Furthermore, after demolding the formed glass blank, transfer it to a muffle furnace that has been heated to 550 °C for annealing. After heat preservation treatment, the glass sample is cooled to room temperature naturally with the furnace.

[0021] Furthermore, the time of the heat preservation treatment is 4 h.

[0022] The present invention also discloses a europium - doped bismuthate radiation - resistant optical glass material prepared by the preparation method according to any of the above.

[0023] Compared with the prior art, the present invention has at least the following beneficial effects:

[0024] 1. The radiation-resistant glass prepared by the present invention can effectively inhibit the formation of color centers in the microstructure after high-dose γ irradiation by adding a new variable-valence element Eu. At the same time, this new variable-valence element Eu can effectively solve the problems of color change and reduction of initial transmittance of radiation-resistant glass caused by the traditional variable-valence element Ce.

[0025] 2. Based on the γ absorption coefficient of elements, the oxide of Bi is used as one of the network formers in the radiation-resistant glass in the present invention. This measure ensures the radiation resistance of the glass while avoiding the toxicity problem of Pb elements. To address the problem that Bi elements cause color change in the glass, resulting in a decrease in the initial transmittance of the glass, adding the oxide of Sb element to the glass composition can effectively inhibit this phenomenon.

[0026] 3. In the composition of the present invention, Bi2O3 has become a suitable substitute for lead oxide in glass preparation because it has a high absorption coefficient for γ rays and is non-toxic. However, the field strength of Bi 3 + ions is small and cannot act as a glass network former alone. It needs to form a larger formation region together with other network formers (such as Si, B, etc.). Borate-based glasses are widely selected because they have high melting temperatures, excellent temperature change resistance, good transparency, high chemical durability, thermal stability, and good rare earth ion solubility. Therefore, B2O3 is selected in the composition to form the glass network former together with Bi2O3.

[0027] The Bi2O3 - B2O3 system glass exhibits strong radiation resistance. This phenomenon is closely related to the high content of heavy metal ions Bi in the glass 3+ because Bi 3+ can inhibit the generation of excited electrons during irradiation, thereby reducing the number of defects. At the same time, it is also related to the fact that Bi2O3 and B2O3 participate in the formation of the glass structure in various stable coordination forms (such as BO3, BO4, BiO3, BiO6). Bismuth polyhedra and borate structural groups have the ability to construct an independent interconnected network, thus effectively improving the glass structure stability.

[0028] The doping of Sb2O3 is used to improve the coloring of the glass caused by Bi elements. This is because Bi 3+ tends to be reduced to a lower valence state during the glass melting process, thereby introducing new absorption peaks in the microstructure. Sb2O3 can effectively inhibit this reduction process and improve the initial transmittance of the glass. In addition, the doping of Sb2O3 can also improve the radiation resistance of the glass. The principle is that: through valence change, Sb 3+ ions react with holes to form Sb 4+ ions, thereby reducing the defects induced by ionizing radiation.

[0029] Adding Eu2O3 is of great significance to the radiation resistance of glass, which can effectively improve the optical stability of glass after high-dose irradiation. Replacing CeO2 with Eu2O3 as a rare-earth dopant helps to improve the radiation resistance of glass because the radiation resistance of CeO2 under low-dose irradiation cannot meet the requirements, and doping CeO2 at high doses will cause the glass to color, thereby reducing the light transmittance. Similar to the Ce element, the Eu element can transform between trivalent and divalent states, and reduce the ionization effect caused by irradiation by means of valence change, thereby inhibiting the formation of irradiation-induced defects.

[0030] As modifiers of the glass network, Na2CO3 and K2CO3 can reduce the viscosity of the glass melt, making it easier to melt, playing a good solubilizing role, and helping to improve the gloss of the glass. However, excessive doping of these components may cause an increase in the thermal expansion coefficient of the glass, thereby affecting its thermal stability, chemical stability, and mechanical strength.

[0031] As a modifier of the glass network, La2O3 can improve the optical, mechanical, and mechanical properties of the glass and can play a fluxing effect. Description of the Drawings

[0032] Figure 1 Shows a physical diagram of the europium-doped bismuthate radiation-resistant optical glass material of the present invention.

[0033] Figure 2 Shows the initial transmittance curves of the europium-doped bismuthate radiation-resistant optical glass materials of Example 1 and Comparative Example 1 of the present invention.

[0034] Figure 3 Shows a comparison diagram of the degree of decrease in transmittance after irradiation of the europium-doped bismuthate radiation-resistant optical glass materials of Examples 1-5 of the present invention. Specific Embodiment Method

[0035] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments and drawings of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0036] Example 1

[0037] A europium-doped bismuthate radiation-resistant optical glass material and its preparation method

[0038] Weigh 56.5 parts of H3BO3, 1.8 parts of La2O3, 2.2 parts of Na2CO3, 5 parts of K2CO3, 33 parts of Bi2O3, and 1.5 parts of Sb2O3 accurately and mix them evenly. Heat the evenly mixed raw materials in a muffle furnace to 960 °C for pre-melting. After keeping the temperature for 1 h, raise the temperature to 1260 °C and stir, clarify and homogenize for 2 - 3 h. Keep the high-temperature glass solution at 1260 °C and pour it out before the muffle furnace cools down. Pour the high-temperature glass liquid into a graphite crucible mold preheated to 500 °C. After demolding the formed glass blank, transfer it to a muffle furnace heated to 550 °C for annealing. After keeping the temperature for 4 h, let the glass sample cool naturally with the furnace to room temperature to obtain the radiation-resistant optical glass.

[0039] Example 2

[0040] A europium-doped bismuthate radiation-resistant optical glass material and its preparation method

[0041] Weigh 56 parts of H3BO3, 1.8 parts of La2O3, 2.2 parts of Na2CO3, 5 parts of K2CO3, 33 parts of Bi2O3, 0.5 part of Eu2O3, and 1.5 parts of Sb2O3 accurately and mix them evenly. Heat the evenly mixed raw materials in a muffle furnace to 960 °C for pre-melting. After keeping the temperature for 1 h, raise the temperature to 1260 °C and stir, clarify and homogenize for 2 - 3 h. Keep the high-temperature glass solution at 1260 °C and pour it out before the muffle furnace cools down. Pour the high-temperature glass liquid into a graphite crucible mold preheated to 500 °C. After demolding the formed glass blank, transfer it to a muffle furnace heated to 550 °C for annealing. After keeping the temperature for 4 h, let the glass sample cool naturally with the furnace to room temperature to obtain the radiation-resistant optical glass.

[0042] Example 3

[0043] A europium-doped bismuthate radiation-resistant optical glass material and its preparation method

[0044] Weigh 55 parts of H3BO3, 1.8 parts of La2O3, 2.2 parts of Na2CO3, 5 parts of K2CO3, 33 parts of Bi2O3, 1.5 parts of Eu2O3, and 1.5 parts of Sb2O3 accurately and mix them evenly. Heat the evenly mixed raw materials in a muffle furnace to 960 °C for pre-melting. After keeping the temperature for 1 h, raise the temperature to 1260 °C and stir, clarify and homogenize for 2 - 3 h. Keep the high-temperature glass solution at 1260 °C and pour it out before the muffle furnace cools down. Pour the high-temperature glass liquid into a graphite crucible mold preheated to 500 °C. After demolding the formed glass blank, transfer it to a muffle furnace heated to 550 °C for annealing. After keeping the temperature for 4 h, let the glass sample cool naturally with the furnace to room temperature to obtain the radiation-resistant optical glass.

[0045] Example 4

[0046] A europium-doped bismuthate radiation-resistant optical glass material and its preparation method

[0047] Weigh 54 parts of H3BO3, 1.8 parts of La2O3, 2.2 parts of Na2CO3, 5 parts of K2CO3, 33 parts of Bi2O3, 2.5 parts of Eu2O3, and 1.5 parts of Sb2O3 accurately and mix them evenly. Heat the evenly mixed raw materials in a muffle furnace to 960 °C for pre-melting. After holding for 1 h, raise the temperature to 1260 °C and stir, clarify and homogenize for 2 - 3 h. Keep the high-temperature glass solution at 1260 °C and pour it out before the muffle furnace cools down. Pour the high-temperature glass liquid into a graphite crucible mold preheated to 500 °C. After demolding the formed glass blank, transfer it to a muffle furnace heated to 550 °C for annealing. After holding for 4 h, let the glass sample cool naturally with the furnace to room temperature to obtain the radiation-resistant optical glass.

[0048] Example 5

[0049] A europium-doped bismuthate radiation-resistant optical glass material and its preparation method

[0050] Weigh 53 parts of H3BO3, 1.8 parts of La2O3, 2.2 parts of Na2CO3, 5 parts of K2CO3, 33 parts of Bi2O3, 3.5 parts of Eu2O3, and 1.5 parts of Sb2O3 accurately and mix them evenly. Heat the evenly mixed raw materials in a muffle furnace to 960 °C for pre-melting. After holding for 1 h, raise the temperature to 1260 °C and stir, clarify and homogenize for 2 - 3 h. Keep the high-temperature glass solution at 1260 °C and pour it out before the muffle furnace cools down. Pour the high-temperature glass liquid into a graphite crucible mold preheated to 500 °C. After demolding the formed glass blank, transfer it to a muffle furnace heated to 550 °C for annealing. After holding for 4 h, let the glass sample cool naturally with the furnace to room temperature to obtain the radiation-resistant optical glass.

[0051] Comparative Example 1

[0052] Weigh 54.5 parts of H3BO3, 1.8 parts of La2O3, 2.2 parts of Na2CO3, 5 parts of K2CO3, 33 parts of Bi2O3, 3.5 parts of Eu2O3 accurately and mix them evenly. Heat the evenly mixed raw materials in a muffle furnace to 960 °C for pre-melting. After holding for 1 h, raise the temperature to 1260 °C and stir, clarify and homogenize for 2 - 3 h. Keep the high-temperature glass solution at 1260 °C and pour it out before the muffle furnace cools down. Pour the high-temperature glass liquid into a graphite crucible mold preheated to 500 °C. After demolding the formed glass blank, transfer it to a muffle furnace heated to 550 °C for annealing. After holding for 4 h, let the glass sample cool naturally with the furnace to room temperature to obtain the radiation-resistant optical glass.

[0053] Test Example 1

[0054] Perform 1×10 on the europium-doped bismuthate radiation-resistant optical glass materials of Examples 1 - 5 4Gy and 5×10 5 γ irradiation at two different doses of Gy. Using a UH4150 ultraviolet-visible-near-infrared spectrophotometer, the transmittance in the range of 400 - 800 nm was measured in the integrating sphere test mode. The wavelength accuracy of the test instrument: ±0.2 nm, and the surface of the tested sample was optically polished.

[0055] It can be seen from Figure 2 that the Eu-doped bismuthate radiation-resistant optical glass material prepared in Example 5 has good optical properties in the visible light region, and the transmittance in the range is close to 90%. Compared with Comparative Example 1 without adding Sb element, the optical properties are significantly improved.

[0056] It can be seen from Figure 3 that Examples 1 - 5 of the present invention have good radiation resistance under the irradiation condition of 1×10 4 Gy, and the average decrease in transmittance in the visible light region is only about 5%. By comparison, Example 5 with the highest Eu element content among Examples 1 - 5 has the best radiation resistance under the high-dose 5×10 5 Gy radiation condition, and the average decrease in transmittance after irradiation is 14.85%, while that of Example 1 without adding Eu element is 65.56%.

[0057] The above are only the preferred embodiments of the present application and are not used to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A europium-doped bismuthate radiation-resistant optical glass material, comprising the following raw materials in proportion by weight: H3BO3 50-56 parts, La2O3 0.9-1.8 parts, Na2CO3 1.1-2.8 parts, K2CO3 4.8-5.5 parts, Bi2O3 30-45 parts, Eu2O3 0.5-3.8 parts, Sb2O3 1.2-4.5 parts.

2. The europium-doped bismuthate radiation-resistant optical glass material according to claim 1, wherein: H3BO3 53-56 parts, La2O3 0.9-1.3 parts, Na2CO3 1.1-2.5 parts, K2CO3 4.8-5.1 parts, Bi2O3 30-41 parts, Eu2O3 1.5-3.8 parts, Sb2O3 1.2-2.5 parts.

3. The europium-doped bismuthate radiation-resistant optical glass material according to claim 1, wherein: 53 parts of H3BO, 1.8 parts of La2O3, 2.2 parts of Na2CO3, 5 parts of K2CO3, 33 parts of Bi2O3, 3.5 parts of Eu2O3, and 1.5 parts of Sb2O3.

4. A method for preparing the europium-doped bismuthate radiation-resistant optical glass material according to any one of claims 1 to 3, comprising: (1) weighing raw materials and mixing them uniformly to obtain a mixture; (2) melting the mixture at high temperature, keeping the temperature for 1 hour, then heating and stirring, and clarifying and homogenizing to obtain high-temperature glass liquid; (3) pouring the high-temperature glass solution into a graphite crucible to obtain a formed glass blank; (4) The formed glass blank is annealed to obtain a europium-doped bismuth salt radiation-resistant optical glass material.

5. The preparation method according to claim 4, wherein: The high temperature melting temperature of step (2) is 960°C, and the temperature is raised to 1260°C before stirring; the clarification and homogenization treatment time is 2 to 3 hours.

6. The preparation method according to claim 4, wherein: The high temperature glass solution in step (3) is 1260°C.

7. The preparation method according to claim 4, wherein: The graphite crucible in step (3) needs to be preheated to 500° C. before use.

8. The preparation method according to claim 4, wherein: The annealing treatment of the formed glass blank in step (4) comprises: After demolding, the formed glass blank is transferred into a muffle furnace heated to 550°C for annealing. After heat preservation treatment, the glass sample is naturally cooled to room temperature along with the furnace.

9. The preparation method according to claim 7, wherein: The time of the heat preservation treatment is 4 hours.

10. A europium-doped bismuthate radiation-resistant optical glass material prepared according to the preparation method according to any one of claims 3 to 9.

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