GLASS MATERIAL WITH HIGH REFRACTIVE INDEX AND RADIATION RESISTANCE, THE METHOD FOR PREPARING THE SAME, AND APPLICATIONS THEREOF

Abstract

A glass material with high refractive index and radiation resistance, the method for preparing the same, and applications thereof, wherein the glass material, by mass percentage, includes 20-40% SiO.sub.2, 0-10% Al.sub.2O.sub.3, 0-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0-5% La.sub.2O.sub.3, 0-2% Nb.sub.2O.sub.5, 0-2% Ta.sub.2O.sub.5, 0-1% Bi.sub.2O.sub.3, and a content of 0-1% of an oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O, and Cs.sub.2O. The glass material has a refractive index1.80, a glass transition temperature560 C., a yield point temperature650 C., and good thermal resistance. Its coefficient of thermal expansion is (85-90)10.sup.7/ C., indicating good thermal processability, suitable for forming large-sized devices. After irradiation with a 4700Gy dose of X-rays, a transmittance reduction is 2%, making it suitable for creating radiation-resistant optical components such as optical glass and fiber optic panels.

Claims

1-21. (canceled)

22. A glass material, comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0-5% La.sub.2O.sub.3, 0-2% Nb.sub.2O.sub.5, 0-2% Ta.sub.2O.sub.5, 0-1% Bi.sub.2O.sub.3, and a content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O, and Cs.sub.2O; wherein, a total content of La.sub.2O.sub.3, Nb.sub.2O.sub.5, Ta.sub.2O.sub.5, and Bi.sub.2O.sub.3 is 1-10%; a content of Na.sub.2O is 0, or the content of Na.sub.2O is 20-50% of the content of alkali metal oxides.

23. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0.5-5% La.sub.2O.sub.3, 0-2% Nb.sub.2O.sub.5, 0-2% Ta.sub.2O.sub.5, 0-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

24. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0-5% La.sub.2O.sub.3, 0.5-2% Nb.sub.2O.sub.5, 0-2% Ta.sub.2O.sub.5, 0-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

25. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0-5% La.sub.2O.sub.3, 0-2% Nb.sub.2O.sub.5, 1-2% Ta.sub.2O.sub.5, 0-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

26. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0-5% La.sub.2O.sub.3, 0-2% Nb.sub.2O.sub.5, 0-2% Ta.sub.2O.sub.5, 0.3-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

27. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0.5-5% La.sub.2O.sub.3, 0.5-2% Nb.sub.2O.sub.5, 0-2% Ta.sub.2O.sub.5, 0-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

28. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0.5-5% La.sub.2O.sub.3, 0-2% Nb.sub.2O.sub.5, 1-2% Ta.sub.2O.sub.5, 0-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

29. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0.5-5% La.sub.2O.sub.3, 0-2% Nb.sub.2O.sub.5, 0-2% Ta.sub.2O.sub.5, 0.3-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

30. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0-5% La.sub.2O.sub.3, 0.5-2% Nb.sub.2O.sub.5, 1-2% Ta.sub.2O.sub.5, 0-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

31. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0-5% La.sub.2O.sub.3, 0.5-2% Nb.sub.2O.sub.5, 0-2% Ta.sub.2O.sub.5, 0.3-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

32. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0-5% La.sub.2O.sub.3, 0-2% Nb.sub.2O.sub.5, 1-2% Ta.sub.2O.sub.5, 0.3-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

33. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0.5-5% La.sub.2O.sub.3, 0.5-2% Nb.sub.2O.sub.5, 1-2% Ta.sub.2O.sub.5, 0-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

34. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0.5-5% La.sub.2O.sub.3, 0.5-2% Nb.sub.2O.sub.5, 0-2% Ta.sub.2O.sub.5, 0.3-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

35. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0.5-5% La.sub.2O.sub.3, 0-2% Nb.sub.2O.sub.5, 1-2% Ta.sub.2O.sub.5, 0.3-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

36. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0-5% La.sub.2O.sub.3, 0.5-2% Nb.sub.2O.sub.5, 1-2% Ta.sub.2O.sub.5, 0.3-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

37. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0.5-5% La.sub.2O.sub.3, 0.5-2% Nb.sub.2O.sub.5, 1.5-2% Ta.sub.2O.sub.5, 0.5-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

38. The glass material according to claim 22, wherein comprising the following components by mass percentage: 20-36% SiO.sub.2, 2-10% Al.sub.2O.sub.3, 1-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0-2% Nb.sub.2O.sub.5, 0-2% Ta.sub.2O.sub.5, 0-1% Bi.sub.2O.sub.3, and the content of 0.8-1% of at least one oxide selected from Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O.

39. The glass material according to claim 22, wherein comprising 43-50% of PbO by mass percentage.

40. The glass material according to claim 39, wherein comprising 44-50% of PbO by mass percentage.

41. The glass material according to claim 22, wherein comprising 5-15% of BaO by mass percentage.

42. The glass material according to claim 41, wherein comprising 5-10% of BaO by mass percentage.

43. The glass material according to claim 22, wherein comprising 1.7-5% of CeO.sub.2 by mass percentage.

44. The glass material according to claim 43, wherein comprising 2-5% of CeO.sub.2 by mass percentage.

45. The glass material according to claim 22, wherein comprising 2-8% of Al.sub.2O.sub.3 by mass percentage.

46. The glass material according to claim 22, wherein comprising 1-4% or 4-5% of CaO by mass percentage.

47. The glass material according to claim 22, wherein comprising 0-1.7% of La.sub.2O.sub.3 by mass percentage.

48. The glass material according to claim 47, wherein comprising 0.5-2% or 2-5% of La.sub.2O.sub.3 by mass percentage.

49. The glass material according to claim 22, wherein comprising 0% of Nb.sub.2O.sub.5 by mass percentage.

50. The glass material according to claim 22, wherein comprising 0-1.5% of Ta.sub.2O.sub.5 by mass percentage.

51. The glass material according to claim 50, wherein comprising 1.5% or 0 of Ta.sub.2O.sub.5 by mass percentage.

52. The glass material according to claim 22, wherein comprising 0% of Bi.sub.2O.sub.3 by mass percentage.

53. The glass material according to claim 22, wherein having a refractive index1.8, a glass transition temperature560 C., a yield point temperature650 C., a coefficient of thermal expansion at 30-300 C. of (85-90)10.sup.7/ C., and a transmittance reduction2% after 4700Gy dose X-ray irradiation.

54. A method of preparing a glass material as claimed in claim 22, comprising: mixing raw materials, melting, clarifying by stirring, molding by cooling, and precision annealing.

55. The method according to claim 54, wherein a temperature of melting is 1450-1550 C., a temperature of molding is 1100-1320 C., and a temperature of precision annealing is 580-630 C.

56. An optical component made from a glass material according to claim 22.

57. An optical glass fiber, having a core made from a glass material according to claim 22.

58. A fiber optic panel prepared with a glass material according to claim 22 as the core glass material.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0144] The accompanying drawings to the specification, which form part of the present application, are used to provide a further understanding of the present application, and the illustrative embodiments of the present application and the description thereof are used to explain the present application and are not unduly limiting the present application. Hereinafter, embodiments of the present application are described in detail with reference to the accompanying drawings, wherein:

[0145] FIG. 1 shows a photograph of a large-sized (140802 mm.sup.3) radiation-resistant fiber optic panel made using the glass material of the present invention.

[0146] FIG. 2 shows the transmittance comparison (at 560 nm) before and after X-ray irradiation (4700Gy dose) for the glass material from Example 3 of the present invention.

[0147] FIG. 3 shows the transmittance comparison (at 560 nm) before and after X-ray irradiation (4700Gy dose) for the glass material from Example 4 of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0148] The present application is further described below with reference to specific embodiments. It should be understood that these embodiments are intended to illustrate the present application only and not to limit the scope of the present application. Experimental methods for which specific conditions are not indicated in the following embodiments generally follow conventional conditions or follow the conditions recommended by the manufacturer.

[0149] Unless otherwise defined, all professional and scientific terms used in the text have the same meaning as those familiar to those skilled in the art. Reagents or raw materials used in the present application are available through conventional means. Unless otherwise specified, reagents or raw materials used in the present application are used in a conventional manner in the field or in accordance with product specifications. In addition, any methods, and materials similar or equivalent to those described herein can be used in the methods of the present disclosure. The preferred embodiments described herein are exemplary only.

[0150] The present invention provides a high refractive index, radiation-resistant glass material. By mass percentage, the glass material comprises, or is composed of, the following components: 20-40% SiO.sub.2, 0-10% Al.sub.2O.sub.3, 0-5% CaO, 5-20% BaO, 40-50% PbO, 1-5% CeO.sub.2, 0-5% La.sub.2O.sub.3, 0-2% Nb.sub.2O.sub.5, 0-2% Ta.sub.2O.sub.5, 0-1% Bi.sub.2O.sub.3, and a content of 0-1% of alkali metal oxide, wherein the alkali metal oxide is selected from at least one of Na.sub.2O, K.sub.2O, Rb.sub.2O and Cs.sub.2O when the content of alkali metal oxide is not 0. The glass material according to the present invention possesses outstanding properties, selected from excellent X-ray absorption and radiation resistance stability, appropriate coefficient of thermal expansion and softening temperature, good processability and adaptability in manufacturing. The glass material according to the present invention can be used as core glass material for optical glass fibers and fiber optic panels. The fiber optic panels made from the glass material also exhibit superior radiation resistance, fundamentally meeting the requirements for applications in radiative environments. This resolves the core material supply challenges and industrial chain security issues for X-ray detectors.

[0151] Specifically, in the present invention, the glass material, when composed of the aforementioned components, exhibits exceptional properties in certain embodiments. For example, in some embodiments, a refractive index of the glass material is 1.8; in some embodiments, a glass transition temperature of the glass material is 560 C.; in some embodiments, a yield point temperature of the glass material is 650 C.; in some embodiments, a thermal expansion coefficient of the glass material is (85-90)10.sup.7/ C. between 30 C. and 300 C.; and in some embodiments, a transmittance of the glass material is over 80% at 560 nm, which remains above 78.5% even after irradiation with a 4700 Gy dose of X-rays, with a transmittance reduction of 2%. Additionally, in some embodiments of the present invention, the glass material combines these superior properties, with a refractive index of 1.8, glass transition temperature of 560 C., a coefficient of thermal expansion of (85-90)10.sup.7/ C., and a reduction in transmittance of 2%, or even1.5%, 1.3%, or 1.2% after 4700 Gy dose of X-ray irradiation, making it particularly suitable for the preparation of optical components or instruments.

[0152] Furthermore, the present invention provides a method of preparing a high refractive index, radiation-resistant glass material, comprising mixing raw materials, melting, clarifying by stirring, molding by cooling, and precision annealing. In some embodiments, the invention provides an optimal preparation method, including mixing raw materials in proportions, melting, and clarifying at high temperatures of 1450 C. to 1550 C., casting at 1100 C. to 1320 C. (both mechanical and manual casting are viable), followed by annealing at 580 C. to 630 C. This method ensures process stability, and the glass material prepared under this process exhibits stable characteristics. These characteristics do not fluctuate significantly with temperature variations within this range and include, but are not limited to, excellent refractive performance, heat resistance, processability, and radiation resistance stability. Understandably, within this temperature range, higher temperatures can shorten the preparation process. If minimizing time costs is necessary, technicians may choose relatively higher temperatures within the disclosed range.

[0153] To further illustrate the present invention in greater detail, specific examples are provided below.

Example 1

[0154] This example of radiation-resistant, high-refractive-index glass material was composed of the following components by mass percentage: 30% SiO.sub.2, 5% Al.sub.2O.sub.3, 3% CaO, 9.2% BaO, 45% PbO, 5% CeO.sub.2, 1% Nb.sub.2O.sub.5, 1% Bi.sub.2O.sub.3, and 0.8% Cs.sub.2O.

[0155] In this example, the radiation-resistant, high-refractive-index glass material was made using quartz sand, aluminum oxide, calcium carbonate, barium carbonate, lead silicate, cerium oxide, niobium pentoxide, bismuth oxide, and cesium carbonate as raw materials. These raw materials were mixed in proportion and then melted at 1500 C. The mixture underwent auxiliary stirring for clarification, followed by mechanical molding at 1236 C., and was finally annealed at 605 C. to obtain the final product.

[0156] The refractive index of the glass sample was tested using a Metricon Model 2010/M Prism Coupler. When a beam of light perpendicular to the plane of incidence entered a V prism, if the refractive index of the sample matched that of the V prism, the light passed through without deviation. If the refractive index of the sample differed from the prism, refraction occurred. By measuring the angle between the refracted and incident light, the refractive index of the sample was calculated using the law of refraction. (GB/T 7962.1-2010)

[0157] The transmittance of glass samples was determined using a Shimadzu UV-3600Plus UV-Visible spectrophotometer. The test wavelength range was 300 nm to 1500 nm, and the tested glass samples were optically polished with a thickness of 5 mm. (GB/T 7962.12-2010)

[0158] The coefficient of thermal expansion of glass samples was tested using a Netzsch DIL 402 dilatometer. The samples were polished into cylindrical rods of (PHi) 650 mm with parallel ends. The heating rate was set at 5 C./min, and the data collection interval was 20 ms. The temperature vs. linear expansion curve was plotted to determine the glass transition and softening temperatures (GB/T 7962.16-2010)

[0159] The radiation-resistant, high-refractive-index glass material produced in this example had a refractive index of 1.81, a transmittance of 80.3% after 4700Gy X-ray irradiation (a decrease of 1.58%), a glass transition temperature of 570 C., a yield point temperature of 677 C., and a coefficient of thermal expansion of 86.810.sup.7/ C.

Example 2

[0160] This example of radiation-resistant, high-refractive-index glass material was composed of the following components by mass percentage: 20% SiO.sub.2, 10% Al.sub.2O.sub.3, 4% CaO, 15% BaO, 48% PbO, 1% CeO.sub.2, 0.5% La.sub.2O.sub.3, 0.5% Bi.sub.2O.sub.3, and 1% K.sub.2O.

[0161] In this example, the radiation-resistant, high-refractive-index glass material was made using quartz sand, aluminum hydroxide, calcium carbonate, barium carbonate, minium (read lead oxide), cerium oxide, lanthanum oxide, bismuth oxide, and potassium nitrate as raw materials. These raw materials were mixed in proportion and then melted at 1485 C. The mixture underwent auxiliary stirring for clarification, followed by mechanical molding at 1202 C., and was finally annealed at 599 C. to obtain the final product.

[0162] The glass material in this example was tested using the same methods as in Example 1, allowing for the determination of the refractive index, transmittance, coefficient of thermal expansion, glass transition temperature, and yield point temperature. The radiation-resistant, high-refractive-index glass material produced in this example had a refractive index of 1.83, a transmittance of 78.62% after 4700Gy X-ray irradiation (a decrease of 1.4%), a glass transition temperature of 568 C., a yield point temperature of 658 C., and a coefficient of thermal expansion of 88.110.sup.7/ C.

Example 3

[0163] This example of radiation-resistant, high-refractive-index glass material was composed of the following components by mass percentage: 27.5% SiO.sub.2, 2% Al.sub.2O.sub.3, 5% CaO, 8% BaO, 50% PbO, 3% CeO.sub.2, 2% La.sub.2O.sub.3, 0.5% Nb.sub.2O.sub.5, 1% Ta.sub.2O.sub.5, 0.5% Rb.sub.2O and 0.5% Cs.sub.2O.

[0164] In this example, the radiation-resistant, high-refractive-index glass material was made using quartz sand, aluminum hydroxide, calcium carbonate, barium nitrate, lead silicate, cerium oxide, lanthanum oxide, niobium pentoxide, tantalum pentoxide, rubidium carbonate, and cesium carbonate as raw materials. These raw materials were mixed in proportion and then melted at 1520 C. The mixture underwent auxiliary stirring for clarification, followed by mechanical molding at 1266 C., and was finally annealed at 611 C. to obtain the final product.

[0165] The glass material in this example was tested using the same methods as in Example 1, allowing for the determination of the refractive index, transmittance, coefficient of thermal expansion, glass transition temperature, and yield point temperature. The radiation-resistant, high-refractive-index glass material produced in this example had a refractive index of 1.83, a transmittance of 80.83% after 4700Gy X-ray irradiation (a decrease of 1.18%), a glass transition temperature of 574 C., a yield point temperature of 680 C., and a coefficient of thermal expansion of 86.210.sup.7/ C.

Example 4

[0166] This example of radiation-resistant, high-refractive-index glass material was composed of the following components by mass percentage: 35% SiO.sub.2, 18.1% BaO, 40% PbO, 1.7% CeO.sub.2, 2% La.sub.2O.sub.3, 1% Nb.sub.2O.sub.5, 1% Ta.sub.2O.sub.5, 0.3% Bi.sub.2O.sub.3, 0.4% Na.sub.2O, and 0.5% K.sub.2O.

[0167] In this example, the radiation-resistant, high-refractive-index glass material was made using quartz sand, barium nitrate, litharge (yellow lead oxide), cerium oxide, lanthanum oxide, niobium pentoxide, tantalum pentoxide, bismuth oxide, sodium carbonate, and potassium carbonate as raw materials. These raw materials were mixed in proportion and then melted at 1465 C. The mixture underwent auxiliary stirring for clarification, followed by manually casting at 1180 C., and was finally annealed at 592 C. to obtain the final product.

[0168] The glass material in this example was tested using the same methods as in Example 1, allowing for the determination of the refractive index, transmittance, coefficient of thermal expansion, glass transition temperature, and yield point temperature. The radiation-resistant, high-refractive-index glass material produced in this example had a refractive index of 1.80, a transmittance of 80.44% after 4700Gy X-ray irradiation (a decrease of 1.57%), a glass transition temperature of 565 C., a yield point temperature of 650 C., and a coefficient of thermal expansion of 89.410.sup.7/ C.

Example 5

[0169] This example of radiation-resistant, high-refractive-index glass material was composed of the following components by mass percentage: 32% SiO.sub.2, 8% Al.sub.2O.sub.3, 2% CaO, 7% BaO, 43% PbO, 1% CeO.sub.2, 1.7% La.sub.2O.sub.3, 1.5% Nb.sub.2O.sub.5, 2% Ta.sub.2O.sub.5, 0.8% Bi.sub.2O.sub.3, 0.5% Na.sub.2O, and 0.5% Cs.sub.2O.

[0170] In this example, the radiation-resistant, high-refractive-index glass material was made using quartz sand, aluminum oxide, calcium carbonate, barium carbonate, lead silicate, cerium oxide, lanthanum oxide, niobium pentoxide, tantalum pentoxide, bismuth oxide, sodium nitrate, and cesium carbonate as raw materials. These raw materials were mixed in proportion and then melted at 1533 C. The mixture underwent auxiliary stirring for clarification, followed by mechanical molding at 1291 C., and was finally annealed at 618 C. to obtain the final product.

[0171] The glass material in this example was tested using the same methods as in Example 1, allowing for the determination of the refractive index, transmittance, coefficient of thermal expansion, glass transition temperature, and yield point temperature. The radiation-resistant, high-refractive-index glass material produced in this example had a refractive index of 1.80, a transmittance of 79.45% after 4700Gy X-ray irradiation (a decrease of 1.43%), a glass transition temperature of 575 C., a yield point temperature of 685 C., and a coefficient of thermal expansion of 85.810.sup.7/ C.

Example 6

[0172] This example of radiation-resistant, high-refractive-index glass material was composed of the following components by mass percentage: 40% SiO.sub.2, 7% Al.sub.2O.sub.3, 1% CaO 5% BaO, 44% PbO, 2% CeO.sub.2, 0.5% La.sub.2O.sub.3 and 0.5% Bi.sub.2O.sub.3.

[0173] In this example, the radiation-resistant, high-refractive-index glass material was made using quartz sand, aluminum oxide, calcium carbonate, barium carbonate, litharge (yellow lead oxide), cerium oxide, lanthanum oxide, and bismuth oxide as raw materials. These raw materials were mixed in proportion and then melted at 1544 C. The mixture underwent auxiliary stirring for clarification, followed by mechanical molding at 1301 C., and was finally annealed at 624 C. to obtain the final product.

[0174] The glass material in this example was tested using the same methods as in Example 1, allowing for the determination of the refractive index, transmittance, coefficient of thermal expansion, glass transition temperature, and yield point temperature. The radiation-resistant, high-refractive-index glass material produced in this example had a refractive index of 1.82, a transmittance of 79.99% after 4700Gy X-ray irradiation (a decrease of 1.23%), a glass transition temperature of 577 C., a yield point temperature of 692 C., and a coefficient of thermal expansion of 85.510.sup.7/ C.

Example 7

[0175] This example of radiation-resistant, high-refractive-index glass material was composed of the following components by mass percentage: 25% SiO.sub.2, 6% Al.sub.2O.sub.3, 20% BaO, 40% PbO, 2% CeO.sub.2, 3% La.sub.2O.sub.3, 2% Nb.sub.2O.sub.5, 1% Bi.sub.2O.sub.3, 0.5% Na.sub.2O, and 0.5% Rb.sub.2O.

[0176] In this example, the radiation-resistant, high-refractive-index glass material was made using quartz sand, aluminum hydroxide, barium carbonate, lead silicate, cerium oxide, lanthanum oxide, niobium pentoxide, bismuth oxide, sodium carbonate and rubidium carbonate as raw materials. These raw materials were mixed in proportion and then melted at 1450 C. The mixture underwent auxiliary stirring for clarification, followed by manually casting at 1100 C., and was finally annealed at 580 C. to obtain the final product.

[0177] The glass material in this example was tested using the same methods as in Example 1, allowing for the determination of the refractive index, transmittance, coefficient of thermal expansion, glass transition temperature, and yield point temperature. The radiation-resistant, high-refractive-index glass material produced in this example had a refractive index of 1.82, a transmittance of 79.04% after 4700Gy X-ray irradiation (a decrease of 1.52%), a glass transition temperature of 560 C., a yield point temperature of 652 C., and a coefficient of thermal expansion of 90.010.sup.7/ C.

Example 8

[0178] This example of radiation-resistant, high-refractive-index glass material was composed of the following components by mass percentage: 30.5% SiO.sub.2, 2% Al.sub.2O.sub.3, 4% CaO, 6% BaO, 45% PbO, 2% CeO.sub.2, 5% La.sub.2O.sub.3, 2% Nb.sub.2O.sub.5, 1.5% Ta.sub.2O.sub.5, 1% Bi.sub.2O.sub.3, 0.2% Na.sub.2O, 0.5% K.sub.2O, and 0.3% Rb.sub.2O.

[0179] In this example, the radiation-resistant, high-refractive-index glass material was made using quartz sand, aluminum oxide, calcium carbonate, barium carbonate, lead silicate, cerium oxide, lanthanum oxide, niobium pentoxide, tantalum pentoxide, bismuth oxide, sodium nitrate, and cesium carbonate as raw materials. These raw materials were mixed in proportion and then melted at 1550 C. The mixture underwent auxiliary stirring for clarification, followed by mechanical molding at 1320 C., and was finally annealed at 630 C. to obtain the final product.

[0180] The glass material in this example was tested using the same methods as in Example 1, allowing for the determination of the refractive index, transmittance, coefficient of thermal expansion, glass transition temperature, and yield point temperature. The radiation-resistant, high-refractive-index glass material produced in this example had a refractive index of 1.81, a transmittance of 80.09% after 4700Gy X-ray irradiation (a decrease of 1.62%), a glass transition temperature of 580 C., a yield point temperature of 699 C., and a coefficient of thermal expansion of 85.010.sup.7/ C.

Example 9

[0181] The radiation-resistant, high-refractive-index glass materials produced in Examples 1 to 8 were used as core glass materials for the fabrication of fiber optic panels. The fiber optic panels were obtained by encapsulating the glass material (serving as core glass material) from Examples 1 to 8 with cladding glass material (silicate glass), then drawing into single or multiple complex fibers, systematically arranging these fibers, followed by melting and pressing them into blank plate segments, and finally, the segments are processed through slicing, grinding, and polishing, resulting in customizable fiber optic panels with sizes up to a meter scale.

[0182] FIG. 1 shows a photograph of a large-sized (140802 mm.sup.3) radiation-resistant fiber optic panel made using the glass material of the present invention.

[0183] The transmittance of the fiber optic panels was tested using the same method as in Example 1. The panels produced in Examples 1 to 8 of the present invention all exhibited good radiation resistance, with a decrease in transmittance at 560 nm of 0.89% before and after irradiation.

Comparative Example 1

[0184] The glass material for this comparative example is composed of the following components by mass percentage: 45% SiO.sub.2, 2% Al.sub.2O.sub.3, 4% CaO, 8% BaO, 32.5% PbO, 1% CeO.sub.2, 2% La.sub.2O.sub.3, 0.5% Nb.sub.2O.sub.5, 1% Ta.sub.2O.sub.5, 2% Bi.sub.2O.sub.3, 1% Na.sub.2O, 0.5% Rb.sub.2O, and 0.5% Cs.sub.2O.

[0185] In this comparative example, the glass material was prepared using quartz sand, aluminum oxide, calcium carbonate, barium carbonate, lead silicate, cerium oxide, lanthanum oxide, niobium pentoxide, tantalum pentoxide, bismuth oxide, sodium carbonate, rubidium carbonate, and cesium carbonate as raw materials, following the method outlined in Example 1.

[0186] The glass material in this example was tested using the same methods as in Example 1, allowing for the determination of the refractive index, transmittance, coefficient of thermal expansion, glass transition temperature, and yield point temperature. In this comparative example, the glass material had a refractive index of 1.60, a transmittance of 73.65% after 4700Gy X-ray irradiation (a decrease of 4.7%), a glass transition temperature of 568 C., a yield point temperature of 670 C., and a coefficient of thermal expansion of 87.010.sup.7/ C.

Comparative Example 2

[0187] The glass material for this comparative example is composed of the following components by mass percentage: 27.5% SiO.sub.2, 2% Al.sub.2O.sub.3, 6% CaO, 58% PbO, 2% La.sub.2O.sub.3, 0.5% Nb.sub.2O.sub.5, 1% Ta.sub.2O.sub.5, 2% Bi.sub.2O.sub.3, 0.5% Rb.sub.2O, and 0.5% Cs.sub.2O.

[0188] In this comparative example, the glass material was prepared using quartz sand, aluminum oxide, calcium carbonate, litharge (yellow lead oxide), lanthanum oxide, niobium pentoxide, tantalum pentoxide, bismuth oxide, rubidium carbonate, and cesium carbonate as raw materials, following the method outlined in Example 1.

[0189] The glass material in this example was tested using the same methods as in Example 1, allowing for the determination of the refractive index, transmittance, coefficient of thermal expansion, glass transition temperature, and yield point temperature. In this comparative example, the glass material had a refractive index of 1.71, a transmittance of 72.01% after 4700Gy X-ray irradiation (a decrease of 4.31%), a glass transition temperature of 601 C., a yield point temperature of 719 C., and a coefficient of thermal expansion of 79.910.sup.7/ C.

Comparative Example 3

[0190] The glass material for this comparative example is composed of the following components by mass percentage: 16% SiO.sub.2, 2% Al.sub.2O.sub.3, 8% CaO, 8% BaO, 50% PbO, 2% La.sub.2O.sub.3, 0.5% Nb.sub.2O.sub.5, 1% Ta.sub.2O.sub.5, 2% Na.sub.2O, 9.5% K.sub.2O, 0.5% Rb.sub.2O, and 0.5% Cs.sub.2O.

[0191] In this comparative example, the glass material was prepared using quartz sand, aluminum oxide, calcium carbonate, barium nitrate, minium (read lead oxide), lanthanum oxide, niobium pentoxide, tantalum pentoxide, bismuth oxide, sodium nitrate, potassium carbonate, rubidium carbonate, and cesium carbonate as raw materials, following the method outlined in Example 1.

[0192] The glass material in this example was tested using the same methods as in Example 1, allowing for the determination of the refractive index, transmittance, coefficient of thermal expansion, glass transition temperature, and yield point temperature. In this comparative example, the glass material had a refractive index of 1.72, a transmittance of 75.28% after 4700Gy X-ray irradiation (a decrease of 2.73%), a glass transition temperature of 548 C., a yield point temperature of 629 C., and a coefficient of thermal expansion of 91.110.sup.7/ C.

Comparative Example 4

[0193] The glass material for this comparative example is composed of the following components by mass percentage: 25% SiO.sub.2, 15% Al.sub.2O.sub.3, 6% CaO, 5% BaO, 35% PbO, 8% CeO.sub.2, 2% Ta.sub.2O.sub.5, 1% Bi.sub.2O.sub.3, 1% Na.sub.2O, 1% K.sub.2O, and 1% Rb.sub.2O.

[0194] In this comparative example, the glass material was prepared using quartz sand, aluminum oxide, calcium carbonate, barium nitrate, litharge (yellow lead oxide), cerium oxide, tantalum pentoxide, bismuth oxide, sodium nitrate, potassium carbonate, and rubidium carbonate as raw materials, following the method outlined in Example 1.

[0195] The glass material in this example was tested using the same methods as in Example 1, allowing for the determination of the refractive index, transmittance, coefficient of thermal expansion, glass transition temperature, and yield point temperature. In this comparative example, the glass material had a refractive index of 1.61, a transmittance of 63.31% after 4700Gy X-ray irradiation (a decrease of 5.71%), a glass transition temperature of 563 C., a yield point temperature of 660 C., and a coefficient of thermal expansion of 87.810.sup.7/ C.

Comparative Example 5

[0196] The glass material for this comparative example is composed of the following components by mass percentage: 28% SiO.sub.2, 10% Al.sub.2O.sub.3, 7% CaO, 10% BaO, 30% PbO, 3% CeO.sub.2, 1% Nb.sub.2O.sub.5, 3% Ta.sub.2O.sub.5, 2% Bi.sub.2O.sub.3, 5% Na.sub.2O, and 1% K.sub.2O.

[0197] In this comparative example, the glass material was prepared using quartz sand, aluminum oxide, calcium carbonate, barium nitrate, minium (read lead oxide), cerium oxide, niobium pentoxide, tantalum pentoxide, bismuth oxide, sodium nitrate, and potassium carbonate as raw materials, following the method outlined in Example 1.

[0198] The glass material in this example was tested using the same methods as in Example 1, allowing for the determination of the refractive index, transmittance, coefficient of thermal expansion, glass transition temperature, and yield point temperature. In this comparative example, the glass material had a refractive index of 1.6, a transmittance of 67.5300 after 4700Gy X-ray irradiation (a decrease of 4.36%), a glass transition temperature of 559 C., a yield point temperature of 646 C., and a coefficient of thermal expansion of 90.210.sup.7/ C.

[0199] In the present invention, the composition and properties of glass samples from Examples 1 to 8, and Comparative Examples 1 to 5, were respectively detailed in Table 1 and Table 2.

TABLE-US-00001 TABLE 1 composition of glass samples from examples 1 to 8, and comparative examples 1 to 5. Example Comparative Example wt % 1 2 3 4 5 6 7 8 1 2 3 4 5 SiO.sub.2 30.0 20.0 27.5 35.0 32.0 40.0 25.0 30.5 45.0 27.5 16.0 25.0 28.0 Al.sub.2O.sub.3 5.0 10.0 2.0 0 8.0 7.0 6.0 2.0 2.0 2.0 2.0 15.0 10.0 CaO 3.0 4.0 5.0 0 2.0 1.0 0 4.0 4.0 6.0 8.0 6.0 7.0 BaO 9.2 15.0 8.0 18.1 7.0 5.0 20.0 6.0 8.0 0 8.0 5.0 10.0 PbO 45.0 48.0 50.0 40.0 43.0 44.0 40.0 45.0 32.5 58.0 50.0 35.0 30.0 CeO.sub.2 5.0 1.0 3.0 1.7 1.0 2.0 2.0 2.0 1.0 0 0 8.0 3.0 La.sub.2O.sub.3 0 0.5 2.0 2.0 1.7 0.5 3.0 5.0 2.0 2.0 2.0 0 0 Nb.sub.2O.sub.5 1.0 0 0.5 1.0 1.5 0 2.0 2.0 0.5 0.5 0.5 0 1.0 Ta.sub.2O.sub.5 0 0 1.0 1.0 2.0 0 0 1.5 1.0 1.0 1.0 2.0 3.0 Bi.sub.2O.sub.3 1.0 0.5 0 0.3 0.8 0.5 1.0 1.0 2.0 2.0 0 1.0 2.0 Na.sub.2O 0 0 0 0.4 0.5 0 0.5 0.2 1.0 0 2.0 1.0 5.0 K.sub.2O 0 1.0 0 0.5 0 0 0 0.5 0 0 9.5 1.0 1.0 Rb.sub.2O 0 0 0.5 0 0 0 0.5 0.3 0.5 0.5 0.5 1.0 0 Cs.sub.2O 0.8 0 0.5 0 0.5 0 0 0 0.5 0.5 0.5 0 0 Sum 100 100 100 100 100 100 100 100 100 100 100 100 100

TABLE-US-00002 TABLE 2 test results of the properties of glass samples from examples 1 to 8, and comparative examples 1 to 5. Example/Comparative Example Example Comparative Example 1 2 3 4 5 6 7 8 1 2 3 4 5 Refractive Index 1.81 1.83 1.83 1.80 1.80 1.82 1.82 1.81 1.60 1.71 1.72 1.61 1.60 Transmit- Before 81.88 80.02 82.01 82.01 80.88 81.22 80.56 81.71 78.35 76.32 78.01 69.02 71.89 tance at X-ray 560 nm Irradiation (%) After 80.3 78.62 80.83 80.44 79.45 79.99 79.04 80.09 73.65 72.01 75.28 63.31 67.53 4700Gy X-Ray Irradiation Difference 1.58 1.4 1.18 1.57 1.43 1.23 1.52 1.62 4.7 4.31 2.73 5.71 4.36 Glass Transition 570 568 574 565 575 577 560 580 568 601 548 563 559 Temperature (Tg) ( C.) Yield point 677 658 680 650 685 692 652 699 670 719 629 660 646 temperature ( C.) Coefficient of 86.8 88.1 86.2 89.4 85.8 85.5 90.0 85.0 87.0 79.9 91.1 87.8 90.2 Thermal Expansion (CTE) (10.sup.7/ C.)

[0200] From Table 2, it was evident that the core glass materials for the radiation-resistant fiber optic panels prepared in each example have a refractive index of 1.80, a glass transition temperature of 560 C., and a yield point temperature of 650 C. These properties indicated good heat resistance. The coefficient of thermal expansion of these materials was (85-90)10.sup.7/ C., indicating good thermal processing properties, which was beneficial for the fabrication of large-sized devices. Furthermore, the transmittance reduction before and after 4700 Gy X-ray irradiation was 2%. FIG. 2 showed a comparison of the transmittance of glass material prepared in Example 3 of the present invention, before and after X-ray irradiation at a dose of 4700 Gy. The glass material prepared in Example 3 of the present invention exhibited very little difference in transmittance before and after irradiation, and its performance was superior to that of the American company Incom.

[0201] Additionally, fiber optic panels made from the glass materials prepared in Examples 1 to 8 were also tested. These panels demonstrated good radiation resistance as well, with a decrease in transmittance at 560 nm of 0.89% before and after irradiation.

[0202] The aforementioned descriptions are only preferred embodiments of the present application and are not intended to limit the scope of the present application. Although the aforementioned embodiments have been described in detail, those skilled in the art can still modify the technical solutions described in the embodiments or replace some technical features with equivalent alternatives. Any modifications, equivalent replacements, improvements, and the like made within the spirit and principles of the present application should be included within the scope of the present application's protection.