Ce < 3 + >-doped silicon-boron-gadolinium scintillation glass as well as preparation method and application thereof

Abstract

The invention discloses Ce < 3 + > doped silicon boron gadolinium scintillation glass and a preparation method and application thereof, and belongs to the technical field of scintillation luminescent materials. The Ce < 3 + > doped silicon boron gadolinium scintillation glass comprises the following main components in percentage by mole: 5% of SiO2, 25% of B2O3, 25% of Gd2O3, 40-10% of GdF3 and 5-35% of X, x is one or more of MgF2, LiF, BaO and BaF2, and the sum of the main components is 100 mol%; the mass ratio of the Ce < 3 + > doped silicon boron gadolinium scintillation glass to the reducing agent is (6-2): 1; and the molar percentage of the externally doped Ce < 3 + > in the main component is 1%-2%. The prepared Ce < 3 + > doped silicon boron gadolinium scintillation glass has high light yield, X-ray imaging resolution and quantum efficiency of high-density scintillation glass, and the preparation cost of the high-density scintillation glass is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of scintillation luminescent materials and relates to a Ce 3+ Doped silicon boron gadolinium scintillating glass and its preparation method and application, especially a Ce scintillating glass with high light yield and high X-ray imaging resolution 3+ Gadolinium-doped borosilicate scintillating glass, preparation method and application thereof. Background Art

[0002] Scintillating materials refer to energy conversion materials that can convert high-energy rays such as X-rays, gamma rays or ionizing radiation of high-energy particles into ultraviolet or visible light under the action of high-energy radiation. Scintillating materials are widely used in high-energy physics, nuclear physics, industrial non-destructive testing, medical imaging and safety testing.

[0003] Compared with traditional scintillating crystals, scintillating glass has the advantages of short preparation cycle, easy adjustment of composition, good sample uniformity, strong transparency, easy processing, and mass production. However, due to the inherent defects inside the glass, it is difficult to ensure high imaging resolution and high light yield while ensuring high density. At present, most of the high light yield scintillators are crystalline materials. The preparation process of crystalline materials is cumbersome, the production cost is high, and it is not easy to mass produce.

[0004] In the past, most scintillating glass had a density of 4.0 g / cm 3 In order to increase the density and light yield of scintillators, the commonly used method is to add oxides with high atomic numbers, add some oxide metal materials that are conducive to luminescence, or increase the concentration of luminescent center materials, which are conducive to absorbing high-energy rays and depositing energy. The scintillating glasses currently studied mainly include silicate glass, germanate glass, phosphate glass and other glasses. Most of the glass components with higher density contain TeO 2 ,GeO 2 , Lu 2 O 3 Compared with oxide scintillating glass, fluoride scintillating glass has better transmittance in the UV-visible region. In 1994, I. Dafinei et al. of France studied Ce 3+ When doped AFG, HFG and ZFG matrix scintillating glass was used, it was found that its light output was low or even no output. The highest HFG437 was only 75.4Ph / MeV, less than 2% of BGO crystal. 3+ The doping concentration can improve the luminescence performance, but the effect is limited; in 2019, Japanese M. Akatsuka et al. further introduced AlPO into the AFG matrix 4 , which can further increase the light output to 94Ph / MeV, 4 times the performance of AFG417.

[0005] Ce 3+ The energy level difference between the 4f-5d orbitals of the ions is small, and the emission wavelength is in the blue-violet region, which can reduce the self-absorption effect of the matrix glass, and the decay time is usually in the range of 20-90ns. 3+ Doped scintillating glass is widely used as a fast decay scintillating material. 3+ After the ions are introduced into the glass matrix as luminescent centers, their energy levels will split under the influence of the surrounding coordination field, which will have a certain impact on the emission spectrum and lifetime. The field of high-energy physics requires rapid detection and identification of particles, and Ce 3+ Doped scintillating glass just meets this demand. At the same time, the field of high-energy physics requires that scintillators need to have high density and high UV-visible transmittance. Heavy metal fluoride glass and oxide glass just meet this demand and are currently the main research objects. Summary of the invention

[0006] In view of the above prior art, the technical problem to be solved by the present invention is to provide a Ce 3+ Doped silicon boron gadolinium scintillating glass and its preparation method and application. 3+ Doped Si-B-Gd scintillating glass is a non-crystalline material with high light yield, high density, high X-ray imaging resolution and high quantum efficiency. 3+ Gd-doped borosilicate glass is prepared by combining Gd 2 O 3 and GdF 3 To significantly increase the density of scintillating glass, reduce the melting temperature of glass, and introduce MgF 2 Materials such as Ce can improve the light yield and X-ray imaging effect of glass, while reducing the preparation cost of high-density scintillating glass. 3+ The density of the gadolinium-doped borosilicate scintillating glass is 5.3-5.9 g / cm 3 , PL quantum efficiency is 59.65%-85.00%, and light yield is 1223-2100ph / Me. X-ray imaging with higher spatial resolution (14-26lp / m) than commercial Csl:TI crystals (10-11lp / mm) is achieved, which makes Ce-based 3+ Scintillating glass has potential practical applications in X-ray imaging.

[0007] In order to solve the above technical problems, a Ce 3+ Doped silicon boron gadolinium scintillating glass, including main component, reducing agent and externally doped Ce 3+ ; The main components include SiO 2 , B 2 O 3 , Gd 2 O3 , GdF 3 and X, SiO 2 , B 2 O 3 , Gd 2 O 3 , GdF 3 , X mole percentages are SiO 2 5 mol%, B 2 O 3 25 mol%, Gd 2 O 3 25 mol%, GdF 3 is 40-10mol%, X is 5-35mol%; X is MgF 2 、LiF、BaO、BaF 2 One or more of the main components, the sum of which is 100 mol%;

[0008] The reducing agent, by mass ratio, Ce 3+ Doped borosilicate gadolinium scintillating glass: reducing agent = (6-2): 1;

[0009] The Ce doped 3+ The molar percentage of the main component is 1 mol%-2 mol%.

[0010] Preferably, the reducing agent is C powder and / or C granules.

[0011] Preferably, the Ce doped 3+ By CeF 3 and / or CeO 2 Introduction.

[0012] The Ce 3+ Doped silicon boron gadolinium scintillating glass, amorphous, density 5.3-5.9g / cm 3 The light output is 1223-2100ph / MeV, the X-ray imaging line number is 14-26lp / mm, and the quantum efficiency is 59.65~85.00%.

[0013] The present invention also includes a Ce 3+ The preparation method of the gadolinium-doped borosilicate scintillating glass comprises the following steps:

[0014] S1: Follow the instructions 3+ Composition of the Si-Bo-Gd-Doped Scintillating Glass Weigh the raw materials, grind and mix them thoroughly to obtain glass raw materials;

[0015] S2: pouring the uniformly mixed glass raw materials into a covered corundum crucible and melting them to obtain a uniform glass melt;

[0016] S3: Pour the uniform glass melt into the preheated mold, cool it into shape, and transfer it to the annealing furnace for constant temperature annealing to eliminate internal stress and obtain Ce 3+ Gadolinium-doped borosilicate scintillating glass.

[0017] Preferably, in step S2, when a corundum crucible is used, the melting temperature is 1200-1250° C., the melting time is 90-120 min, and the melting atmosphere is air atmosphere;

[0018] Preferably, in step S3, the preheating temperature of the mold is 450-500°C.

[0019] Preferably, in step S3, the annealing temperature is 450-500° C., and the annealing time is 6-8 hours.

[0020] Preferably, in step S3, after the annealing, the step further includes: cooling the temperature, including cooling the temperature to 150° C. at a cooling rate of 2-5° C. / min, and then cooling the temperature to room temperature in the furnace.

[0021] The present invention also includes a Ce 3+ Application of Gadolinium-doped Silicate Boron Scintillating Glass, the Ce 3+ Doped borosilicate gadolinium scintillating glass or Ce prepared by the above preparation method 3+ Gadolinium-doped borosilicate scintillating glass is used in X-ray medical imaging, radiation detection, and industrial non-destructive testing.

[0022] An optical element, comprising the Ce 3+ Gadolinium-doped borosilicate scintillating glass.

[0023] Compared with the prior art, the Ce 3+ The borosilicate gadolinium-doped scintillating glass and its preparation method and application have the following beneficial effects:

[0024] The present invention does not use compounds of heavy metal elements such as W, Pb, Lu, Ge, La, Tl, etc., and only uses Gd 2 O 3 and GdF 3 Significantly increase the glass density to more than 5g / cm 3 The total content of rare earth element compounds in the glass components can be as high as 35 mol%. The present invention has the advantage of high light yield, and the light yield test result is 2100ph / Me, and its luminous integral intensity can reach 50%-80% of BGO scintillating crystal. At the same time, it has high X-ray imaging resolution effect, the X-ray imaging line number is 26lp / mm, and has high quantum efficiency, and the quantum efficiency test can reach 85%.

[0025] Ce of the present invention 3+Gadolinium-doped borosilicate scintillating glass is a non-crystalline material with a simple preparation process, low production cost and easy mass production.

[0026] In the present invention, GdF 3 As heavy metal fluorides, they have high density and can reduce the melting temperature and viscosity of glass. They can also improve the openness of the glass network structure and the solubility of rare earth oxides in glass. 2 O 3 When used together, it can also reduce the manufacturing cost of glass. 2 O 3 The preparation temperature of scintillating glass can be reduced, thereby reducing the difficulty of manufacturing scintillating glass. 2 The introduction of LiF or LiF can change the physical and chemical properties of glass, effectively and significantly improve the light yield, X-ray imaging effect and quantum efficiency of glass. The scintillating glass of the present invention does not contain Pb, which is more friendly to the human body and the environment; it does not contain GeO 2 He Lu 2 O 3 The high-priced raw materials have lower preparation costs and will not introduce radiation background; it does not contain TeO 2 、Bi 2 O 3 , WO 3 Raw materials with variable valence characteristics such as ferrous metals and ferrous metals will not cause glass coloring during the melting process. The use of corundum crucibles improves the corrosion of molten glass to corundum crucibles, and more directly and effectively improves the density and stability of the glass. The introduction of C powder or C granule reducing agent can effectively provide a reducing atmosphere during the melting process of the glass, which can ensure that Ce 3+ The invention is convenient for large-scale preparation and can be prepared into large-scale optical devices. 3+ The high light yield and high X-ray imaging gadolinium-doped borosilicate scintillating glass has excellent chemical and physical stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The morphology of the scintillating glass of Examples 1-5.

[0028] Figure 2 It is a comparison chart of X-ray excitation emission spectra of the scintillating glass and BGO crystal of Examples 1-5.

[0029] Figure 3 It is the transmission spectrum diagram of Example 1-5.

[0030] Figure 4 It is the DSC test spectrum of Example 1-5.

[0031] Figure 51 and 2 are X-ray imaging and resolution diagrams of Example 1; (a) is an X-ray imaging resolution diagram; (b) is an X-ray imaging chip diagram.

[0032] Figure 6 1 and 2 are X-ray imaging and resolution diagrams of Example 5; (a) is an X-ray imaging resolution diagram; (b) is an X-ray imaging chip diagram. DETAILED DESCRIPTION

[0033] The present invention is further described in detail below in conjunction with embodiments.

[0034] The technical scheme of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. The described embodiments are only partial examples of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] Example 1

[0036] A Ce 3+ Doped borosilicate gadolinium scintillating glass, comprising a main component and an externally doped Ce 3+ The molar percentage is: 5SiO 2 -25B 2 O 3 -25Gd 2 O 3 -40GdF 3 -5MgF 2 -1CeF 3 ;

[0037] 1. Weigh the raw materials according to the above glass components and grind and mix them thoroughly to obtain glass raw materials;

[0038] 2. Pour the mixed glass raw materials into a covered corundum crucible, put a large corundum crucible on the corundum crucible filled with raw materials, spread 10g of graphite powder as a reducing agent on the bottom of the large corundum crucible, cover it and sinter it in an air atmosphere, the melting temperature is 1250℃, and the melting time is 120min;

[0039] 3. Pour the glass melt into a mold preheated at 500℃ and cool it to shape. Then transfer it to a 500℃ annealing furnace for constant temperature annealing to eliminate internal stress. After annealing for 6 hours, reduce the temperature to 150℃ at a rate of 2℃ / min, and then cool it to room temperature with the furnace to obtain Ce 3+ Gadolinium-doped borosilicate scintillating glass.

[0040] Example 2

[0041] A Ce 3+Doped borosilicate gadolinium scintillating glass, comprising a main component and an externally doped Ce 3+ The molar percentage of the composition is: 5SiO 2 -25B 2 O 3 -25Gd 2 O 3 -35GdF 3 -10MgF 2 -1CeF 3 ;

[0042] 1. Weigh the raw materials according to the above glass components and grind and mix them thoroughly to obtain glass raw materials;

[0043] 2. Pour the mixed glass raw materials into a covered corundum crucible, put a large corundum crucible on the corundum crucible filled with raw materials, spread 10g of graphite powder as a reducing agent on the bottom of the large corundum crucible, cover it and sinter it in an air atmosphere, the melting temperature is 1250℃, and the melting time is 120min;

[0044] 3. Pour the glass melt into a mold preheated at 500℃ and cool it to shape. Then transfer it to a 500℃ annealing furnace for constant temperature annealing to eliminate internal stress. After annealing for 6 hours, reduce the temperature to 150℃ at a rate of 2℃ / min, and then cool it to room temperature with the furnace to obtain Ce 3+ Gadolinium-doped borosilicate scintillating glass.

[0045] Example 3

[0046] A Ce 3+ Doped borosilicate gadolinium scintillating glass, comprising a main component and an externally doped Ce 3+ The molar percentage of the composition is: 5SiO 2 -25B 2 O 3 -25Gd 2 O 3 -30GdF 3 -15MgF 2 -1CeF 3 ;

[0047] 1. Weigh the raw materials according to the above glass components and grind and mix them thoroughly to obtain glass raw materials;

[0048] 2. Pour the mixed glass raw materials into a covered corundum crucible, put a large corundum crucible on the corundum crucible filled with raw materials, spread 10g of graphite powder as a reducing agent on the bottom of the large corundum crucible, cover it and sinter it in an air atmosphere, the melting temperature is 1250℃, and the melting time is 120min;

[0049] 3. Pour the glass melt into a mold preheated at 500℃ and cool it to shape. Then transfer it to a 500℃ annealing furnace for constant temperature annealing to eliminate internal stress. After annealing for 6 hours, reduce the temperature to 150℃ at a rate of 2℃ / min, and then cool it to room temperature with the furnace to obtain Ce 3+ Gadolinium-doped borosilicate scintillating glass.

[0050] Example 4

[0051] A Ce 3+ Doped borosilicate gadolinium scintillating glass, comprising a main component and an externally doped Ce 3+ The molar percentage of the composition is: 5SiO 2 -25B 2 O 3 -25Gd 2 O 3 -20GdF 3 -25MgF 2 -1CeF 3 ;

[0052] 1. Weigh the raw materials according to the above glass components and grind and mix them thoroughly to obtain glass raw materials;

[0053] 2. Pour the mixed glass raw materials into a covered corundum crucible, put a large corundum crucible on the corundum crucible filled with raw materials, spread 10g of graphite powder as a reducing agent on the bottom of the large corundum crucible, cover it and sinter it in an air atmosphere, the melting temperature is 1250℃, and the melting time is 120min;

[0054] 3. Pour the glass melt into a mold preheated at 500℃ and cool it to shape. Then transfer it to a 500℃ annealing furnace for constant temperature annealing to eliminate internal stress. After annealing for 6 hours, reduce the temperature to 150℃ at a rate of 2℃ / min, and then cool it to room temperature with the furnace to obtain Ce 3+ Gadolinium-doped borosilicate scintillating glass.

[0055] Example 5

[0056] A Ce 3+ Doped borosilicate gadolinium scintillating glass, comprising a main component and an externally doped Ce 3+ The molar percentage of the composition is: 5SiO 2 -25B 2 O 3 -25Gd 2 O 3 -10GdF 3 -35MgF 2 -1CeF 3 ;

[0057] 1. Weigh the raw materials according to the above glass components and grind and mix them thoroughly to obtain glass raw materials;

[0058] 2. Pour the mixed glass raw materials into a covered corundum crucible, put a large corundum crucible on the corundum crucible filled with raw materials, spread 10g of graphite powder as a reducing agent on the bottom of the large corundum crucible, cover it and sinter it in an air atmosphere, the melting temperature is 1250℃, and the melting time is 120min;

[0059] 3. Pour the glass melt into a mold preheated at 500℃ and cool it to shape. Then transfer it to a 500℃ annealing furnace for constant temperature annealing to eliminate internal stress. After annealing for 6 hours, reduce the temperature to 150℃ at a rate of 2℃ / min, and then cool it to room temperature with the furnace to obtain Ce 3+ Gadolinium-doped borosilicate scintillating glass.

[0060] Example 6

[0061] A Ce 3+ Doped borosilicate gadolinium scintillating glass, comprising a main component and an externally doped Ce 3+ The molar percentage of the composition is: 5SiO 2 -25B 2 O 3 -25Gd 2 O 3 -10GdF 3 -35LiF-1CeF 3 ;

[0062] 1. Weigh the raw materials according to the above glass components and grind and mix them thoroughly to obtain glass raw materials;

[0063] 2. Pour the mixed glass raw materials into a covered corundum crucible, put a large corundum crucible on the corundum crucible filled with raw materials, spread 10g of graphite powder as a reducing agent on the bottom of the large corundum crucible, cover it and sinter it in an air atmosphere, the melting temperature is 1250℃, and the melting time is 120min;

[0064] 3. Pour the glass melt into a mold preheated at 500℃ and cool it to shape. Then transfer it to a 500℃ annealing furnace for constant temperature annealing to eliminate internal stress. After annealing for 6 hours, reduce the temperature to 150℃ at a rate of 2℃ / min, and then cool it to room temperature with the furnace to obtain Ce 3+ After LiF is doped into the glass, the density of the glass decreases slightly due to the low atomic number of Li, and the density is 5.3 g / cm 3 The introduction of LiF helps to reduce the melting temperature of the glass, and the glass forming effect is better. Li contributes to the luminescence of the glass. The light yield of the glass is 1950ph / MeV, and the line pair number of the X-ray imaging resolution is 18lp / mm.

[0065] Example 7

[0066] A Ce 3+ Doped borosilicate gadolinium scintillating glass, comprising a main component and an externally doped Ce 3+ The molar percentage of the composition is: 5SiO 2 -25B 2 O 3 -25Gd 2 O 3 -10GdF 3 -10BaF 2 -25BaO-1CeF 3 ;

[0067] 1. Weigh the raw materials according to the above glass components and grind and mix them thoroughly to obtain glass raw materials;

[0068] 2. Pour the mixed glass raw materials into a covered corundum crucible, put a large corundum crucible on the corundum crucible filled with raw materials, spread 10g of graphite powder as a reducing agent on the bottom of the large corundum crucible, cover it and sinter it in an air atmosphere, the melting temperature is 1250℃, and the melting time is 120min;

[0069] 3. Pour the glass melt into a mold preheated at 500℃ and cool it to shape. Then transfer it to a 500℃ annealing furnace for constant temperature annealing to eliminate internal stress. After annealing for 6 hours, reduce the temperature to 150℃ at a rate of 2℃ / min, and then cool it to room temperature with the furnace to obtain Ce 3+ Doped silicon boron gadolinium scintillating glass. In this embodiment, BaF 2 and BaO, the density of glass has increased to 5.9g / cm 3 However, the introduction of Ba leads to the deterioration of the physical properties of the glass, and the glass is easy to break during processing. However, the transmittance of the glass is not affected. The X-ray imaging resolution of the glass is 16lp / mm, which is compared with the introduction of MgF 2 The effect is poor.

[0070] Comparative Example 1

[0071] Same as Example 1, except that the molar percentage of glass composition is: 5SiO 2 -25B 2 O 3 -25Gd 2 O 3 -40GdF 3 -5MgF 2

[0072] -5CeF 3 ; Due to CeF 3The introduction of more leads to incomplete glass reduction, and the scintillator glass appears light yellow. The luminous intensity of the glass becomes lower, the light yield is quenched, the test result of the light yield is significantly reduced, the density of the glass does not change significantly, the X-ray resolution effect of the glass is reduced, and the quantum efficiency is reduced.

[0073] Comparative Example 2

[0074] Same as in Example 1, the glass composition molar percentage is: 5SiO 2 -25B 2 O 3 -25Gd 2 O 3 -40GdF 3 -5MgF 2 -1CeF 3 The difference is that the melting temperature of the glass is 1150℃ and the annealing temperature is 500℃. Due to the lower melting temperature of the glass, the glass has phase separation and turbidity, the density of the glass has not changed significantly, and the luminous intensity of the glass has been significantly reduced. The light yield of the glass is reduced, the X-ray imaging effect is reduced, and the quantum efficiency is reduced.

[0075] Comparative Example 3

[0076] Same as in Example 1, the glass composition molar percentage is: 5SiO 2 -25B 2 O 3 -25Gd 2 O 3 -40GdF 3 -5MgF 2 -1CeF 3 The difference is that the melting temperature of the glass is 1250°C and the annealing temperature is 550°C. Due to the increase in the annealing temperature of the glass, crystallization occurs on the glass surface, the density of the glass does not change significantly, the luminous intensity of the glass decreases, the light yield decreases, the X-ray imaging effect deteriorates, and the quantum efficiency decreases.

[0077] Comparative Example 4

[0078] Same as Example 5, except that the molar percentage of glass composition is: 5SiO 2 -25B 2 O 3 -25Gd 2 O 3 -5GdF 3 -

[0079] 40MgF 2 -1CeF 3 ; Due to MgF 2 :GdF 38:1, MgF 2 The increase in content leads to a large amount of crystallization in the glass, and the interior of the glass becomes turbid and opaque. The density of the glass decreases, the luminous intensity decreases, the X-ray imaging has no recognition, the quantum efficiency of the glass decreases, and the light yield of the glass decreases.

[0080] Comparative Example 5

[0081] Same as Example 5, except that the molar percentage of glass composition is: 5SiO 2 -10B 2 O 3 -25Gd 2 O 3 -20GdF 3 -

[0082] 40MgF 2 -1CeF 3 ; Due to B 2 O 3 The content is reduced, and boric acid plays a fluxing role in the glass. Therefore, a large amount of solid infusible material remains in the glass after sintering. Since the Gd compound cannot be fully melted, although the density of the glass increases, the glass cannot transmit light, the luminous intensity of the glass decreases, the quantum efficiency decreases, the X-ray imaging effect deteriorates, and the light yield decreases.

[0083] The density of all scintillating glasses was measured by Archimedean principle using a precision balance immersed in alcohol. The X-ray stimulated luminescence (XEL) spectra of all scintillating glasses were measured by a Zolix Omni-λ300i spectrometer in reflection mode. Figure 1 The morphology pictures of the scintillating glass of Examples 1-5 show that the scintillating glass is colorless and transparent, and the glass does not turn yellow, which proves that the reduction effect is good. Figure 2 The X-ray excitation emission spectra of the scintillating glass and BGO crystal prepared in Examples 1-5 are compared. By comparing, it can be seen that MgF 2 The introduction of MgF has an enhanced effect on the luminescence of glass. The light yield of glass increases with the increase of MgF 2 The introduction of is gradually increasing. Figure 3 1 is the transmission spectrum diagram of Examples 1-5. It can be seen from the diagram that the transmittance of the scintillating glass is good, and the transmittance of all samples is 85%. Figure 4 The DSC test spectrum of Example 1-5 shows that the transition temperature and crystallization starting temperature of the scintillation glass are relatively high, which proves that the glass has good stability. 2 The melting point of MgF 2 With the introduction of , the glass transition temperature and crystallization starting temperature gradually move toward the low temperature, which is in line with the law. Figure 5This is the X-ray imaging and resolution diagram of Example 1. From this diagram, we can see that the resolution line pair number of the glass is 14pl / mm, and the pins of the chip can be clearly seen, proving that the glass responds well to X-rays. Figure 6 This is the X-ray imaging and resolution diagram of Example 5. From this diagram, we can see that the resolution line logarithm of the glass is 26 pl / mm, proving that with the increase of MgF 2 The introduction of further improves the resolution of the glass and makes the glass more sensitive to X-rays. The density, quantum efficiency and light yield of the scintillator glass of Examples 1-5 and Comparative Examples 1-5 are shown in Table 1. 3+ The gadolinium-doped borosilicate scintillating glass has high light yield, high X-ray imaging resolution line logarithm, high quantum detection efficiency, high density, and low cost. Therefore, it is suitable for medical imaging, radiation detection, industrial non-destructive testing, etc.

[0084] Table 1 Performance of scintillation glass prepared in Examples and Comparative Examples

[0085]

Claims

1. A Ce 3+ The gadolinium-doped borosilicate scintillating glass is characterized by: The Ce 3+ Doped silicon boron gadolinium scintillating glass, including main component, reducing agent and externally doped Ce 3+ ; The main components include components and their respective molar percentages are SiO2 5%, B2O3 25%, Gd2O3 25%, GdF3 40-10%, X 5-35%; X is one or more of MgF2, LiF, BaO, BaF2, and the sum of the main components is 100 mol%; By mass ratio, Ce 3+ Doped borosilicate gadolinium scintillating glass: reducing agent = (6-2): 1; Externally doped Ce 3+ The molar percentage of the main component is 1%-2%.

2. Ce according to claim 1 3+ The gadolinium-doped borosilicate scintillating glass is characterized by: The reducing agent is C powder and / or C particles.

3. Ce according to claim 1 3+ The gadolinium-doped borosilicate scintillating glass is characterized by: The Ce doped 3+ Introduced by CeF3 and / or CeO2.

4. Ce according to claim 1 3+ The gadolinium-doped borosilicate scintillating glass is characterized by: The Ce 3+ The gadolinium-doped borosilicate scintillating glass is amorphous with a density of 5.3-5.9 g / cm 3 The light output is 1223-2100ph / MeV, the X-ray imaging line number is 14-26lp / mm, and the quantum efficiency is 59.65~85.00%.

5. Ce according to any one of claims 1 to 4 3+ The preparation method of the gadolinium-doped borosilicate scintillating glass is characterized by: The following steps are involved: S1: Follow the instructions 3+ Composition of the Si-Bo-Gd-Doped Scintillating Glass Weigh the raw materials, grind and mix them thoroughly to obtain glass raw materials; S2: pouring the uniformly mixed glass raw materials into a covered corundum crucible and melting them to obtain a uniform glass melt; S3: Pour the uniform glass melt into the preheated mold, cool it into shape, and transfer it to the annealing furnace for constant temperature annealing to eliminate internal stress and obtain Ce 3+ Gadolinium-doped borosilicate scintillating glass.

6. Ce according to claim 5 3+ The preparation method of the gadolinium-doped borosilicate scintillating glass is characterized by: In step S2, when a corundum crucible is used, the melting temperature is 1200-1250°C, the melting time is 90-120 minutes, and the melting atmosphere is air atmosphere.

7. Ce according to claim 5 3+ The preparation method of the gadolinium-doped borosilicate scintillating glass is characterized by: In step S3, the preheating temperature of the mold is 450-500° C.; and / or, the annealing temperature is 450-500° C. for 6-8 hours.

8. Ce according to claim 5 3+ The preparation method of the gadolinium-doped borosilicate scintillating glass is characterized by: In step S3, after the annealing, the step further includes: cooling, including cooling to 150° C. at a cooling rate of 5-10° C. / min, and then cooling to room temperature in the furnace.

9. A Ce 3+ Application of gadolinium-doped borosilicate scintillating glass, characterized by: Ce according to any one of claims 1 to 4 3+ Ce doped with borosilicate gadolinium scintillating glass or prepared by the preparation method according to any one of claims 5 to 8 3+ Gadolinium-doped borosilicate scintillating glass is used in X-ray medical imaging, radiation detection, and industrial non-destructive testing.

10. An optical element, characterized in that: Comprising Ce according to any one of claims 1 to 4 3+ Ce doped with borosilicate gadolinium scintillating glass or prepared by the preparation method according to any one of claims 5 to 8 3+ Gadolinium-doped borosilicate scintillating glass.

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