Rare-earth-ion-doped CaI2 microcrystalline glass and preparation method thereof

[0022] Example 1: Table 1 shows the glass formula of Example 1 and the first crystallization temperature value.

[0023] Table 1

[0024]

[0025] The specific preparation process is as follows: In the first step, weigh 50 grams of analytically pure raw materials according to the formula in Table 1, and add 2.5 grams of NH 4 HF 2 , 2.5 grams of NH 4 HI 2 , After mixing the raw materials evenly, pour them into a corundum crucible and melt them at a melting temperature of 1450°C. Keep holding for 1 hour. Pour the glass melt into a cast iron mold, then place it in a muffle furnace for annealing, and keep it at the glass transition temperature Tg 2 After hours, the temperature is reduced to 50°C at a rate of 10°C/hour, the muffle furnace is turned off and the temperature is automatically reduced to room temperature, and the glass is taken out; in the second step, according to the thermal analysis (DTA) experimental data of the glass, the first crystallization temperature is 737 ℃, put the prepared glass in a nitrogen precision annealing furnace at 761℃ for 4 hours, and then reduce the temperature to 50℃ at a rate of 5℃/hour, turn off the power of the precision annealing furnace and automatically cool to room temperature to obtain transparent Eu 2+ Ion-doped CaI 2 Glass-ceramic.

[0026] For prepared CaI 2 X-ray diffraction test for glass-ceramics, the XRD pattern obtained after glass-ceramic treatment is as follows figure 1 As shown, the results are as follows: XRD diffraction peaks and CaI of the sample obtained by heat treatment 2 The main diffraction peaks of the standard XRD pattern of the crystalline phase are consistent, so the material obtained is CaI 2 Crystalline glass with devitrification phase. And the X-ray excited Eu 2+ Ion doped CaI 2 The fluorescence spectrum of glass-ceramics is as figure 2 As shown, the fluorescence peak intensity is great. Eu doped 2+ Ion CaI 2 The light output of glass-ceramic can reach 110000ph/MeV.

[0027] Example 2: Table 2 shows the glass formula of Example 2 and the first crystallization temperature value.

[0028] Table 2

[0029]

[0030] The specific preparation process is as follows: In the first step, weigh 50 grams of analytically pure raw materials according to the formula in Table 2, and add 2.5 grams of NH 4 HF 2 , 2.5 grams of NH 4 HI 2 , After mixing the raw materials evenly, pour them into a quartz crucible and melt them at a melting temperature of 1350°C. Keep holding for 2 hours. Pour the glass melt into a cast iron mold, then put it in a muffle furnace for annealing, and keep it at the glass transition temperature Tg. After hours, the temperature is reduced to 50°C at a rate of 10°C/hour, the muffle furnace is turned off and the temperature is automatically cooled to room temperature, and the glass is taken out; the second step, according to the thermal analysis (DTA) experimental data of the glass, the first crystallization temperature 731 is obtained ℃, put the prepared glass in a nitrogen precision annealing furnace at 751℃ for 6 hours, and then reduce the temperature to 50℃ at a rate of 5℃/hour, turn off the power of the precision annealing furnace and automatically cool down to room temperature to obtain transparent Ce 3+ Doped CaI 2 Glass-ceramic samples.

[0031] For prepared CaI 2 Spectral properties test of glass ceramics, Ce excited by X-ray 3+ Ion doped CaI 2 The fluorescence spectrum of glass-ceramics is as image 3 As shown, the result shows that Ce:CaI is produced after heat treatment 2 Compared with the corresponding glass matrix, the luminous intensity of the microcrystal has been significantly improved, indicating that Ce:CaI 2 The luminous properties of glass-ceramics are better.

[0032] Example 3: Table 3 shows the glass formula and the first crystallization temperature value of Example 3.

[0033] table 3

[0034]

[0035] The specific preparation process is as follows: In the first step, weigh 50 grams of analytically pure raw materials according to the formula in Table 3, and add 2.5 grams of NH 4 HF 2 , 2.5 grams of NH 4 HI 2 , After mixing the raw materials evenly, pour them into a quartz crucible and melt them at a melting temperature of 1400°C and hold for 1.5 hours. Pour the glass melt into a cast iron mold, then place it in a muffle furnace for annealing, and keep it at the glass transition temperature Tg 2 After hours, the temperature is lowered to 50°C at a rate of 10°C/hour, the muffle furnace is turned off and the temperature is automatically lowered to room temperature, and the glass is taken out. In the second step, according to the thermal analysis (DTA) experimental data of the glass, the first crystallization temperature is 742℃. The glass is heat treated at 785℃ for 5 hours in a nitrogen precision annealing furnace, and then 5℃/hour The temperature is lowered to 50℃ at the rate of temperature, and the power of the precision annealing furnace is turned off and the temperature is automatically lowered to room temperature to obtain transparent Tb 3+ Ion-doped CaI 2 Glass-ceramic.

[0036] For prepared CaI 2 Spectral properties test of glass-ceramic, Tb excited by X-ray 3+ Ion doped CaI 2 The fluorescence spectrum of glass-ceramics is as Figure 4 As shown, the result shows that Tb:CaI is produced after heat treatment 2 Compared with the corresponding glass matrix, the luminous intensity of the microcrystal has been significantly improved, indicating that Tb: CaI 2 The luminescence properties of glass-ceramics are better, and the luminescence intensity is obviously improved; the rare earth ion doped CaI obtained by the above preparation process 2 Glass-ceramics are transparent and have excellent physical and chemical properties.