Rare-earth-ion-doped LiGdI4 microcrystalline glass and preparation method thereof

[0021] Example 1: Table 1 shows the glass formulation and the first crystallization temperature value of Example 1.

[0022] Table 1

[0023]

[0024] The specific preparation process is as follows: the first step, according to the formula in Table 1, weigh 50 grams of analytically pure raw materials, add 2.5 grams of NH 4 HF 2 , 2.5 g NH 4 HI 2 , Mix the raw materials evenly and pour them into a quartz crucible for melting, the melting temperature is 800 ℃, and the temperature is kept for 2 hours. After an hour, the temperature was lowered to 50°C at a rate of 10°C/hour, the power of the muffle furnace was turned off, and the temperature was automatically lowered to room temperature, and the glass was taken out; in the second step, according to the experimental data of thermal analysis (DTA) of the glass, the first crystallization temperature was obtained 445 ℃, the prepared glass was placed in a nitrogen precision annealing furnace for heat treatment at 470 ℃ for 6 hours, then cooled to 50 ℃ at a rate of 5 ℃/hour, and the power of the precision annealing furnace was turned off to automatically cool down to room temperature to obtain transparent Ce 3+ Doped LiGdI 4 Glass-ceramic samples.

[0025] For the prepared LiGdI 4 The glass-ceramic is tested by transmission electron microscope, and the transmission electron microscope image after the glass is micro-crystallized is as follows figure 1 The results are as follows: in the photo, the glass matrix and the precipitated nanocrystallites are relatively clear, and the black dots distributed in the glass matrix are microcrystal particles. X-ray diffraction test shows that the crystal phase is LiGdI 4 phase, so the resulting material is LiGdI 4 Devitrified glass-ceramic. X-ray excited Ce 3+ Ion-doped LiGdI 4 The fluorescence spectrum of glass-ceramic such as figure 2 As shown, the fluorescence peak intensity is larger. Doped with Ce 3+ ionic LiGdI 4 The glass-ceramic light output is 32000ph/MeV with a decay time of 55ns.

[0026] Example 2: Table 2 shows the glass formulation and the first crystallization temperature value of Example 2.

[0027] Table 2

[0028]

[0029] The specific preparation process is as follows: the first step, according to the formula in Table 2, weigh 50 grams of analytically pure raw materials, add 2.5 grams of NH 4 HF 2 , 2.5 g NH 4 HI 2 , Mix the raw materials evenly and pour them into a corundum crucible for melting. The melting temperature is 850 ° C, and the temperature is kept for 1 hour. The glass melt is poured into the cast iron mold, and then placed in a muffle furnace for annealing, and the temperature is kept at the glass transition temperature Tg for 1 After one hour, the temperature was lowered to 50°C at a rate of 10°C/hour, the power of the muffle furnace was turned off and the temperature was automatically lowered to room temperature, and the glass was taken out; in the second step, according to the experimental data of thermal analysis (DTA) of the glass, the first crystallization temperature of 450°C was obtained. ℃, the prepared glass was placed in a nitrogen precision annealing furnace for heat treatment at 470 ℃ for 4 hours, then cooled to 50 ℃ at a rate of 5 ℃/hour, and the power of the precision annealing furnace was turned off to automatically cool down to room temperature to obtain transparent Eu 3+ Ion-doped LiGdI 4 glass-ceramic.

[0030] For the prepared LiGdI 4 Spectroscopic properties testing of glass-ceramic, X-ray excited Eu 3+ Ion-doped LiGdI 4 The fluorescence spectrum of glass-ceramic such as image 3 , the results show that Eu:LiGdI is produced after heat treatment 4Compared with the corresponding glass matrix, the luminous intensity of the crystallites has been significantly improved, indicating that Eu:LiGdI 4 The luminescent properties of glass-ceramic are better.

[0031] Example 3: Table 3 shows the glass formulation and the first crystallization temperature value of Example 3.

[0032] table 3

[0033]

[0034] The specific preparation process is as follows: the first step, according to the formula in Table 3, weigh 50 grams of analytically pure raw materials, add 2.5 grams of NH 4 HF 2 , 2.5 g NH 4 HI 2 , after mixing the raw materials evenly, pour it into a quartz crucible for melting, the melting temperature is 900 ° C, and the temperature is kept for 1.5 hours. The glass melt is poured into a cast iron mold, and then placed in a muffle furnace for annealing. After an hour, the temperature was lowered to 50°C at a rate of 10°C/hour, the power of the muffle furnace was turned off, and the temperature was automatically lowered to room temperature, and the glass was taken out. In the second step, according to the thermal analysis (DTA) experimental data of the glass, the first crystallization temperature of 453°C was obtained, and the prepared glass was placed in a nitrogen precision annealing furnace at 472°C for heat treatment for 5 hours, and then at 5°C/hour. The temperature is lowered to 50 °C at a rate of 3+ Ion-doped LiGdI 4 glass-ceramic.

[0035] For the prepared LiGdI 4 Spectroscopic properties testing of glass-ceramic, X-ray excited Tb 3+ Ion-doped LiGdI 4 The fluorescence spectrum of glass-ceramic such as Figure 4 , the results show that Tb:LiGdI is produced after heat treatment 4 Compared with the corresponding glass matrix, the luminescence intensity of the crystallites has been significantly improved, indicating that the Tb:LiGdI 4 The luminescent properties of glass-ceramics are better; the rare earth ion-doped LiGdI obtained by the above preparation process 4 Glass-ceramic is transparent and has excellent physical and chemical properties.