CN-120903832-B - High-crystallinity transparent glass ceramic material containing multi-scale bi-crystalline phase

Abstract

The invention discloses a high-crystallinity transparent glass ceramic material containing a multi-scale bi-crystalline phase, the composition formula of the glass ceramic material is 20BaO-20Al 2 O 3 -20LaF 3 -40SiO 2 -xTbF 3 , laF 3 nano crystals and BaAl 2 Si 2 O 8 micron crystals are separated out from the glass ceramic material, laF 3 nano crystals and BaAl 2 Si 2 O 8 micron crystals form a multi-scale bi-crystalline phase structure, the doped concentration x of TbF 3 doped with Tb 3+ ,Tb 3+ in the glass ceramic material is 0< x less than or equal to 26mol%, and the doped Tb 3+ partially replaces La 3+ lattice sites in the LaF 3 nano crystals and Ba 2+ lattice sites in the BaAl 2 Si 2 O 8 micron crystals. The glass ceramic material has high crystallinity, high transmittance and strong scintillation luminescence property, has a thermal quenching resistance effect on the luminescence intensity within a temperature range of 303-523K and has reversible heat recovery property, and has great potential in the field of static X-ray imaging when being applied to X-ray imaging.

Inventors

• LIU XUEYUN
• CHEN LONG
• Xia Kelun
• LIU ZIJUN

Assignees

• 宁波大学

Dates

Publication Date

20260508

Application Date

20250620

Claims (6)

1. 1. The transparent glass ceramic material with high crystallinity containing multi-scale bi-crystalline phase is characterized in that the composition formula of the glass ceramic material is 20BaO-20Al 2 O 3 -20LaF 3 -40SiO 2 -xTbF 3 , laF 3 nanocrystals and BaAl 2 Si 2 O 8 microcrystals are precipitated in the glass ceramic material, the LaF 3 nanocrystals and the BaAl 2 Si 2 O 8 microcrystals form a multi-scale bi-crystalline phase structure, the BaAl 2 Si 2 O 8 microcrystals are hexagonal-phase BaAl 2 Si 2 O 8 crystalline phases, tbF 3 is doped in the glass ceramic material, the doping concentration x of Tb 3+ ,Tb 3+ is 2< x less than or equal to 26 mol%, and the doped Tb 3+ partially replaces La 3+ lattice sites in the LaF 3 nanocrystals and Ba 2+ lattice sites in the BaAl 2 Si 2 O 8 microcrystals.
2. 2. The high crystallinity transparent glass-ceramic material comprising a multiscale bi-crystalline phase according to claim 1, wherein the average size of LaF 3 nanocrystals is 30 to 60nm and the average size of BaAl 2 Si 2 O 8 nanocrystals is 50 to 70 μm.
3. 3. The high crystallinity transparent glass-ceramic material containing a multiscale bi-crystalline phase according to claim 1, wherein the LaF 3 nanocrystals are hexagonal phase LaF 3 crystalline phase.
4. 4. The high-crystallinity transparent glass-ceramic material containing a multi-scale bi-crystalline phase according to claim 1, wherein the crystallinity of the glass-ceramic material is 80-85% when the doping concentration x of Tb 3+ is 22-mol%, the transmittance of the glass-ceramic material at 543-nm wavelength is not less than 70%, and the BaAl 2 Si 2 O 8 μm crystal is a hexagonal phase BaAl 2 Si 2 O 8 crystal phase.
5. 5. The transparent glass-ceramic material with high crystallinity containing a multiscale bi-crystalline phase according to claim 1, wherein the luminous intensity of the glass-ceramic material has a thermal quenching effect and reversible thermal recovery performance in the temperature range of 303 to 523K.
6. 6. The transparent glass-ceramic material of claim 1, wherein the glass-ceramic material has a spatial resolution of up to 16 LP/mm when used in X-ray imaging.

Description

High-crystallinity transparent glass ceramic material containing multi-scale bi-crystalline phase Technical Field The invention belongs to the technical field of glass ceramics, and particularly relates to a high-crystallinity transparent glass ceramic material containing multi-scale bi-crystalline phases. Background The scintillator is used as a core functional material in the technical field of radiation detection, can convert X-rays, gamma rays or high-energy particles into detectable ultraviolet-visible light signals, and has important application value in the fields of high-energy physical experiments, nuclear medicine imaging, industrial nondestructive detection, safety inspection, environmental monitoring, astronomical observation and the like. Along with the continuous improvement of the requirements of the application fields on detection precision, environmental adaptability and the like, the development of novel scintillator materials with high light output, excellent energy resolution and strong irradiation resistance becomes a current research hot spot. Compared with the traditional single crystal scintillator, the rare earth ion doped glass scintillator has the advantages of high doping concentration, large-size preparation, easy molding and processing, low cost and the like, but the glass has a disordered structure and higher phonon energy, so that the luminous efficiency is lower, and the light yield and the energy resolution are limited. The glass ceramic is a composite optical material composed of a glass phase and a crystal phase, has excellent processability of glass and high-efficiency luminescence performance of the crystal, and is widely focused in the field of light conversion. Particularly, the glass ceramic with high crystal phase volume ratio is focused by researchers because of the unique structural advantages, on one hand, the crystal phase can provide an orderly crystal field environment with low phonon energy for a luminescent center (such as rare earth ions), on the other hand, the non-radiative transition probability is remarkably reduced, the luminescent efficiency is improved, and on the other hand, the defect concentration in the matrix amorphous phase can be reduced due to higher crystallinity, so that the stability of the glass ceramic is improved. The characteristics lead the glass ceramic with high crystal phase volume ratio to have great potential in the aspect of scintillator performance optimization, so the development of the glass ceramic with high crystal phase volume ratio has important scientific value and application prospect. However, glass ceramics with high volume ratios of crystalline phases generally suffer from the problem that when the grain size is controlled to be much smaller than the wavelength of visible light (< 400 nm) to reduce light scattering, the crystallinity tends to be difficult to increase (the glass phase ratio is too high), whereas to achieve high crystallinity, an exact match of the refractive indices of the crystalline and glass phases must be met, while the components are required to achieve a continuous uniform evolution during crystallization (e.g. by a phase separation crystallization mechanism). This requirement puts more stringent regulatory requirements on the crystalline phase composition, grain size distribution, spatial distribution, etc. of the glass system. Therefore, a novel glass ceramic material with high crystallinity, high transparency and excellent luminescence performance is obtained through reasonable design of a component system and cooperative optimization of a preparation process, and technical support is provided for developing a high-efficiency scintillator light conversion material. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a high-crystallinity transparent glass ceramic material containing a multi-scale bi-crystalline phase, which contains a multi-scale bi-crystalline phase structure formed by LaF 3 nano crystals and BaAl 2Si2O8 micro crystals and is doped with luminescent ions Tb 3+, and the balance of high crystallinity (more than or equal to 80%) and high transmittance (the transmittance at 543nm wavelength is more than or equal to 70%) is realized through the multi-scale bi-crystalline phase collaborative design, and the scintillation and luminescence properties of the glass ceramic material are obviously improved. The technical scheme adopted by the invention for solving the technical problems is that the high-crystallinity transparent glass ceramic material containing the multi-scale bi-crystalline phase has the composition formula of 20BaO-20Al 2O3-20LaF3-40SiO2-xTbF3, laF 3 nanocrystals and BaAl 2Si2O8 microcrystals are separated out from the glass ceramic material, the LaF 3 nanocrystals and the BaAl 2Si2O8 microcrystals form a multi-scale bi-crystalline phase structure, the doped concentration x of Tb 3+,Tb3+ in the glass ceramic material in the form of Tb