CN116751047A - Co-doped lutetium aluminum garnet scintillating ceramic and preparation method thereof - Google Patents
Co-doped lutetium aluminum garnet scintillating ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 105
- 239000002223 garnet Substances 0.000 title claims abstract description 20
- -1 lutetium aluminum Chemical compound 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 10
- 229910004261 CaF 2 Inorganic materials 0.000 claims abstract description 10
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 4
- 238000000137 annealing Methods 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 20
- 238000000498 ball milling Methods 0.000 claims description 17
- 239000011812 mixed powder Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 235000015895 biscuits Nutrition 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000004697 Polyetherimide Substances 0.000 claims description 9
- 238000009694 cold isostatic pressing Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 229920001601 polyetherimide Polymers 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 239000011268 mixed slurry Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 239000012856 weighed raw material Substances 0.000 claims description 2
- 238000002059 diagnostic imaging Methods 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 description 42
- 239000000203 mixture Substances 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 5
- 229910001634 calcium fluoride Inorganic materials 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910003443 lutetium oxide Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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Abstract
The invention discloses a co-doped lutetium aluminum garnet scintillating ceramic and a preparation method thereof, wherein the scintillating ceramic adopts Lu 2 O 3 、Al 2 O 3 、CeO 2 And CaF 2 The powder is used as raw material powder and prepared by a solid phase reaction method, and the scintillating ceramic has a garnet structure and a general formula (Lu) 0.997‑x Ca x Ce 0.003 ) 3 Al 5 O 12 Wherein x is more than 0 and less than or equal to 0.005, ca 2+ After co-doping, the scintillation property of Ce-LuAG ceramic is greatly improved. The scintillating ceramic has higher light yield, faster scintillation decay time and better thermal stability, solves the problems of low light yield value, larger slow component in scintillation response, poor thermal stability and the like of the scintillating ceramic prepared by the prior art, and is preparedThe preparation method is simple, short in time and low in cost, is suitable for industrial production, and can be applied to medical imaging and high-energy physical (HEP) experiments.
Description
Technical Field
The invention relates to the technical field of fluorescent ceramics, in particular to co-doped lutetium aluminum garnet scintillating ceramic and a preparation method thereof
Background
Scintillating materials have been successfully used in various fields of application as an optically functional material capable of absorbing high-energy rays or particles and converting them into low-energy photons. Over the last several decades, as requirements for scintillation performance have become more stringent for medical imaging and High Energy Physics (HEP) experiments, various scintillation materials have been developed. Among them, lutetium aluminum garnet (Ce: luAG) having cerium as a luminescence center is one of the most promising scintillators due to its excellent scintillation performance. However, the low light yield value and the relatively large slow component of the scintillation response greatly limit the practical use of Ce-LuAG.
There are a great deal of literature currently on scintillating ceramics of garnet systems in an effort to optimize the performance of the scintillating ceramics. First, literature (j.am. Ceram. Soc.,2018, doi: 10.1111/jace.16038) anneals Ce by deep oxygen atmosphere, mg: luAG scintillating ceramic to eliminate oxygen vacancy defects while lifting Ce 3+ →Ce 4+ Thereby significantly improving the scintillation efficiency of the ceramic material. Subsequently, literature (J.Eur. Ceram. Soc.,2018, 38:3246-3254) discloses the effect of Ce ion doping concentration on the luminescence properties of Ce, mg: luAG scintillating ceramics, and screens out the optimal Ce ion doping concentration, but too high Ce ion doping concentration causes self-absorption phenomena, which is detrimental to Ce, mg: fast scintillation response of LuAG ceramics. Furthermore, literature (Effect of Mg 2+ Co-doping on the scintillation performance of LuAG Ce ceramics, phys State solid-R.2014; 8 (1): 105-9) discloses a method for preparing the same with Mg 2+ Co-doped Ce-LuAG-ceramic optical yield is greatly improved, however, mg 2+ Impurity ions remain in the LuAG lattice. Excess Mg in LuAG-Ce ceramics 2+ Leading to limited carrier transport processes and reduced scintillation performance. CN 104557012a discloses that red light ion Pr is doped to increase the light yield of scintillating ceramics, but the light yield increase is limited, the energy efficiency is low, and the prevention of X-rays is limited.
Disclosure of Invention
One of the purposes of the invention is to provide a co-doped lutetium aluminum garnet scintillating ceramic which has the advantages of high light yield and fast scintillation decay time as a scintillating material.
The second purpose of the invention is to provide a preparation method of the co-doped lutetium aluminum garnet scintillating ceramic, which has the advantages of simple preparation method, short time consumption and low cost, and is suitable for industrialized production.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a co-doped lutetium aluminum garnet scintillating ceramic having a chemical formula (Lu 0.997-x Ca x Ce 0.003 ) 3 Al 5 O 12 Wherein x is Ca 2+ Doping Lu 2+ Mole percent of bits, 0 < x.ltoreq.0.005, the scintillating ceramic being Lu 2 O 3 、Al 2 O 3 、CeO 2 And CaF 2 The powder is used as scintillating ceramic raw material powder and is prepared by a solid phase reaction method.
In the present invention, by using Ca 2+ Codoping Ce, luAG, ce 3+ Partial oxidation to Ce 4+ ，Ca 2+ Co-doping greatly reduces defects in the Ce-LuAG-ceramic scintillator, greatly improves light yield and thermal stability of the scintillating ceramic, and quickens scintillation decay time.
The scintillating ceramic is along with Ca 2+ Co-doping in Ca 2+ When the doping concentration is 0.1-0.5 at%, ca, ce and LuAG scintillating ceramicThe light yield is up to 20000-28400 ph/MeV, the scintillation decay time is less than 50ns, which is far higher than that of the non-doped Ca 2+ 12000-16800 ph/MeV, scintillation decay time less than 90ns, ca when the temperature is increased from 80K to 320K 2+ When the doping concentration is 0.1-0.5 at%, the RL strength can still keep 85-140% of the initial strength.
In a second aspect, the present invention also provides a method for preparing the co-doped lutetium aluminum garnet scintillating ceramic, which adopts a solid phase reaction method for sintering, and specifically comprises the following steps:
(1) According to the chemical formula (Lu) 0.997-x Ca x Ce 0.003 ) 3 Al 5 O 12 The stoichiometric ratio of each element is respectively measured and Lu is obtained 2 O 3 、Al 2 O 3 、CeO 2 And CaF 2 As a starting material, wherein x is Ca 2+ Doping Lu 2+ Mole percent of the position is more than 0 and less than or equal to 0.005;
(2) Mixing the weighed raw material powder and the dispersant polyetherimide, adding absolute ethyl alcohol, ball-milling and mixing, drying and sieving the obtained mixed slurry, and then placing the mixed powder in a muffle furnace for calcination;
(3) Placing the calcined powder into a grinding tool for dry pressing and forming, and then performing cold isostatic pressing to obtain a biscuit with the relative density of 50-55%;
(4) And (3) sintering the biscuit in vacuum, cooling to room temperature, putting the ceramic into a muffle furnace for annealing, and finally cutting and polishing the ceramic to obtain the scintillating ceramic.
Preferably, in the step (2), the adding amount of the dispersant polyetherimide is 0.8-1 wt.% of the total mass of the raw material powder, and the mass ratio of the total mass of the raw material powder to the absolute ethyl alcohol is 1:1.5-3.
Preferably, in the step (2), the ball milling rotating speed is 180-250 rpm, and the ball milling time is 15-30 h.
Preferably, in the step (2), the drying temperature is 50-80 ℃ and the drying time is 8-12 h.
Preferably, in the step (2), the temperature rising system of the calcination is that the temperature is raised to 600-800 ℃ at the temperature rising rate of 2-10 ℃/min, and the temperature is kept for 5-7 h.
Preferably, in the step (3), the cold isostatic pressing holding pressure is 150-200 Mpa, and the holding time is 5-10 min.
Preferably, in the step (4), the vacuum sintering temperature is 1300-1650 ℃ and the heat preservation time is 10-24 h.
Preferably, in the step (4), the annealing temperature is 1100-1500 ℃ and the annealing time is 4-10 h.
Compared with the prior art, the invention has the following beneficial effects:
1. the scintillation ceramic Ca prepared by the invention 2+ Codoping Ce, luAG, ce 3+ Partial oxidation to Ce 4+ When Ca is 2+ When the doping concentration is 0.1-0.5 at%, the light yield of Ca, ce and LuAG scintillating ceramic is up to 20000-28400 ph/MeV, and the scintillation decay time is less than 50ns and is far higher than that of the scintillating ceramic without doping Ca 2+ 12000-16800 ph/MeV, scintillation decay time less than 90ns, ca when the temperature is increased from 80K to 320K 2+ When the doping concentration is 0.1 to 0.5at%, the XEL intensity is kept about 100 to 140% of the initial intensity. When Ca is 2+ When the doping concentration is 0.2at percent, the light yield of Ca, ce and LuAG scintillating ceramic reaches 28400ph/MeV.
2. The scintillating ceramic prepared by the invention has the characteristics of high light yield and high thermal stability, greatly improves the scintillating performance of the scintillating ceramic, has simple preparation method, short time and low cost, is suitable for industrial production, and can be applied to medical imaging and high-energy physical (HEP) experiments.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction chart of the scintillating ceramics prepared in examples 1 to 5 of the present invention;
FIG. 2 shows LY values of the scintillating ceramic Ce, ca: luAG at different times of 1-12. Mu.s prepared in examples 1-5 of the present invention;
FIG. 3 is a graph showing normalized XEL intensity as a function of temperature for the scintillating ceramics of examples 1-5 of the present invention;
FIG. 4 is a diagram of Ca in example 2 of the present invention 2+ And (3) carrying out SEM image of powder after ball milling of Ca and Ce and LuAG when the doping concentration is 0.2 at%.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples.
The raw material powders used in the following examples were all commercially available and had purities of more than 99.9%.
Example 1: when Ca is 2+ At a doping concentration of 0.1at%, the scintillating ceramic sample composition was (Lu 0.996 Ca 0.001 Ce 0.003 ) 3 Al 5 O 12 Is a scintillating ceramic of (2).
The mass of the target product was set to 60g according to Lu 0.996 Ca 0.001 Ce 0.003 ) 3 Al 5 O 12 The stoichiometric ratio of each element is respectively measured and Lu is obtained 2 O 3 、CeO 2 、Al 2 O 3 And CaF 2 As raw material powder. Mixing 400 mu L of polyether imide serving as a dispersing agent, adding absolute ethyl alcohol, mixing, namely, stirring the materials of lutetium oxide, cerium oxide, aluminum oxide and calcium fluoride powder and the absolute ethyl alcohol in a mass ratio of 1:1.5, adopting a planetary ball mill to carry out full mixing, carrying out ball milling at a rotating speed of 180rpm for 20h, drying the ball-milled mixed slurry in an oven at 80 ℃ for 13h to obtain mixed powder, sieving the mixed powder by a 200-mesh sieve for two times, and calcining the mixed powder at 800 ℃ for 5h. And then drying and pressing the mixture in a steel mould to obtain a biscuit, and carrying out cold isostatic pressing for 200MPa and 5min to obtain the biscuit with the relative density of 50%. Vacuum sintering is then performed: the sintering temperature is 1550 ℃, the heat preservation is carried out for 10 hours, then the ceramic after vacuum sintering is put into a high-temperature muffle furnace for annealing, the annealing temperature is 1500 ℃, the annealing time is 4 hours, and finally the ceramic is cut and polished to obtain the scintillating ceramic. The scintillating ceramic is about 17mm in diameter and 2mm in thickness.
The embodiment will be described(Lu) 0.996 Ca 0.001 Ce 0.003 ) 3 Al 5 O 12 XRD testing of the scintillating ceramic showed that: 0.1at% Ca 2+ Successfully enters the LuAG lattice as shown in fig. 1.
The scintillating ceramic prepared by the example is tested by light yield, the light output reaches 27600ph/MeV, and the scintillation decay time is 54ns, as shown in figure 2. The ceramic is compared with the undoped sample, ca 2+ The XEL intensity of the co-doped ceramic does not change significantly with temperature rise, and can still keep about 100% -110% of the initial intensity, as shown in figure 3.
Example 2: when Ca is 2+ At a doping concentration of 0.2at%, the scintillating ceramic sample composition was (Lu 0.995 Ca 0.002 Ce 0.003 ) 3 Al 5 O 12 Is a scintillating ceramic of (2).
The mass of the target product was set to 60g according to Lu 0.995 Ca 0.002 Ce 0.003 ) 3 Al 5 O 12 The stoichiometric ratio of each element is respectively measured and Lu is obtained 2 O 3 、CeO 2 、Al 2 O 3 And CaF 2 As raw material powder. And (3) adding 400 mu L of dispersant polyetherimide into the mixture after blending, wherein the mass ratio of the total mass of the raw materials lutetium oxide, cerium oxide, aluminum oxide and calcium fluoride to the absolute ethanol is 1:1.5, fully mixing the raw materials by adopting a planetary ball mill, and performing ball milling for 20 hours at a speed of 180rpm, wherein an SEM image of the powder after ball milling is shown in FIG. 4. And drying the ball-milled mixed slurry in an oven at 60 ℃ for 10 hours to obtain mixed powder, sieving the mixed powder by a 200-mesh sieve for two times, and calcining the mixed powder at 800 ℃ for 5 hours. And then drying and pressing the mixture in a steel mould to obtain a biscuit, and carrying out cold isostatic pressing for 150MPa and dwell time for 6min to obtain the biscuit with the relative density of 53%. Vacuum sintering is then performed: the sintering temperature is 1500 ℃, the heat preservation is carried out for 10 hours, then the ceramic after vacuum sintering is put into a high-temperature muffle furnace for annealing, the annealing temperature is 1450 ℃, the annealing time is 6 hours, and finally the ceramic is cut and polished to obtain the scintillating ceramic. The scintillating ceramic is about 17mm in diameter and 2mm in thickness.
The Lu obtained in this example was used 0.995 Ca 0.002 Ce 0.003 ) 3 Al 5 O 12 XRD testing of the scintillating ceramic showed that: 0.2at% Ca 2+ Successfully enters the LuAG lattice as shown in fig. 1.
The scintillating ceramic prepared by the example is subjected to light yield test, the light output reaches 28400ph/MeV, and the scintillation decay time is 48ns, as shown in figure 2. The ceramic is compared with the undoped sample, ca 2+ The XEL intensity of the co-doped ceramic does not change significantly with temperature rise, and can still keep about 100% -109% of the initial intensity, as shown in figure 3.
Example 3: when Ca is 2+ At a doping concentration of 0.3at%, the scintillating ceramic sample composition was (Lu 0.994 Ca 0.003 Ce 0.003 ) 3 Al 5 O 12 Is a scintillating ceramic of (2).
The mass of the target product was set to 60g according to ((Lu) 0.994 Ca 0.003 Ce 0.003 ) 3 Al 5 O 12 The stoichiometric ratio of each element is respectively measured and Lu is obtained 2 O 3 、CeO 2 、Al 2 O 3 And CaF 2 As raw material powder. Mixing 400 mu L of polyether imide serving as a dispersing agent, adding absolute ethyl alcohol, and enabling the mass ratio of the total mass of lutetium oxide, cerium oxide, aluminum oxide and calcium fluoride serving as raw materials to the absolute ethyl alcohol to be 1:2; fully mixing by adopting a planetary ball mill, wherein the ball milling rotating speed is 250rpm, ball milling is carried out for 30 hours, the ball-milled mixed slurry is dried in an oven at 50 ℃ for 12 hours to obtain mixed powder, the mixed powder is screened by a 200-mesh screen for two times, and the mixed powder is calcined for 7 hours at 600 ℃. And then drying and pressing the mixture in a steel mould to obtain a biscuit, and carrying out cold isostatic pressing for 170MPa and dwell time for 7min to obtain the biscuit with the relative density of 52%. Vacuum sintering is then performed: the sintering temperature is 1450 ℃, the heat preservation is carried out for 10 hours, then the ceramic after vacuum sintering is put into a high-temperature muffle furnace for annealing, the annealing temperature is 1400 ℃, the annealing time is 8 hours, and finally the ceramic is cut and polished to obtain the scintillating ceramic. The scintillating ceramic is about 17mm in diameter and 2mm in thickness.
The ((Lu) obtained in this example 0.994 Ca 0.003 Ce 0.003 ) 3 Al 5 O 12 XRD testing of the scintillating ceramic showed that:0.3at％Ca 2+ successfully enters the LuAG lattice as shown in fig. 1.
The scintillating ceramic prepared by the example is subjected to light yield test, the light output reaches 27400ph/MeV, and the scintillation decay time is 48ns, as shown in figure 2. The ceramic is compared with the undoped sample, ca 2+ The XEL intensity of the co-doped ceramic does not change significantly with the temperature rise, and still can keep about 98% -104% of the initial intensity, as shown in figure 3.
Example 4: when Ca is 2+ At a doping concentration of 0.4at%, the scintillating ceramic sample composition was (Lu 0.993 Ca 0.004 Ce 0.003 ) 3 Al 5 O 12 Is a scintillating ceramic of (2).
The mass of the target product was set to 60g, according to (Lu 0.993 Ca 0.004 Ce 0.003 ) 3 Al 5 O 12 The stoichiometric ratio of each element is respectively measured and Lu is obtained 2 O 3 、CeO 2 、Al 2 O 3 And CaF 2 As raw material powder. Mixing 400 mu L of polyether imide serving as a dispersing agent, adding absolute ethyl alcohol, and enabling the mass ratio of the total mass of lutetium oxide, cerium oxide, aluminum oxide and calcium fluoride serving as raw materials to the absolute ethyl alcohol to be 1:2.5; fully mixing by adopting a planetary ball mill, wherein the ball milling rotating speed is 200rpm, ball milling is carried out for 20 hours, the mixed slurry after ball milling is dried in an oven at 80 ℃ for 9 hours to obtain mixed powder, sieving the mixed powder by a 200-mesh sieve for two times, and calcining the mixed powder for 6 hours at 800 ℃. And then drying and pressing the mixture in a steel mould to obtain a biscuit, and carrying out cold isostatic pressing for 200MPa and 10min to obtain the biscuit with the relative density of 54%. Vacuum sintering is then performed: the sintering temperature is 1400 ℃, the heat preservation is carried out for 10 hours, then the ceramic after vacuum sintering is put into a high-temperature muffle furnace for annealing, the annealing temperature is 1350 ℃, the annealing time is 8 hours, and finally the ceramic is cut and polished to obtain the scintillating ceramic. The scintillating ceramic is about 17mm in diameter and 2mm in thickness.
The (Lu 0.993 Ca 0.004 Ce 0.003 ) 3 Al 5 O 12 XRD testing of the scintillating ceramic showed that: 0.4at% Ca 2+ Successfully enters the LuAG lattice as shown in fig. 1.
The scintillating ceramic prepared by the example is tested by light yield, the light output reaches 24000ph/MeV, and the scintillation decay time is 45ns, as shown in figure 2. The ceramic is compared with the undoped sample, ca 2+ The XEL intensity of the co-doped ceramic does not change significantly with temperature rise, and can still keep about 84% -100% of the initial intensity, as shown in figure 3.
Example 5: when Ca is 2+ At a doping concentration of 0.5at%, the scintillating ceramic sample composition was (Lu 0.995 Ca 0.005 Ce 0.003 ) 3 Al 5 O 12 Is a scintillating ceramic of (2).
The mass of the target product was set to 60g, according to (Lu 0.992 Ca 0.005 Ce 0.003 ) 3 Al 5 O 12 The stoichiometric ratio of each element is respectively measured and Lu is obtained 2 O 3 、CeO 2 、Al 2 O 3 And CaF 2 As raw material powder. Mixing 400 mu L of polyether imide serving as a dispersing agent, adding absolute ethyl alcohol, and enabling the mass ratio of the total mass of lutetium oxide, cerium oxide, aluminum oxide and calcium fluoride serving as raw materials to the absolute ethyl alcohol to be 1:3; fully mixing by adopting a planetary ball mill, wherein the ball milling rotating speed is 180rpm, ball milling is carried out for 30 hours, the ball-milled mixed slurry is dried in an oven at 80 ℃ for 8 hours to obtain mixed powder, the mixed powder is sieved by a 200-mesh sieve for 2 times, and the mixed powder is calcined for 5 hours at 800 ℃. And then drying and pressing the mixture in a steel mould to form a biscuit, and carrying out cold isostatic pressing for 150MPa and holding time for 10min. Vacuum sintering is then performed: the sintering temperature is 1350 ℃, the temperature is kept for 10 hours, then the ceramic after vacuum sintering is put into a high-temperature muffle furnace for annealing, the annealing temperature is 1350 ℃, the annealing time is 8 hours, and finally the ceramic is cut and polished to obtain the scintillating ceramic. The scintillating ceramic is about 17mm in diameter and 2mm in thickness.
The (Lu 0.992 Ca 0.005 Ce 0.003 ) 3 Al 5 O 12 XRD testing of the scintillating ceramic showed that: 0.5at% Ca 2+ Successfully enters the LuAG lattice as shown in fig. 1.
The scintillating ceramic prepared by the example is tested by light yield, the light output reaches 23000ph/MeV, the scintillation decay time is 49ns, as shown in the figure2. The ceramic is compared with the undoped sample, ca 2+ The XEL strength of the co-doped ceramic does not change significantly with increasing temperature, and remains around 104-139% of the initial strength, as shown in fig. 3.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (9)
1. A co-doped lutetium aluminum garnet scintillating ceramic is characterized in that the scintillating ceramic has a chemical formula (Lu 0.997- x Ca x Ce 0.003 ) 3 Al 5 O 12 Wherein x is Ca 2+ Doping Lu 2+ Mole percent of bits, 0 < x.ltoreq.0.005, the scintillating ceramic being Lu 2 O 3 、Al 2 O 3 、CeO 2 And CaF 2 The powder is used as scintillating ceramic raw material powder and is prepared by a solid phase reaction method.
2. A method of preparing a co-doped lutetium aluminum garnet ceramic according to claim 1, comprising the steps of:
(1) According to the chemical formula (Lu) 0.997-x Ca x Ce 0.003 ) 3 Al 5 O 12 The stoichiometric ratio of each element is respectively measured and Lu is obtained 2 O 3 、Al 2 O 3 、CeO 2 And CaF 2 As a starting material, wherein x is Ca 2+ Doping Lu 2+ Mole percent of the position is more than 0 and less than or equal to 0.005;
(2) Mixing the weighed raw material powder and the dispersant polyetherimide, adding absolute ethyl alcohol, ball-milling and mixing, drying and sieving the obtained mixed slurry, and then placing the mixed powder in a muffle furnace for calcination;
(3) Placing the calcined powder into a grinding tool for dry pressing and forming, and then performing cold isostatic pressing to obtain a biscuit with the relative density of 50-55%;
(4) And (3) sintering the biscuit in vacuum, cooling to room temperature, putting the ceramic into a muffle furnace for annealing, and finally cutting and polishing the ceramic to obtain the scintillating ceramic.
3. The method for preparing a co-doped lutetium aluminum garnet ceramic according to claim 2, wherein in the step (2), the adding amount of the dispersant polyetherimide is 0.8-1 wt.% of the total mass of the raw material powder, and the mass ratio of the total mass of the raw material powder to the absolute ethyl alcohol is 1:1.5-3.
4. The method for preparing a co-doped lutetium aluminum garnet ceramic according to claim 2, wherein in the step (2), the ball milling speed is 180-250 rpm, and the ball milling time is 15-30 h.
5. The method for preparing a co-doped lutetium aluminum garnet ceramic according to claim 2, wherein in the step (2), the drying temperature is 50-80 ℃ and the drying time is 8-12 h.
6. The method for preparing a co-doped lutetium aluminum garnet ceramic according to claim 2, wherein in the step (2), the temperature rise degree of calcination is raised to 600-800 ℃ at room temperature at a temperature rise rate of 2-10 ℃/min, and the temperature is kept for 5-7 h.
7. The method of preparing a co-doped lutetium aluminum garnet ceramic according to claim 2, wherein in step (3), the cold isostatic pressing holding pressure is 150-200 Mpa and the holding time is 5-10 min.
8. The method for preparing a co-doped lutetium aluminum garnet ceramic according to claim 2, wherein in the step (4), the vacuum sintering temperature is 1300-1650 ℃ and the heat preservation time is 10-24 h.
9. The method of preparing a co-doped lutetium aluminum garnet ceramic according to claim 2, wherein in step (4), the annealing temperature is 1100-1500 ℃ and the annealing time is 4-10 h.
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| JP2010235388A (en) * | 2009-03-31 | 2010-10-21 | World Lab:Kk | Transparent ceramic, method of manufacturing the same and device using the transparent ceramic |
| CN106588012A (en) * | 2015-10-15 | 2017-04-26 | 中国科学院上海硅酸盐研究所 | Low-valence ion doped multicomponent composite ceramic scintillator and preparation method thereof |
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| JP2010235388A (en) * | 2009-03-31 | 2010-10-21 | World Lab:Kk | Transparent ceramic, method of manufacturing the same and device using the transparent ceramic |
| CN106588012A (en) * | 2015-10-15 | 2017-04-26 | 中国科学院上海硅酸盐研究所 | Low-valence ion doped multicomponent composite ceramic scintillator and preparation method thereof |
| JP2020200206A (en) * | 2019-06-07 | 2020-12-17 | クアーズテック株式会社 | Ce;LuAP BAKING BODY, POSITRON FAULT-MEASURING APPARATUS, AND METHOD FOR PRODUCING THE BAKING BODY |
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