CN107417276B - Textured cerium-doped lutetium silicate scintillating ceramic and preparation method thereof - Google Patents

Textured cerium-doped lutetium silicate scintillating ceramic and preparation method thereof Download PDF

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CN107417276B
CN107417276B CN201710574070.1A CN201710574070A CN107417276B CN 107417276 B CN107417276 B CN 107417276B CN 201710574070 A CN201710574070 A CN 201710574070A CN 107417276 B CN107417276 B CN 107417276B
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施鹰
范灵聪
谢建军
雷芳
章蕾
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University of Shanghai for Science and Technology
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Abstract

The invention discloses a textured cerium-doped lutetium silicate scintillating ceramic and a preparation method thereof. The method comprises the steps of preparing an LSO-Ce green body with a certain grain orientation degree by molding a high-dispersion LSO-Ce slurry in a strong magnetic field, sintering the green body at 1550-1750 ℃ to obtain a ceramic sintered body with the relative density of more than 95%, carrying out hot isostatic pressing on the LSO-Ce ceramic sintered body to obtain high-density textured ceramic with the relative density of 99.8%, and finally annealing to obtain the high-transparency LSO-Ce scintillating ceramic. The crystal grain orientation degree of the LSO-Ce scintillating ceramic can reach 28%, the linear transmittance at the luminescent wavelength of 420nm can reach 6.6%, and the LSO-Ce scintillating ceramic can be used as a detector material in an X-ray CT or gamma-ray PET scanning imager.

Description

Textured cerium-doped lutetium silicate scintillating ceramic and preparation method thereof
Technical Field
The invention relates to polycrystalline scintillating ceramic and a preparation method thereof, in particular to rare earth element doped lutetium silicate scintillating ceramic and a preparation method thereof, and belongs to the technical field of polycrystalline optical ceramic and preparation thereof.
Background
Cerium doped lutetium silicate (Lu)2SiO5Ce, LSO Ce) is a key detector material used in the radiation detection fields of high-energy physics, nuclear medicine imaging, oil well exploration and the like. Due to Ce3+And Lu3+Is different by 22%, so that Ce3+A gradient distribution is present in the LSO: Ce crystal ingot, so that the scintillation properties of the LSO: Ce crystal fluctuate. In addition, the melting point of LSO is higher than 2050 ℃, maintenance costs in the iridium crucible used in the single crystal growth process and the single crystal growth furnace are high. The LSO-Ce scintillating ceramic prepared by adopting the polycrystalline transparent ceramic process not only overcomes the problems, but also ensures that the high light yield of the LSO-Ce scintillating ceramic can reach the single crystal light yieldMore than 95 percent, the short decay time is equivalent to that of a single crystal, and the scintillation property is excellent. The crystal structure of LSO: Ce belongs to a monoclinic system, the maximum refractive index difference of the LSO: Ce is 0.028 and is about 4 times of that of alpha-alumina, so that light is subjected to birefringence when passing through a crystal boundary to form strong scattering, the emergent light intensity is obviously weakened, and the use of LSO: Ce ceramic on a positron emission computed tomography (PET) is limited.
And under a strong magnetic field, a green body with certain grain orientation degree is obtained by slip casting, and then the non-pressure sintering or pressure-assisted sintering is combined to prepare the high-density textured ceramic so as to obviously improve the optical transmittance of the optical anisotropic material. Commercial alpha-Al with average particle size of 400nm, such as Yi of Shanghai silicate research institute of Chinese academy of sciences2O3The powder is used as raw material, and the high-density alpha-Al with the c-axis orientation degree reaching 97 percent is obtained by slip casting under a strong magnetic field and vacuum sintering2O3Ceramics, such that 1mm thick α -Al2O3The in-line transmittance of the ceramic at 600nm was increased from 22.5% at 0T to 70.3% at 12T, achieving high transparency. Akiyama et al, Japan institute of molecular science, prepared Ca by slip casting under a strong magnetic field of 1.4T in combination with pressureless sintering and Hot Isostatic Pressing (HIP) post-treatment5(PO4)3F, Nd and Ca5(PO4)3The straight-line transmittance of the Yb laser ceramic at 1080nm reaches 83.8 percent. At present, no report related to the preparation of LSO: Ce polycrystalline ceramics by slip casting in a strong magnetic field and combining with a hot isostatic pressing post-treatment process is seen, and the preparation of LSO: Ce scintillation ceramics with low cost and high optical performance becomes a technical problem to be solved urgently because the preparation of LSO: Ce scintillation single crystals is high in cost, high in preparation difficulty and difficult to control.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide the textured cerium-doped lutetium silicate scintillating ceramic and the preparation method thereof. The LSO-Ce scintillating ceramic prepared by the invention has high density and low cost, the crystal grain orientation degree of the LSO-Ce scintillating ceramic can reach 28 percent, the linear transmittance at the luminescent wavelength (420nm) can reach 6.6 percent, and the LSO-Ce scintillating ceramic can be used as a detector material in an X-ray CT or gamma-ray PET scanning imager. The invention is beneficial to further improving the optical transmittance of the LSO-Ce scintillating ceramic and can effectively promote the practical process of the polycrystalline LSO-Ce scintillating ceramic.
In order to achieve the purpose, the invention adopts the following technical scheme:
a textured cerium-doped lutetium silicate scintillating ceramic is characterized in that: the chemical formula of the material is as follows: (Lu)1-xCex)2SiO5Ce, where x is 0.001-0.05, grain edge of textured cerium-doped lutetium silicate scintillating ceramic [ -402 []The crystal orientation axes are arranged.
As a preferred technical scheme of the invention, the grain size range of the textured cerium-doped lutetium silicate scintillation ceramic is 0.45-3.50 μm.
As a preferred technical scheme of the invention, the relative density of the material of the textured cerium-doped lutetium silicate scintillating ceramic is not lower than 99.8 percent by taking the density of the LSO-Ce scintillating single crystal material as the density of a reference substance.
The invention relates to a preparation method of textured cerium-doped lutetium silicate scintillating ceramic, which comprises the following steps:
preparing LSO and Ce slurry:
according to the chemical formula of (Lu)1-xCex)2SiO5Preparing LSO Ce powder from Ce target cerium-doped lutetium silicate scintillating ceramic components, preparing mixed slurry from the LSO Ce powder and deionized water according to the volume ratio of 1 (1-4), putting the mixed slurry into a ball milling tank containing zirconia or silica for ball milling, and then carrying out ball milling in a planetary ball mill for 5-40 hours to obtain uniformly dispersed LSO Ce slurry; in the preparation process of the LSO-Ce slurry, preferably, LSO-Ce powder and deionized water are prepared into mixed slurry according to the mass ratio of 74 (36-54);
b. grouting and forming process:
b, placing the porous mold in a strong magnetic field with the magnetic field intensity of 2-26T, introducing the LSO-Ce slurry prepared in the step a into the porous mold, enabling the LSO-Ce powder particles in the slurry to be distributed along a certain direction under the action of the magnetic field, absorbing water in the LSO-Ce slurry by the porous mold, and curing the directionally distributed LSO-Ce powder particles to form an LSO-Ce green body with a certain grain orientation degree after the LSO-Ce slurry is dewatered and cured; in the slip casting process, the porous mold is preferably a porous gypsum mold, so that the cost is low and the water removal effect is good; in the slip casting process, preferably adopting a strong magnetic field with the magnetic field intensity of 2-9T to perform the strong magnetic field slip casting process;
c. the ceramic pre-sintering process comprises the following steps:
and c, sintering the LSO: Ce green blank prepared in the step b after slip casting in a high-temperature sintering furnace, wherein the pre-sintering temperature system is controlled as follows:
firstly, heating, wherein the heating rate is controlled to be 5-10 ℃/min below 1200 ℃; when the temperature reaches 1200 ℃, the temperature is raised to the sintering temperature of 1550-; finally, cooling the ceramic sintered body with the temperature of 1200 ℃ at the cooling rate of 2-10 ℃/min, and then cooling the ceramic sintered body with the furnace to obtain the LSO-Ce ceramic sintered body with the relative density of the material not lower than 95%, wherein the relative density takes the density of the LSO-Ce scintillation single crystal material as the density of a reference substance; in the ceramic pre-sintering process, the sintering temperature is preferably controlled to be 1600-1700 ℃, and the sintering time is preferably 2-4 hours;
d. and (3) hot isostatic pressing sintering process:
and c, sintering the LSO-Ce ceramic sintered body prepared by pre-sintering in the step c again, wherein the sintering temperature system is controlled as follows:
firstly, heating, controlling the heating rate to be 5-20 ℃/min below 900 ℃, continuously heating to reach a sintering temperature of 1600-1700 ℃ at the heating rate of 2-10 ℃/min above 900 ℃, controlling the gas pressure of the sintering atmosphere in a high-temperature sintering furnace to be 100-190MPa, carrying out hot isostatic pressing sintering process treatment on the LSO: Ce ceramic sintered body for 1-20 hours under the conditions of the sintering temperature and the sintering atmosphere pressure, and then cooling along with the furnace to obtain the LSO: Ce ceramic reinforced sintered body; in the hot isostatic pressing sintering process, the sintering temperature is preferably controlled to be 1600-1700 ℃, the sintering atmosphere pressure is preferably controlled to be 150-180MPa, and the sintering time is preferably 2-20 hours;
e. the annealing treatment process comprises the following steps:
firstly, heating, controlling the heating rate to be 5-10 ℃/min, heating to the annealing temperature of 1100-1450 ℃, and annealing the LSO: Ce ceramic reinforced sintered body prepared in the step d for 2-20 hours under the annealing temperature condition and in the air or oxygen atmosphere to finally obtain the transparent LSO: Ce scintillating ceramic. In the annealing treatment process, the annealing temperature is preferably controlled to be 1300-1350 ℃, and the annealing treatment is preferably carried out for 4-10 hours.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the single-phase and high-density textured LSO-Ce scintillating ceramic can be obtained by hot isostatic pressing sintering, and the relative density of the ceramic can reach 99.8 percent;
2. the crystal grains of the ceramic are arranged along the [ -402] crystal orientation, and the crystal grain orientation degree of the ceramic can reach 28%;
3. the grain size range of the prepared fine-grain LSO is 0.45-3.50 mu m, the average grain size is 1.65 mu m, and the linear transmittance of the ceramic at the light-emitting wavelength of 420nm can reach 6.6 percent;
4. the textured cerium-doped lutetium silicate scintillating ceramic has a simple preparation process and is easy to control and implement.
Drawings
FIG. 1 is an XRD pattern of a textured LSO-Ce ceramic and a comparative sample with no applied magnetic field, prepared according to example one of the present inventions.
FIG. 2 is a graph comparing the distribution of the electron backscatter diffraction grain orientations of LSO: Ce ceramic prepared according to example one of the present invention and a comparative sample without applied magnetic field and the corresponding pole figures.
FIG. 3 is a graph comparing the linear transmittance curves of LSO to Ce ceramic prepared according to example one of the present invention and a comparative sample without applied magnetic field, all at 1mm thickness.
Detailed Description
The preferred embodiments of the invention are detailed below:
the first embodiment is as follows:
in this embodiment, a preparation method of a textured cerium-doped lutetium silicate scintillating ceramic includes the following steps:
preparing LSO and Ce slurry:
according to the chemical formula of (Lu)0.995Ce0.005)2SiO5Preparing LSO Ce powder by the target Ce doped lutetium silicate scintillation ceramic component of Ce, weighing 74 g of LSO Ce powder and 54 g of deionized water, mixing to prepare mixed slurry, putting the mixed slurry into a ball milling tank containing zirconia ball milling, and carrying out ball milling for 20 hours in a planetary ball mill at the rotating speed of 250 revolutions per minute to obtain uniformly dispersed LSO Ce slurry;
b. grouting and forming process:
b, placing the porous gypsum mould into a strong magnetic field with the magnetic field intensity of 9T, introducing 3ml of LSO and Ce slurry prepared in the step a into the porous gypsum mould, enabling the LSO and Ce powder particles in the slurry to be distributed along a certain direction under the action of the magnetic field, absorbing water in the LSO and Ce slurry by the porous mould, and after waiting for 1 hour and when the LSO and Ce slurry is dewatered and solidified, solidifying the directionally distributed LSO and Ce powder particles to form an LSO and Ce green compact with a certain grain orientation degree;
c. the ceramic pre-sintering process comprises the following steps:
and c, sintering the LSO: Ce green blank prepared in the step b after slip casting in a high-temperature muffle furnace, wherein the pre-sintering temperature system is controlled as follows:
firstly, heating, wherein the heating rate is controlled to be 5 ℃/min below 1200 ℃; when the temperature reaches 1200 ℃, the temperature is increased to 1600 ℃ at the heating rate of 2.5 ℃/min, and then the temperature is kept for 4 hours under the condition of sintering temperature; finally, cooling the ceramic sintered body with the temperature of 1200 ℃ at the cooling rate of 2 ℃/min, and then cooling the ceramic sintered body with the furnace to obtain the LSO to Ce ceramic sintered body with the relative density of the material not lower than 95%, wherein the relative density takes the density of the LSO to Ce scintillation single crystal material as the density of a reference substance;
d. and (3) hot isostatic pressing sintering process:
and c, sintering the LSO-Ce ceramic sintered body prepared by pre-sintering in the step c again, wherein the sintering temperature system is controlled as follows:
firstly, heating, controlling the heating rate to be 10 ℃/min below 900 ℃, continuously heating to reach the sintering temperature of 1600 ℃ at the heating rate of 5 ℃/min above 900 ℃, controlling the gas pressure of the sintering atmosphere in a high-temperature sintering furnace to be 150MPa, carrying out hot isostatic pressing sintering process on the LSO to Ce ceramic sintered body for 2 hours under the conditions of the sintering temperature and the sintering atmosphere pressure, and then cooling along with the furnace to obtain the LSO to Ce ceramic reinforced sintered body with the relative density of 99.8 percent, wherein the relative density takes the density of the LSO to Ce single crystal material as the density of a reference substance;
e. the annealing treatment process comprises the following steps:
firstly, heating, controlling the heating rate to be 5 ℃/min, heating to the annealing temperature of 1300 ℃, and annealing the LSO: Ce ceramic reinforced sintered body prepared by HIP treatment in the step d for 10 hours under the condition of the annealing temperature and in the air atmosphere to eliminate oxygen vacancies in the ceramic, thereby finally obtaining the transparent textured LSO: Ce scintillating ceramic. The chemical formula of the cerium-doped lutetium silicate scintillating ceramic prepared in the embodiment is (Lu)0.995Ce0.005)2SiO5Ce, textured cerium doped lutetium silicate (Lu)0.995Ce0.005)2SiO5The grain size range of the Ce scintillating ceramic is 0.45-3.50 μm, and the average grain size is 1.65 μm. In the embodiment, the cerium-doped lutetium silicate scintillating ceramic is prepared by slip casting and hot isostatic pressing post-treatment processes in a strong magnetic field, so that the optical transmittance of the optical anisotropic material can be obviously improved.
Comparative example:
in the comparative example, a preparation method of cerium-doped lutetium silicate scintillating ceramic comprises the following steps:
preparing LSO and Ce slurry:
according to the chemical formula of (Lu)0.995Ce0.005)2SiO5Preparing LSO and Ce powder by the target Ce doped lutetium silicate scintillation ceramic component of Ce, wherein x is 0.001-0.05, weighing 74 g of LSO and Ce powder and 54 g of deionized water, mixing to prepare mixed slurry, putting the mixed slurry into a ball milling tank containing zirconia or silica for ball milling, and then carrying out ball milling in a planetary ball mill at the rotating speed of 250 revolutions per minute for 20 hours to obtain uniformly dispersed LSO and Ce slurry;
b. grouting and forming process:
b, introducing the LSO: Ce slurry with the volume of 3ml prepared in the step a into a porous gypsum mould, so that water in the LSO: Ce slurry is absorbed by the porous mould, and after waiting for 1 hour, curing the LSO: Ce slurry after removing water to form LSO: Ce powder particles to form an LSO: Ce green compact;
c. the ceramic pre-sintering process comprises the following steps:
and c, sintering the LSO: Ce green blank prepared in the step b after slip casting in a high-temperature muffle furnace, wherein the pre-sintering temperature system is controlled as follows:
firstly, heating, wherein the heating rate is controlled to be 5 ℃/min below 1200 ℃; when the temperature reaches 1200 ℃, the temperature is increased to 1650 ℃ at the heating rate of 2.5 ℃/min, and then the temperature is preserved for 4 hours under the condition of sintering temperature; finally, cooling the ceramic sintered body with the temperature of 1200 ℃ at the cooling rate of 2 ℃/min, and then cooling the ceramic sintered body with the furnace to obtain the LSO to Ce ceramic sintered body with the relative density of the material not lower than 95%, wherein the relative density takes the density of the LSO to Ce scintillation single crystal material as the density of a reference substance;
d. and (3) hot isostatic pressing sintering process:
and c, sintering the LSO-Ce ceramic sintered body prepared by pre-sintering in the step c again, wherein the sintering temperature system is controlled as follows:
firstly, heating, controlling the heating rate to be 10 ℃/min below 900 ℃, continuously heating to reach the sintering temperature of 1650 ℃ at the heating rate of 5 ℃/min above 900 ℃, controlling the gas pressure of the sintering atmosphere in a high-temperature sintering furnace to be 150MPa, carrying out hot isostatic pressing sintering process on the LSO: Ce ceramic sintered body for 2 hours under the conditions of the sintering temperature and the sintering atmosphere pressure, and then cooling along with the furnace to obtain the LSO: Ce ceramic reinforced sintered body with the relative density of 99.9 percent, wherein the relative density takes the density of the LSO: Ce scintillation single crystal material as the density of a reference substance;
e. the annealing treatment process comprises the following steps:
firstly, heating, controlling the heating rate to be 5 ℃/min, heating to the annealing temperature of 1300 ℃, and annealing the LSO: Ce ceramic reinforced sintered body prepared by HIP treatment in the step d for 10 hours under the condition of the annealing temperature and in the air atmosphere to eliminate oxygen vacancies in the ceramic, thereby finally obtaining the LSO: Ce scintillating ceramic. The chemical formula of the cerium-doped lutetium silicate scintillating ceramic prepared by the comparative example is (Lu)0.995Ce0.005)2SiO5Ce is the same as in the first embodiment.
Experimental test analysis:
comparative experimental tests and comparative analyses were performed on the textured LSO: Ce scintillating ceramic prepared in example one and the LSO: Ce scintillating ceramic prepared in comparative example, and FIG. 1 is a comparative plot of the XRD patterns of the textured LSO: Ce ceramic prepared in example one and the LSO: Ce scintillating ceramic prepared in comparative example, where 9T represents the textured LSO: Ce scintillating ceramic prepared in example one and 0T represents the comparative sample LSO: Ce ceramic prepared in comparative example without an applied magnetic field. The XRD patterns of 0T and 9T LSO-Ce ceramics are completely matched with the positions and relative intensities of diffraction peaks of cards No. 41-0239 in the International Joint Committee for Powder Diffraction Standards (JCPDS), a single lutetium silicate phase is presented, but the relative intensity of the diffraction peak of the 9T textured ceramic at a crystal face (-402) is obviously enhanced, a strong texturing characteristic is presented, and the degree of grain orientation is 28%.
Fig. 2 is an electron back-scattered diffraction grain orientation profile and corresponding pole figure comparison of textured LSO: Ce ceramic prepared in example one and a comparative sample LSO: Ce ceramic prepared without application of a magnetic field. Wherein FIGS. 2(a) and 2(b) are electron back-scattered diffraction grain orientation profiles and corresponding pole figures for the LSO: Ce ceramics of the comparative samples; fig. 2(c) and 2(d) are electron backscatter diffraction grain orientation profiles and corresponding pole figures for textured LSO: Ce ceramics prepared in example one. The grain orientation distribution pattern of the untextured ceramic prepared by the comparative example exhibited various grayscales, and the distribution of the polar patterns of {101} and { -402} also exhibited a dispersion, indicating that the grains of the ceramic exhibited a random distribution characteristic. While the distribution profile of the textured ceramic (9T) prepared in example one tends to be gray scale, {101} pole figure exhibits a distribution near the center, and { -402} pole figure exhibits an annular distribution, which is characteristic of a distribution of grain orientation along the [ -402] crystal orientation.
The linear transmittance of the textured LSO-Ce ceramic prepared in the first example and the comparative sample LSO-Ce ceramic prepared in the comparative example without applying a magnetic field are shown in FIG. 3, the linear transmittance of two pieces of LSO-Ce ceramic with the thickness of 1mm is obtained after annealing and polishing, the linear transmittance of the untextured ceramic prepared in the comparative example at the 420nm luminescence peak position is only 1.4%, and the linear transmittance of the textured ceramic prepared in the first example reaches 6.6%. The chemical formulas of the cerium-doped lutetium silicate scintillating ceramics prepared in the first example and the comparative example are both (Lu)0.995Ce0.005)2SiO5Ce, the cerium-doped lutetium silicate scintillating ceramic prepared in example one is a textured LSO-Ce ceramic material, while the cerium-doped lutetium silicate scintillating ceramic prepared in comparative example is an untextured LSO-Ce ceramic material. Direct visual observation of the textured LSO-Ce ceramic prepared in the first example and the comparative sample LSO-Ce ceramic prepared in the comparative example without applying a magnetic field shows that the textured ceramic prepared in the first example has good transparency which is obviously better than that of the non-textured ceramic sample prepared in the comparative example. In the first embodiment, the textured cerium-doped lutetium silicate scintillating ceramic is prepared by slip casting and hot isostatic pressing post-treatment processes in a strong magnetic field, the grain orientation degree of the textured LSO-Ce scintillating ceramic can reach 28%, the linear transmittance at the light emitting wavelength of 420nm can reach 6.6%, and the textured LSO-Ce scintillating ceramic can be used as a detector material in an X-ray CT or gamma-ray PET scanning imager and can be applied to a detector of the PET scanning imager.
Example two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, a preparation method of a textured cerium-doped lutetium silicate scintillating ceramic includes the following steps:
preparing LSO and Ce slurry:
according to the chemical formula of (Lu)0.95Ce0.05)2SiO5Preparing LSO Ce powder by the target Ce doped lutetium silicate scintillation ceramic component of Ce, weighing 74 g of LSO Ce powder and 36 g of deionized water, mixing to prepare mixed slurry, putting the mixed slurry into a ball milling tank containing zirconia ball milling, and carrying out ball milling for 20 hours in a planetary ball mill at the rotating speed of 300 revolutions per minute to obtain uniformly dispersed LSO Ce slurry;
b. grouting and forming process:
b, placing the porous gypsum mould into a strong magnetic field with the magnetic field intensity of 2T, introducing 5ml of LSO and Ce slurry prepared in the step a into the porous gypsum mould, enabling the LSO and Ce powder particles in the slurry to be distributed along a certain direction under the action of the magnetic field, absorbing water in the LSO and Ce slurry by the porous mould, and after waiting for 2 hours, and after the LSO and Ce slurry is dewatered and solidified, solidifying the directionally distributed LSO and Ce powder particles to form an LSO and Ce green compact with a certain grain orientation degree;
c. the ceramic pre-sintering process comprises the following steps:
and c, sintering the LSO: Ce green blank prepared in the step b after slip casting in a high-temperature sintering furnace, wherein the pre-sintering temperature system is controlled as follows:
firstly, heating, wherein the heating rate is controlled to be 5 ℃/min below 1200 ℃; when the temperature reaches 1200 ℃, the temperature is increased to 1700 ℃ at the heating rate of 1.5 ℃/min, and then the temperature is kept for 2 hours under the condition of sintering temperature; finally, cooling the ceramic sintered body with the temperature of 1200 ℃ at the cooling rate of 2 ℃/min, and then cooling the ceramic sintered body with the furnace to obtain the LSO to Ce ceramic sintered body with the relative density of 95-97 percent, wherein the relative density takes the density of the LSO to Ce scintillation single crystal material as the density of a reference substance;
d. and (3) hot isostatic pressing sintering process:
and c, sintering the LSO-Ce ceramic sintered body prepared by pre-sintering in the step c again, wherein the sintering temperature system is controlled as follows:
firstly, heating, controlling the heating rate to be 15 ℃/min below 900 ℃, continuously heating to reach the sintering temperature of 1700 ℃ at the heating rate of 8 ℃/min above 900 ℃, controlling the gas pressure of the sintering atmosphere in a high-temperature sintering furnace to be 180MPa, carrying out hot isostatic pressing sintering process on the LSO to Ce ceramic sintered body for 2 hours under the conditions of the sintering temperature and the sintering atmosphere pressure, and then cooling along with the furnace to obtain the LSO to Ce ceramic reinforced sintered body with the relative density of 99.8 percent, wherein the relative density takes the density of the LSO to Ce single crystal material as the density of a reference substance;
e. the annealing treatment process comprises the following steps:
firstly, heating, controlling the heating rate to be 5 ℃/min, heating to the annealing temperature of 1350 ℃, and annealing the LSO: Ce ceramic reinforced sintered body prepared by HIP treatment in the step d for 4 hours under the condition of the annealing temperature and in the air atmosphere to eliminate oxygen vacancies in the ceramic, thereby finally obtaining the transparent textured LSO: Ce scintillating ceramic. The chemical formula of the cerium-doped lutetium silicate scintillating ceramic prepared in the embodiment is (Lu)0.95Ce0.05)2SiO5:Ce。
The textured ceramic prepared in this example exhibited good transparency, which was significantly better than the untextured ceramic sample prepared in the comparative example. In the embodiment, the textured cerium-doped lutetium silicate scintillating ceramic is prepared by slip casting and hot isostatic pressing post-treatment process HIP in a strong magnetic field, the grain orientation degree of the textured LSO, Ce scintillating ceramic reaches 26%, the linear transmittance at the light emitting wavelength of 420nm reaches 6.3%, and the textured LSO can be used as a detector material in an X-ray CT or gamma-ray PET scanning imager and can be applied to a detector of the PET scanning imager.
Example three:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of a textured cerium-doped lutetium silicate scintillating ceramic includes the following steps:
preparing LSO and Ce slurry:
according to the chemical formula of (Lu)0.999Ce0.001)2SiO5Ce target cerium doped lutetium silicate scintillationsPreparing LSO Ce powder according to a ceramic component ratio, weighing LSO Ce powder and deionized water according to a volume ratio of 1:1, mixing the LSO Ce powder and water to prepare mixed slurry, putting the mixed slurry into a ball milling tank containing zirconia ball milling, and carrying out ball milling for 5 hours in a planetary ball mill at a rotating speed of 300 revolutions per minute to obtain uniformly dispersed LSO Ce slurry;
b. grouting and forming process:
b, placing the porous gypsum mould into a strong magnetic field with the magnetic field intensity of 26T, introducing 5ml of LSO-Ce slurry prepared in the step a into the porous gypsum mould, enabling the LSO-Ce powder particles in the slurry to be distributed along a certain direction under the action of the magnetic field, absorbing water in the LSO-Ce slurry by the porous mould, and after waiting for 2 hours, and after the LSO-Ce slurry is dewatered and solidified, solidifying the directionally distributed LSO-Ce powder particles to form an LSO-Ce green body with a certain grain orientation degree;
c. the ceramic pre-sintering process comprises the following steps:
and c, sintering the LSO: Ce green blank prepared in the step b after slip casting in a high-temperature sintering furnace, wherein the pre-sintering temperature system is controlled as follows:
firstly, heating, wherein the heating rate is controlled to be 10 ℃/min below 1200 ℃; when the temperature reaches 1200 ℃, the temperature is increased to 1550 ℃ at the heating rate of 1 ℃/minute, and then the temperature is kept for 20 hours under the condition of sintering temperature; finally, cooling the ceramic sintered body with the temperature of 1200 ℃ at the cooling rate of 10 ℃/min, and then cooling the ceramic sintered body with the furnace to obtain the LSO to Ce ceramic sintered body with the relative density of 95-97 percent, wherein the relative density takes the density of the LSO to Ce scintillation single crystal material as the density of a reference substance;
d. and (3) hot isostatic pressing sintering process:
and c, sintering the LSO-Ce ceramic sintered body prepared by pre-sintering in the step c again, wherein the sintering temperature system is controlled as follows:
firstly, heating, controlling the heating rate to be 5 ℃/min below 900 ℃, continuously heating to reach the sintering temperature of 1600 ℃ at the heating rate of 2 ℃/min above 900 ℃, controlling the gas pressure of the sintering atmosphere in a high-temperature sintering furnace to be 190MPa, carrying out hot isostatic pressing sintering process on the LSO to Ce ceramic sintered body for 20 hours under the conditions of the sintering temperature and the sintering atmosphere pressure, and then cooling along with the furnace to obtain the LSO to Ce ceramic reinforced sintered body with the relative density of 99.8 percent, wherein the relative density takes the density of the LSO to Ce single crystal material as the density of a reference substance;
e. the annealing treatment process comprises the following steps:
firstly, heating, controlling the heating rate to be 10 ℃/min, heating to the annealing temperature of 1450 ℃, and annealing the LSO: Ce ceramic reinforced sintered body prepared by HIP treatment in the step d for 2 hours under the annealing temperature condition and in the oxygen atmosphere to eliminate oxygen vacancies in the ceramic, thereby finally obtaining the transparent textured LSO: Ce scintillating ceramic. The chemical formula of the cerium-doped lutetium silicate scintillating ceramic prepared in the embodiment is (Lu)0.999Ce0.001)2SiO5:Ce。
The textured ceramic prepared in this example exhibited good transparency, which was significantly better than the untextured ceramic sample prepared in the comparative example. In the embodiment, the textured cerium-doped lutetium silicate scintillating ceramic is prepared by slip casting and hot isostatic pressing post-treatment process HIP in a strong magnetic field, the grain orientation degree of the textured LSO, Ce scintillating ceramic reaches 29%, the linear transmittance at the light emitting wavelength of 420nm can reach 6.8%, and the textured LSO can be used as a detector material in an X-ray CT or gamma-ray PET scanning imager and can be applied to a detector of the PET scanning imager.
Example four:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of a textured cerium-doped lutetium silicate scintillating ceramic includes the following steps:
preparing LSO and Ce slurry:
according to the chemical formula of (Lu)0.999Ce0.001)2SiO5Preparing LSO to Ce powder by mixing target Ce doped lutetium silicate scintillation ceramic component of Ce, measuring LSO to Ce powder and deionized water according to the volume ratio of 1:4, and then adding the LSO to Ce powder and deionized waterMixing LSO Ce powder and water to prepare mixed slurry, then putting the mixed slurry into a ball milling tank containing zirconia for ball milling, and then carrying out ball milling for 40 hours in a planetary ball mill at the rotating speed of 300 revolutions per minute to obtain uniformly dispersed LSO Ce slurry;
b. grouting and forming process:
b, placing the porous gypsum mould into a strong magnetic field with the magnetic field intensity of 26T, introducing 5ml of LSO-Ce slurry prepared in the step a into the porous gypsum mould, enabling the LSO-Ce powder particles in the slurry to be distributed along a certain direction under the action of the magnetic field, absorbing water in the LSO-Ce slurry by the porous mould, and after waiting for 2 hours, and after the LSO-Ce slurry is dewatered and solidified, solidifying the directionally distributed LSO-Ce powder particles to form an LSO-Ce green body with a certain grain orientation degree;
c. the ceramic pre-sintering process comprises the following steps:
and c, sintering the LSO: Ce green blank prepared in the step b after slip casting in a high-temperature sintering furnace, wherein the pre-sintering temperature system is controlled as follows:
firstly, heating, wherein the heating rate is controlled to be 10 ℃/min below 1200 ℃; when the temperature reaches 1200 ℃, the temperature is increased to 1750 ℃ at the heating rate of 1 ℃/min, and then the temperature is kept for 2 hours under the condition of the sintering temperature; finally, cooling the ceramic sintered body with the temperature of 1200 ℃ at the cooling rate of 10 ℃/min, and then cooling the ceramic sintered body with the furnace to obtain the LSO to Ce ceramic sintered body with the relative density of 98 percent, wherein the relative density takes the density of the LSO to Ce scintillation single crystal material as the density of a reference substance;
d. and (3) hot isostatic pressing sintering process:
and c, sintering the LSO-Ce ceramic sintered body prepared by pre-sintering in the step c again, wherein the sintering temperature system is controlled as follows:
firstly, heating, controlling the heating rate to be 20 ℃/min below 900 ℃, continuously heating to reach the sintering temperature of 1700 ℃ at the heating rate of 10 ℃/min above 900 ℃, controlling the gas pressure of the sintering atmosphere in a high-temperature sintering furnace to be 100MPa, carrying out hot isostatic pressing sintering process on the LSO to Ce ceramic sintered body for 1 hour under the conditions of the sintering temperature and the sintering atmosphere pressure, and then cooling along with the furnace to obtain the LSO to Ce ceramic reinforced sintered body with the relative density of 99.8 percent, wherein the relative density takes the density of the LSO to Ce single crystal material as the density of a reference substance;
e. the annealing treatment process comprises the following steps:
firstly, heating, controlling the heating rate to be 10 ℃/min, heating to the annealing temperature of 1100 ℃, and annealing the LSO: Ce ceramic reinforced sintered body prepared after the HIP treatment in the step d for 20 hours under the annealing temperature condition and in the oxygen atmosphere to eliminate oxygen vacancies in the ceramic, thereby finally obtaining the transparent textured LSO: Ce scintillating ceramic. The chemical formula of the cerium-doped lutetium silicate scintillating ceramic prepared in the embodiment is (Lu)0.999Ce0.001)2SiO5:Ce。
The textured ceramic prepared in this example exhibited good transparency, which was significantly better than the untextured ceramic sample prepared in the comparative example. In the embodiment, the textured cerium-doped lutetium silicate scintillating ceramic is prepared by slip casting and hot isostatic pressing post-treatment process HIP in a strong magnetic field, the grain orientation degree of the textured LSO, Ce scintillating ceramic reaches 33%, the linear transmittance at the light emitting wavelength of 420nm reaches 6.9%, and the textured LSO can be used as a detector material in an X-ray CT or gamma-ray PET scanning imager and can be applied to a detector of the PET scanning imager.
While the embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the present invention should be replaced by equivalents thereof, so long as the objects of the present invention are met, and the present invention is within the protection scope of the present invention without departing from the technical principles and inventive concept of the textured cerium doped lutetium silicate scintillating ceramic and the preparation method thereof.

Claims (10)

1. A textured cerium-doped lutetium silicate scintillating ceramic is characterized in that: the chemical formula of the material is as follows: (Lu)1-xCex)2SiO5Ce, whichWherein x is 0.001-0.05, the grain edge of textured cerium doped lutetium silicate scintillation ceramic is [ -402 []Arranging crystal orientation shafts;
the textured cerium-doped lutetium silicate scintillating ceramic is prepared by the following preparation method steps:
preparing LSO and Ce slurry:
according to the chemical formula of (Lu)1-xCex)2SiO5Preparing LSO Ce powder from Ce target cerium-doped lutetium silicate scintillating ceramic components, preparing mixed slurry from the LSO Ce powder and deionized water according to the volume ratio of 1 (1-4), putting the mixed slurry into a ball milling tank containing zirconia or silica for ball milling, and then carrying out ball milling in a planetary ball mill for 5-40 hours to obtain uniformly dispersed LSO Ce slurry;
b. grouting and forming process:
b, placing the porous mold in a strong magnetic field with the magnetic field intensity of 2-26T, introducing the LSO-Ce slurry prepared in the step a into the porous mold, enabling the LSO-Ce powder particles in the slurry to be distributed along a certain direction under the action of the magnetic field, absorbing water in the LSO-Ce slurry by the porous mold, and curing the directionally distributed LSO-Ce powder particles to form an LSO-Ce green body with a certain grain orientation degree after the LSO-Ce slurry is dewatered and cured;
c. the ceramic pre-sintering process comprises the following steps:
and c, sintering the LSO: Ce green blank prepared in the step b after slip casting in a high-temperature sintering furnace, wherein the pre-sintering temperature system is controlled as follows:
firstly, heating, wherein the heating rate is controlled to be 5-10 ℃/min below 1200 ℃; when the temperature reaches 1200 ℃, the temperature is raised to the sintering temperature of 1550-; finally, cooling the ceramic sintered body with the temperature of 1200 ℃ at the cooling rate of 2-10 ℃/min, and then cooling the ceramic sintered body with the furnace to obtain the LSO-Ce ceramic sintered body with the relative density of the material not lower than 95%, wherein the relative density takes the density of the LSO-Ce scintillation single crystal material as the density of a reference substance;
d. and (3) hot isostatic pressing sintering process:
and c, sintering the LSO-Ce ceramic sintered body prepared by pre-sintering in the step c again, wherein the sintering temperature system is controlled as follows:
firstly, heating, controlling the heating rate to be 5-20 ℃/min below 900 ℃, continuously heating to reach a sintering temperature of 1600-1700 ℃ at the heating rate of 2-10 ℃/min above 900 ℃, controlling the gas pressure of the sintering atmosphere in a high-temperature sintering furnace to be 100-190MPa, carrying out hot isostatic pressing sintering process treatment on the LSO: Ce ceramic sintered body for 1-20 hours under the conditions of the sintering temperature and the sintering atmosphere pressure, and then cooling along with the furnace to obtain the LSO: Ce ceramic reinforced sintered body;
e. the annealing treatment process comprises the following steps:
firstly, heating, controlling the heating rate to be 5-10 ℃/min, heating to the annealing temperature of 1100-1450 ℃, and annealing the LSO: Ce ceramic reinforced sintered body prepared in the step d for 2-20 hours under the annealing temperature condition and in the air or oxygen atmosphere to finally obtain the transparent LSO: Ce scintillating ceramic.
2. The textured cerium-doped lutetium silicate scintillating ceramic of claim 1, wherein: the grain size of the textured cerium-doped lutetium silicate scintillating ceramic is in the range of 0.45-3.50 μm.
3. The textured cerium-doped lutetium silicate scintillating ceramic of claim 1 or 2, wherein: and the relative density of the textured cerium-doped lutetium silicate scintillation ceramic is not lower than 99.8 percent by taking the density of the LSO-Ce scintillation single crystal material as the density of a reference substance.
4. The preparation method of the textured cerium-doped lutetium silicate scintillating ceramic of claim 1, which is characterized by comprising the following steps:
preparing LSO and Ce slurry:
according to the chemical formula of (Lu)1-xCex)2SiO5Preparing LSO-Ce powder from Ce target cerium doped lutetium silicate scintillating ceramic component, preparing mixed slurry from the LSO-Ce powder and deionized water according to the volume ratio of 1 (1-4), and then putting the mixed slurry into a container containing oxygenIn a ball milling tank for zirconium or silicon oxide ball milling, then carrying out ball milling for 5-40 hours in a planetary ball mill to obtain uniformly dispersed LSO and Ce slurry;
b. grouting and forming process:
b, placing the porous mold in a strong magnetic field with the magnetic field intensity of 2-26T, introducing the LSO-Ce slurry prepared in the step a into the porous mold, enabling the LSO-Ce powder particles in the slurry to be distributed along a certain direction under the action of the magnetic field, absorbing water in the LSO-Ce slurry by the porous mold, and curing the directionally distributed LSO-Ce powder particles to form an LSO-Ce green body with a certain grain orientation degree after the LSO-Ce slurry is dewatered and cured;
c. the ceramic pre-sintering process comprises the following steps:
and c, sintering the LSO: Ce green blank prepared in the step b after slip casting in a high-temperature sintering furnace, wherein the pre-sintering temperature system is controlled as follows:
firstly, heating, wherein the heating rate is controlled to be 5-10 ℃/min below 1200 ℃; when the temperature reaches 1200 ℃, the temperature is raised to the sintering temperature of 1550-; finally, cooling the ceramic sintered body with the temperature of 1200 ℃ at the cooling rate of 2-10 ℃/min, and then cooling the ceramic sintered body with the furnace to obtain the LSO-Ce ceramic sintered body with the relative density of the material not lower than 95%, wherein the relative density takes the density of the LSO-Ce scintillation single crystal material as the density of a reference substance;
d. and (3) hot isostatic pressing sintering process:
and c, sintering the LSO-Ce ceramic sintered body prepared by pre-sintering in the step c again, wherein the sintering temperature system is controlled as follows:
firstly, heating, controlling the heating rate to be 5-20 ℃/min below 900 ℃, continuously heating to reach a sintering temperature of 1600-1700 ℃ at the heating rate of 2-10 ℃/min above 900 ℃, controlling the gas pressure of the sintering atmosphere in a high-temperature sintering furnace to be 100-190MPa, carrying out hot isostatic pressing sintering process treatment on the LSO: Ce ceramic sintered body for 1-20 hours under the conditions of the sintering temperature and the sintering atmosphere pressure, and then cooling along with the furnace to obtain the LSO: Ce ceramic reinforced sintered body;
e. the annealing treatment process comprises the following steps:
firstly, heating, controlling the heating rate to be 5-10 ℃/min, heating to the annealing temperature of 1100-1450 ℃, and annealing the LSO: Ce ceramic reinforced sintered body prepared in the step d for 2-20 hours under the annealing temperature condition and in the air or oxygen atmosphere to finally obtain the transparent LSO: Ce scintillating ceramic.
5. The method for preparing the textured cerium-doped lutetium silicate scintillating ceramic of claim 4, which is characterized in that: and b, in the step a, preparing the LSO-Ce slurry by using LSO-Ce powder and deionized water according to the mass ratio of 74 (36-54) to prepare mixed slurry.
6. The method for preparing the textured cerium-doped lutetium silicate scintillating ceramic of claim 4, which is characterized in that: in the step b, adopting a porous gypsum mould as the porous mould in the grouting forming process.
7. The method for preparing the textured cerium-doped lutetium silicate scintillating ceramic of claim 4, which is characterized in that: and c, in the step b, performing high-intensity magnetic field grouting forming by adopting a high-intensity magnetic field with the magnetic field intensity of 2-9T.
8. The method for preparing the textured cerium-doped lutetium silicate scintillating ceramic of claim 4, which is characterized in that: in the ceramic pre-sintering process in the step c, the sintering temperature is controlled to be 1600-1700 ℃, and the sintering time is controlled to be 2-4 hours.
9. The method for preparing the textured cerium-doped lutetium silicate scintillating ceramic of claim 4, which is characterized in that: in the step d hot isostatic pressing sintering process, the sintering temperature is controlled to be 1600-.
10. The method for preparing the textured cerium-doped lutetium silicate scintillating ceramic of claim 4, which is characterized in that: in the annealing treatment process in the step e, the annealing temperature is controlled to be 1300-1350 ℃, and the annealing treatment is carried out for 4-10 hours.
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