CN117418315A - Lutetium silicate monocrystal with crystal face orientation and preparation method thereof - Google Patents
Lutetium silicate monocrystal with crystal face orientation and preparation method thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 71
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052765 Lutetium Inorganic materials 0.000 title claims abstract description 34
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 77
- 239000000919 ceramic Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000003825 pressing Methods 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 8
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 7
- 238000003980 solgel method Methods 0.000 claims abstract description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 34
- 238000000498 ball milling Methods 0.000 claims description 30
- ANDNPYOOQLLLIU-UHFFFAOYSA-N [Y].[Lu] Chemical compound [Y].[Lu] ANDNPYOOQLLLIU-UHFFFAOYSA-N 0.000 claims description 24
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000011362 coarse particle Substances 0.000 claims description 2
- 239000002612 dispersion medium Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 7
- 238000005204 segregation Methods 0.000 abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract 2
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 6
- 239000003755 preservative agent Substances 0.000 description 6
- 230000002335 preservative effect Effects 0.000 description 6
- 238000003892 spreading Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002109 crystal growth method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910003443 lutetium oxide Inorganic materials 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 description 3
- 238000002600 positron emission tomography Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005090 crystal field Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005658 nuclear physics Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 238000003325 tomography Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/34—Silicates
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/12—Single-crystal growth directly from the solid state by pressure treatment during the growth
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a lutetium silicate monocrystal with crystal face orientation and a preparation method thereof, wherein a cerium doped lutetium silicate precursor is prepared by a sol-gel method, cerium doped lutetium silicate can be simply called LSO: ce, LSO: ce ceramic powder is obtained by calcining at 1000 ℃ for 2 hours, the synthesized LSO: ce powder and the lutetium silicate monocrystal with crystal face orientation are formed into a green body by dry pressing and cold isostatic pressing, and then are sintered at high temperature and high pressure in an argon atmosphere, in the sintering process, crystal grains continuously grow along seed crystals by solid phase diffusion, single crystallization occurs under the solid state condition, and finally the oriented LSO: ce monocrystal is obtained. The directional LSO Ce monocrystal prepared by the method has the characteristics of compact structure, controllable growth crystal size, thick growth monocrystal layer and no element segregation, can be innovatively grown on two sides, and has the advantages of being capable of changing Lu into other rare earth elements or doping rare earth with different proportions.
Description
Technical Field
The application belongs to the technical field of single crystal growth, and particularly relates to a lutetium silicate single crystal with crystal plane orientation and a preparation method thereof.
Background
Scintillation crystals are increasingly used in nuclear detection technology, mainly in X-ray tomography (XCT), positron Emission Tomography (PET), industrial tomographyIndustrial CT), oil well exploration, covert explosives detection, nuclear physics, and high energy physics. Cerium doped lutetium silicate (LSO: ce) crystal is a scintillation crystal with excellent performance, and is particularly suitable for PET devices. The LSO-Ce scintillator has excellent comprehensive performance (high density, high effective atomic number, fast attenuation and high light yield), and the prepared gamma-ray detector has very wide potential application, and many scientific research institutions and companies strengthen the research on LSO-Ce. Currently, although commercial PET has appeared in the marketplace, LSO: ce crystals have not been dominant in the scintillation crystal field due to both technical and marketing considerations. Since the melting point of LSO is as high as 2000-2100 ℃, the temperature is close to the limit use temperature of the iridium crucible and the heat insulation material, and the growth of crystals is very difficult; meanwhile, the crystal is cracked due to the difference of the thermal expansion coefficients of the seed crystal and the iridium rod during the growth of the crystal; in addition, LSO crystals are usually grown by adopting a Czochralski method, and the segregation coefficient is 0.22 due to the difference of atomic radii of Ce and Lu, so that the solid Ce is not uniformly distributed in the crystal, and the initial growth content is smaller than that of the late growth. The sol-gel method is adopted for the calibration of a shakeout machine of university of california in the United states to prepare the crystal phase Lu 2 SiO 5 The scintillation performance of the polycrystalline powder is close to that of single crystals grown by a Czochralski method. The method has relatively low processing temperatures, controllable stoichiometry, and atomic scale uniformity. In recent years, more and more researchers have prepared single crystals by a solid-state crystal growth method in which single crystals are grown without melting, so that a phenomenon of segregation of doping ions does not occur, which is advantageous in comparison with single crystals prepared by conventional melt growth and solution growth methods; and simultaneously, the SSCG growth rate is higher than that of the CZ method.
Disclosure of Invention
The invention aims at solving the problems, and provides a crystal with crystal face orientation lutetium silicate and a preparation method thereof, wherein the lutetium silicate powder with fine crystal grains is prepared by a sol-gel method, sintered in an argon atmosphere by hot pressing, and the lutetium silicate single crystal with crystal face orientation is prepared by a solid crystal growth method.
In order to solve the technical problems and achieve the purposes of the invention, the invention provides a preparation method of lutetium silicate single crystal with crystal face orientation, which comprises the following steps:
(1) Preparing cerium doped lutetium silicate precursor by sol-gel method, calcining at 1000deg.C for 2 hr to obtain coarse particle (Lu) 0.995 Ce 0.005 ) 2 SiO 5 Ceramic powder, abbreviated as LSO: ce;
(2) The prepared (Lu 0.995 Ce 0.005 ) 2 SiO 5 Ball milling and crushing the ceramic powder for 24 hours by taking alcohol as a dispersion medium to obtain depolymerized fine-grain LSO (LSO: ce ceramic powder);
(3) Placing a lutetium yttrium silicate monocrystal with grain orientation into fine-grain LSO/Ce ceramic powder, preparing a green body of the lutetium yttrium silicate monocrystal wrapped by the fine-grain LSO/Ce ceramic powder through dry pressing, wherein the molding pressure is 8-10 MPa, and carrying out 180MPa cold isostatic pressing to further densify the green body of the wrapped monocrystal;
(4) And (3) placing the green body obtained in the step (3) into a graphite crucible, and sintering the green body in an argon atmosphere at 1650-1780 ℃ and under a pressure of 30-80 Mpa to obtain the LSO/Ce monocrystal which grows directionally along the oriented crystal face of the lutetium yttrium silicate monocrystal.
Further, in the step (1), the lutetium silicate precursor powder is calcined at 1000 ℃ for 2 hours to obtain X1 type LSO: ce ceramic powder.
Further, in the step (1), the sol-gel method is as follows: lu with purity of more than 99.99% 2 O 3 Adding hydrochloric acid into the powder for dissolution, wherein the mol ratio of Cl to Lu is 6:1, and adding CeCl with Ce content of 0.5 at% 3 The solution was stirred continuously and the Lucl was obtained by rotary evaporation 3 ·6H 2 O, adding isopropanol, propylene oxide and tetraethyl orthosilicate, wherein the amount of the tetraethyl orthosilicate is half of that of Lu and Ce, mechanically stirring for 48 hours, and drying in a blowing drying oven at 80 ℃ for 24 hours to obtain a precursor.
In the step (2), the mass ratio of the LSO to the Ce ceramic powder to the zirconia ball mill is 1:6, the alcohol content is consistent with the powder content, the rotating speed of the planetary ball mill is 250rpm, and the median particle diameter of the fine grain powder after 24h ball milling is 142nm.
Further, the dry press molding method in the step (3) comprises the following steps: adding a certain amount of LSO-Ce ceramic powder into a stainless steel mold for prepressing, wherein the prepressing pressure is 2MPa, placing the yttrium lutetium silicate monocrystal in the mold and directly above the LSO-Ce green compact, adding a certain amount of LSO-Ce ceramic powder to cover the yttrium lutetium silicate monocrystal, and then pressing and forming under the pressure of 8-10 MPa.
Further, in the step (3), the density of the green body is 50-55%.
Further, the sintering process in the step (4) is to raise the temperature from room temperature 5 ℃/min to 1000 ℃, and apply 20-100 MPa pressure at 800 ℃, raise the temperature to 1650-1780 ℃ at 10 ℃/min, keep the temperature for 6 hours, and then lower the temperature to 1000 ℃ at 5 ℃/min, and then cool the mixture naturally by water cooling.
In addition, the invention also provides a lutetium silicate single crystal with crystal face orientation, which is prepared by adopting any one of the preparation methods.
The beneficial effects are that: compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
(1) The application adopts the sol-gel method to prepare the lutetium silicate powder, and can accurately control the stoichiometric ratio of lutetium and cerium.
(2) The application adopts 1000 ℃ calcination for 2 hours, and can obtain fine-grained LSO-Ce ceramic powder.
(3) The green compact with high density is prepared by combining dry press forming and cold isostatic pressing.
(4) The monocrystalline structure manufactured by the solid crystal growth method is compact, the size of the grown crystal is controllable, the thickness of the grown monocrystalline layer is thick, and no element segregation exists.
Drawings
FIG. 1 shows the result of calcining the precursor powder at 1000℃for 2 hours (Lu) 0.995 Ce 0.005 ) 2 SiO 5 Powder XRD pattern.
FIG. 2 is a graph showing the particle size distribution of the powder after ball milling for 24 hours.
FIG. 3 is an XRD pattern for a single crystal of lutetium silicate having a crystal plane orientation in accordance with the first embodiment of the present invention.
FIG. 4 is an XRD pattern for a single crystal of lutetium silicate having a crystal plane orientation in example two of the present invention.
FIG. 5 is an XRD pattern for a single crystal of lutetium silicate having a crystal plane orientation in example III of the present invention.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present application, the following will further describe with reference to specific examples.
In the technical scheme of the application, the lutetium silicate single crystal with crystal face orientation can be prepared by following steps:
(1) Lu with purity of more than 99.99% 2 O 3 Adding hydrochloric acid into the powder for dissolution, wherein the mol ratio of Cl to Lu is 6:1, and adding CeCl with Ce content of 0.5 at% 3 The solution was stirred continuously and the LuCl was obtained by rotary evaporation 3 ·6H 2 O, isopropanol, propylene oxide and tetraethyl orthosilicate are added, wherein the amount of tetraethyl orthosilicate substance is half of the amount of Lu and Ce substances. After mechanical stirring for 48 hours, the mixture is dried in a blowing drying oven at 80 ℃ for 24 hours to obtain a precursor.
(2) Calcining at 1000 ℃ for 2 hours to obtain coarse-grained X1 type LSO/Ce ceramic powder, wherein the mass ratio of the prepared coarse-grained powder to the material balls of the zirconia ball mill is 1:6, the alcohol content is consistent with the powder content, the rotating speed of the planetary ball mill is 250rpm, and the median particle diameter of the fine-grained powder after ball milling for 24 hours is 142nm.
(3) Placing a lutetium yttrium silicate monocrystal with grain orientation into fine-grain LSO/Ce ceramic powder, preparing a green body of the lutetium yttrium silicate monocrystal wrapped by the fine-grain LSO/Ce ceramic powder through dry pressing and forming, wherein the forming pressure is 8-10 MPa, and then performing 180MPa cold isostatic pressing to further densify the green body of the wrapped monocrystal, wherein the density of the green body is 50-55%.
(4) Placing the green body in a graphite mold, heating to 1000 ℃ from 5 ℃/min at room temperature in argon atmosphere or vacuum, applying 20-100 MPa pressure at 800 ℃, heating to 1650-1780 ℃ at 10 ℃/min, preserving heat for 6h, cooling with water after cooling to 1000 ℃ at 5 ℃/min, and naturally cooling to obtain the LSO/Ce monocrystal growing along the oriented crystal face of the lutetium yttrium silicate monocrystal.
Next, a preparation process for a single crystal having crystal plane orientation lutetium silicate will be described in specific examples.
Example 1
(a) Weighing 138.422g lutetium oxide powder in beaker, adding 422.2g hydrochloric acid, magnetically stirring at 80deg.C to dissolve completely, adding 9.98ml CeCl 0.35mol/L 3 Transferring the whole solution into a round bottom flask, and performing rotary evaporation at 55-85 ℃ and vacuum degree lower than 0.02MPa to obtain LuCl 3 ·6H 2 O, and CeCl 3 ·7H 2 O, taking down the round-bottom flask, immediately sealing the round-bottom flask by using a preservative film to prevent water absorption, and weighing the sealed round-bottom flask and LuCl 3 ·6H 2 O, and CeCl 3 ·7H 2 The total mass of O crystals can be obtained as LuCl in the flask 3 ·6H 2 O, and CeCl 3 ·7H 2 O mass according to the previously added Lu 3+ Calculated theoretical LuCl 3 ·6H 2 O, and CeCl 3 ·7H 2 And judging the evaporation effect by the mass of O.
(b) After weighing, taking down the preservative film, immediately adding isopropanol into the round-bottomed flask, shaking, and adding LuCl 3 ·6H 2 O、CeCl 3 ·7H 2 The mixture of O and isopropanol was transferred to a beaker and the flask was repeatedly washed with isopropanol, the wash was also transferred to a beaker, isopropanol was added continuously to a volume of 2058ml, and dispersion was continued for half an hour by mechanical stirring. To be LuCl 3 ·6H 2 O, and CeCl 3 ·7H 2 After O is uniformly dispersed in isopropanol, 73.34g of TEOS is added into a large beaker, the beaker for weighing the TEOS is washed by propylene oxide, propylene oxide is continuously added to ensure that the volume of the beaker reaches 1029ml, and mechanical stirring is continuously carried out for 48 hours until full reaction is carried out, so that a precursor is obtained. Calcining the precursor at 1000 ℃ for 2 hours to obtain X1 type LSO: ce powder, wherein the powder XRD is shown in figure 1.
(c) Adding calcined X1 type LSO/Ce ceramic powder into a zirconia ball milling tank according to the mass ratio of the LSO/Ce powder to the zirconia ball mill balls of 1:6, adding a proper amount of absolute ethyl alcohol according to the solid content of the powder of 30vol.% as a ball milling medium, performing planetary ball milling for 24 hours at the rotating speed of 250rpm, and after the ball milling is finished, placing the ball milling tank into a blast drying box and drying for 24 hours at the temperature of 80 ℃.
(d) The particle size of the powder after ball milling was 142nm as measured by a nano particle size analyzer, and the particle size distribution after ball milling of the powder is shown in fig. 2.
(e) Adding 4.5g of LSO (yttrium aluminum oxide) Ce powder after ball milling and drying into a stainless steel die with the diameter of 20mm, pre-pressing the powder at the pre-pressing pressure of 2MPa for 10s, then placing the yttrium lutetium silicate monocrystal directly above the LSO Ce green compact in the die, adding 5.5g of LSO (yttrium aluminum oxide) Ce powder to cover the yttrium lutetium silicate monocrystal, then pressing and forming the yttrium lutetium silicate monocrystal under the pressure of 10MPa, and then performing 180MPa cold isostatic pressing to further densify the green compact coated with the monocrystal, wherein the density of the green compact is 55%, and the diameter is 18.8mm.
(f) Spraying a layer of BN into the inner cavity of a graphite mold with the diameter of 20mm, facilitating demolding, spreading 1g of LSO/Ce powder in the cavity, placing the pressed green body in the center of the mold, and spreading and adding 2g of LSO/Ce powder. Sintering the graphite mould in a vacuum hot-pressing furnace, heating to 1000 ℃ from 5 ℃/min at room temperature in argon atmosphere, applying 40MPa pressure at 800 ℃, heating to 1700 ℃ at 10 ℃/min, preserving heat for 6 hours, cooling to 1000 ℃ at 5 ℃/min, and naturally cooling by water cooling to obtain LSO/Ce single crystal which grows directionally along the crystal orientation crystal face of lutetium yttrium silicate single crystal, wherein the thickness of a growth layer is 1.8mm. As shown in figure 3, XRD of the single crystal with the lutetium silicate in the crystal face orientation after sintering, the texture factor of (-112) crystal face orientation is up to 92.6% through XRD data calculation.
Example two
(a) Weighing 138.422g lutetium oxide powder in beaker, adding 422.2g hydrochloric acid, magnetically stirring at 80deg.C to dissolve completely, adding 9.98ml CeCl 0.35mol/L 3 Transferring the whole solution into a round bottom flask, and performing rotary evaporation at 55-85 ℃ and vacuum degree lower than 0.02MPa to obtain LuCl 3 ·6H 2 O, and CeCl 3 ·7H 2 O, taking down the round-bottom flask, immediately sealing the round-bottom flask by using a preservative film to prevent water absorption, and weighing the sealed round-bottom flask and LuCl 3 ·6H 2 O, and CeCl 3 ·7H 2 O crystalCan be obtained from the total mass of LuCl in the flask 3 ·6H 2 O, and CeCl 3 ·7H 2 O mass according to the previously added Lu 3+ Calculated theoretical LuCl 3 ·6H 2 O, and CeCl 3 ·7H 2 And judging the evaporation effect by the mass of O.
(b) After weighing, taking down the preservative film, immediately adding isopropanol into the round-bottomed flask, shaking, and adding LuCl 3 ·6H 2 O、CeCl 3 ·7H 2 The mixture of O and isopropanol was transferred to a beaker and the flask was repeatedly washed with isopropanol, the wash was also transferred to a beaker, isopropanol was added continuously to a volume of 2058ml, and dispersion was continued for half an hour by mechanical stirring. To be LuCl 3 ·6H 2 O, and CeCl 3 ·7H 2 After O is uniformly dispersed in isopropanol, 73.34g of TEOS is added into a large beaker, the beaker for weighing the TEOS is washed by propylene oxide, propylene oxide is continuously added to ensure that the volume of the beaker reaches 1029ml, and mechanical stirring is continuously carried out for 48 hours until full reaction is carried out, so that a precursor is obtained. Calcining the precursor at 1000 ℃ for 2 hours to obtain X1 type LSO: ce powder, wherein the powder XRD is shown in figure 1.
(c) Adding calcined X1 type LSO/Ce ceramic powder into a zirconia ball milling tank according to the mass ratio of the LSO/Ce powder to the zirconia ball mill balls of 1:6, adding a proper amount of absolute ethyl alcohol according to the solid content of the powder of 30vol.% as a ball milling medium, performing planetary ball milling for 24 hours at the rotating speed of 250rpm, and after the ball milling is finished, placing the ball milling tank into a blast drying box and drying for 24 hours at the temperature of 80 ℃.
(d) The particle size of the powder after ball milling was 142nm as measured by a nano particle size analyzer, and the particle size distribution after ball milling of the powder is shown in fig. 2.
(e) Adding 4.5g of LSO (yttrium aluminum oxide) Ce powder after ball milling and drying into a stainless steel die with the diameter of 20mm, pre-pressing the powder at the pre-pressing pressure of 2MPa for 10s, then placing the yttrium lutetium silicate monocrystal directly above the LSO Ce monocrystal in the die, adding 5.5g of LSO (yttrium aluminum oxide) Ce powder to cover the yttrium lutetium silicate monocrystal, and then pressing and forming the monocrystal under the pressure of 10MPa to further densify the monocrystal-coated green body, wherein the density of the green body is 55%, and the diameter of the green body is 18.8mm.
(f) Spraying a layer of BN into the inner cavity of a graphite mold with the diameter of 20mm, facilitating demolding, spreading 1g of LSO/Ce powder in the cavity, placing the pressed green body in the center of the mold, and spreading and adding 2g of LSO/Ce powder. Placing the graphite mould in a vacuum hot-pressing furnace for sintering, heating to 1000 ℃ from 5 ℃/min at room temperature in argon atmosphere, applying 30MPa pressure at 800 ℃, heating to 1700 ℃ at 10 ℃/min, preserving heat for 6 hours, cooling to 1000 ℃ at 5 ℃/min, and naturally cooling by water cooling to obtain the LSO/Ce monocrystal which grows directionally along the oriented crystal face of the lutetium yttrium silicate monocrystal, wherein the thickness of a growth layer is 1mm. As shown in FIG. 4, XRD of the single crystal with lutetium silicate in crystal face orientation after sintering, the texture factor in (-606) crystal face orientation obtained by XRD data calculation reaches 41.1%.
Example III
(a) Weighing 138.422g lutetium oxide powder in beaker, adding 422.2g hydrochloric acid, magnetically stirring at 80deg.C to dissolve completely, adding 9.98ml CeCl 0.35mol/L 3 Transferring the whole solution into a round bottom flask, and performing rotary evaporation at 55-85 ℃ and vacuum degree lower than 0.02MPa to obtain LuCl 3 ·6H 2 O, and CeCl 3 ·7H 2 O, taking down the round-bottom flask, immediately sealing the round-bottom flask by using a preservative film to prevent water absorption, and weighing the sealed round-bottom flask and LuCl 3 ·6H 2 O, and CeCl 3 ·7H 2 The total mass of O crystals can be obtained as LuCl in the flask 3 ·6H 2 O, and CeCl 3 ·7H 2 O mass according to the previously added Lu 3+ Calculated theoretical LuCl 3 ·6H 2 O, and CeCl 3 ·7H 2 And judging the evaporation effect by the mass of O.
(b) After weighing, taking down the preservative film, immediately adding isopropanol into the round-bottomed flask, shaking, and adding LuCl 3 ·6H 2 O、CeCl 3 ·7H 2 The mixture of O and isopropanol was transferred to a beaker and the flask was repeatedly washed with isopropanol, the wash was also transferred to a beaker, isopropanol was added continuously to a volume of 2058ml, and dispersion was continued for half an hour by mechanical stirring. To be LuCl 3 ·6H 2 O, and CeCl 3 ·7H 2 O is in isopropanolAfter being evenly dispersed, 73.34g of TEOS is added into a big beaker, the beaker for weighing the TEOS is washed by propylene oxide, propylene oxide is continuously added to enable the volume of the beaker to reach 1029ml, and mechanical stirring is continuously carried out for 48 hours until full reaction is carried out, so that a precursor is obtained. Calcining the precursor at 1000 ℃ for 2 hours to obtain X1 type LSO: ce powder, wherein the powder XRD is shown in figure 1.
(c) Adding calcined X1 type LSO/Ce ceramic powder into a zirconia ball milling tank according to the mass ratio of the LSO/Ce powder to the zirconia ball mill balls of 1:6, adding a proper amount of absolute ethyl alcohol according to the solid content of the powder of 30vol.% as a ball milling medium, performing planetary ball milling for 24 hours at the rotating speed of 250rpm, and after the ball milling is finished, placing the ball milling tank into a blast drying box and drying for 24 hours at the temperature of 80 ℃.
(d) The particle size of the powder after ball milling was 142nm as measured by a nano particle size analyzer, and the particle size distribution after ball milling of the powder is shown in fig. 2.
(e) Adding 4.5g of LSO (yttrium aluminum oxide) Ce powder after ball milling and drying into a stainless steel die with the diameter of 20mm, pre-pressing the powder at the pre-pressing pressure of 2MPa for 10s, then placing the yttrium lutetium silicate monocrystal directly above the LSO Ce green compact in the die, adding 5.5g of LSO (yttrium aluminum oxide) Ce powder to cover the yttrium lutetium silicate monocrystal, then pressing and forming the yttrium lutetium silicate monocrystal under the pressure of 10MPa, and then performing 180MPa cold isostatic pressing to further densify the green compact coated with the monocrystal, wherein the density of the green compact is 55%, and the diameter is 18.8mm.
(f) Spraying a layer of BN into the inner cavity of a graphite mold with the diameter of 20mm, facilitating demolding, spreading 1g of LSO/Ce powder in the cavity, placing the pressed green body in the center of the mold, and spreading and adding 2g of LSO/Ce powder. Sintering the graphite mould in a vacuum hot-pressing furnace, heating to 1000 ℃ from 5 ℃/min at room temperature in argon atmosphere, applying 40MPa pressure at 800 ℃, heating to 1700 ℃ at 10 ℃/min, preserving heat for 6 hours, cooling to 1000 ℃ at 5 ℃/min, and naturally cooling by water cooling to obtain the LSO/Ce monocrystal directionally growing along the oriented crystal face of the lutetium yttrium silicate monocrystal, wherein the thickness of a growing layer is 1.2mm. As shown in FIG. 5, XRD of the single crystal with lutetium silicate in crystal face orientation after sintering, the texture factor in (-325) crystal face orientation obtained by XRD data calculation reaches 67.1%.
Finally, it should be noted that those skilled in the art will understand that many technical details are presented in the embodiments of the present application in order to better understand the present application. However, the technical solutions claimed in the claims of the present application can be basically implemented without these technical details and various changes and modifications based on the above embodiments. Accordingly, in actual practice, various changes may be made in the form and details of the above-described embodiments without departing from the spirit and scope of the present application.
Claims (8)
1. A method for preparing lutetium silicate single crystal with crystal face orientation, which is characterized by comprising the following steps:
(1) Preparing cerium doped lutetium silicate precursor by sol-gel method, calcining at 1000deg.C for 2 hr to obtain coarse particle (Lu) 0.995 Ce 0.005 ) 2 SiO 5 Ceramic powder, abbreviated as LSO: ce;
(2) The prepared (Lu 0.995 Ce 0.005 ) 2 SiO 5 Ball milling and crushing the ceramic powder for 24 hours by taking alcohol as a dispersion medium to obtain depolymerized fine-grain LSO (LSO: ce ceramic powder);
(3) Placing a lutetium yttrium silicate monocrystal with grain orientation into fine-grain LSO/Ce ceramic powder, preparing a green body of the lutetium yttrium silicate monocrystal wrapped by the fine-grain LSO/Ce ceramic powder through dry pressing, wherein the molding pressure is 8-10 MPa, and carrying out 180MPa cold isostatic pressing to further densify the green body of the wrapped monocrystal;
(4) And (3) placing the green body obtained in the step (3) into a graphite crucible, and sintering the green body in an argon atmosphere at 1650-1780 ℃ and under 30-80 Mpa pressure to obtain the LSO/Ce monocrystal which grows directionally along the oriented crystal face of the lutetium yttrium silicate monocrystal.
2. The method of claim 1, wherein in step (1), the lutetium silicate precursor powder is calcined at 1000 ℃ for 2 hours to obtain an X1 type LSO: ce ceramic powder.
3. The process of claim 1, wherein in step (1), the solvent is selected from the group consisting ofThe gel method comprises the following steps: lu with purity of more than 99.99% 2 O 3 Adding hydrochloric acid into the powder for dissolution, wherein the mol ratio of Cl to Lu is 6:1, and adding CeCl with Ce content of 0.5 at% 3 The solution was stirred continuously and the Lucl was obtained by rotary evaporation 3 ·6H 2 O, adding isopropanol, propylene oxide and tetraethyl orthosilicate, wherein the amount of the tetraethyl orthosilicate is half of that of Lu and Ce, mechanically stirring for 48 hours, and drying in a blowing drying oven at 80 ℃ for 24 hours to obtain a precursor.
4. The preparation method according to claim 1, wherein in the step (2), the mass ratio of LSO: ce ceramic powder to zirconia ball mill is 1:6, the alcohol content is consistent with the powder content, the rotating speed of the planetary ball mill is 250rpm, and the median particle diameter of the fine grain powder after 24h ball milling is 142nm.
5. The method of claim 1, wherein the dry press molding method of step (3) is: adding a certain amount of LSO-Ce ceramic powder into a stainless steel mold for prepressing, wherein the prepressing pressure is 2MPa, placing the yttrium lutetium silicate monocrystal in the mold and directly above the LSO-Ce green compact, adding a certain amount of LSO-Ce ceramic powder to cover the yttrium lutetium silicate monocrystal, and then pressing and forming under the pressure of 8-10 MPa.
6. The method according to claim 1, wherein in the step (3), the green compact density is 50 to 55%.
7. The method according to claim 1, wherein the sintering process in the step (4) is to raise the temperature from room temperature 5 ℃/min to 1000 ℃, and the pressure of 20-100 MPa is applied at 800 ℃, then raise the temperature to 1650-1780 ℃ at 10 ℃/min, and after heat preservation for 6 hours, the temperature is lowered to 1000 ℃ at 5 ℃/min, and then cooled naturally by water cooling.
8. A lutetium silicate single crystal having a crystal plane orientation, characterized in that the lutetium silicate single crystal having a crystal plane orientation is produced by the production method of any one of claims 1 to 7.
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