CN101456734A - Rare earth oxide solid solution ceramic scintillator and preparation method thereof - Google Patents
Rare earth oxide solid solution ceramic scintillator and preparation method thereof Download PDFInfo
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- CN101456734A CN101456734A CNA2008101634920A CN200810163492A CN101456734A CN 101456734 A CN101456734 A CN 101456734A CN A2008101634920 A CNA2008101634920 A CN A2008101634920A CN 200810163492 A CN200810163492 A CN 200810163492A CN 101456734 A CN101456734 A CN 101456734A
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Abstract
The invention discloses a rare earth oxide solid solution ceramic scintillator and a preparation method thereof. The main component of the ceramic scintillator is Gd2xLu2yY2(1-x-y-z)Eu2zO3 (the x is more than or equal to 0.1 and less than or equal to 0.6, the y is more than or equal to 0.1 and is less than or equal to 0.4, and the z is more than or equal to 0.01 and less than or equal to 0.1), and the ceramic scintillator has a crystal structure with a cubic Ia3 point group. Ceramic powder can be synthesized by a chemical coprecipitation method. The coprecipitation method adopts ammonia, ammonium hydrogen carbonate or a mixed solution of the ammonium water and the ammonium hydrogen carbonate as a precipitating agent, titrates the precipitating agent into a solution of gadolinium nitrate, lutecium nitrate, yttrium nitrate and europium nitrate to obtain a precipitate, and then the precipitate is dried and calcined to obtain nano-powder. The obtained powder is pressed into a ceramic blank through an isostatic compaction method, then the pressureless sintering is performed in vacuum or hydrogen atmosphere, the sintering temperature is between 1,600 and 1,900 DEG C, transparent Gd2xLu2yY2(1-x-y-z)Eu2zO3 ceramic can be obtained, a ceramic product with the needed dimension is prepared after the cutting, grinding and polishing, and the transmission rate of the ceramic in a visible region (400-800 nanometers) is more than or equal to 65 percent. The ceramic scintillator emits red light with a main wavelength of 610 nanometers under the excitation of ultraviolet light or X rays, and can be used for scintillating materials of imaging and detection of medical and industrial X rays.
Description
Technical field
The present invention relates to functional materials and technology of preparing thereof, be specifically related to a kind of rare earth oxide solid solution ceramic scintillator and preparation method thereof.Belong to ceramic flashing material field.
Background technology
Rare earth ion Eu
3+Adulterated cube of phase Gd
2O
3It is a kind of very important luminous and scintillation material.Just study its characteristics of luminescence as far back as Bril in 1964 and Wanmaker, be subjected to people's extensive concern in recent years as fluorescent material and thin-film material.As red fluorescence powder efficiently, has important application prospects in fields such as plasma imaging, high definition television, projection TV, flat pannel display.As scintillator, Gd
2O
3: Eu is a kind of ceramic scintillator of high comprehensive performance, in high resolution X-CT, X ray safety check imaging device and CCD coupling large area x-ray imaging field very important application prospect will be arranged.Gd
2O
3Has high-density (7.64g/cm
3), high effective atomic number (Zeff=64), so it is very strong to X ray and gamma-ray receptivity, between Lu
2O
3And LuAG (Lu
3Al
5O
12) between, far above Y
2O
3: Eu and (Y, Gd)
2O
3: Eu also is higher than Gd
2O
2S:Pr; Gd
2O
3: the luminous efficiency of Eu is very high, and its twinkling light is output as 18465 ± 5000ph./MeV during the film attitude, with Lu
2O
3: Eu is suitable; Gd
2O
3: the luminous predominant wavelength of Eu is 610nm, and is good with the photorectifier coupling, detection efficiency height, and UFC (Gd
2O
2S:Pr) predominant wavelength is positioned at 510nm, and the efficient of photorectifier has only 40%~50%, the optical detection weak effect; Gd during 10ms under excitation of X-rays
2O
3: the twilight sunset of Eu is 10-3 (0.1%), by adding Tb
3+Plasma can reduce time of persistence.In addition, Gd
2O
3Chemical property is stable, satisfactory mechanical property.
Because Gd
2O
3: the Eu cost of material is cheap, the luminescent properties brilliance, and market outlook are good, however because Gd
2O
3There is structural phase transition at 1250 ℃, Gd under the low temperature
2O
3Belong to body-centered cubic structure (C type), be higher than 1250 ℃ and change monocline (Type B) into, and have only the Gd of cube phase
2O
3: Eu just has high luminous efficiency, is difficult to growth cube phase large single crystal because of technical, and preparation can practical ceramic scintillator under its fusing point and the transformation temperature so the researchist makes great efforts to explore being lower than.For overcoming Gd
2O
3Phase transformation, GE company adopts a large amount of doping Y
2O
3Prepare (Y, Gd)
2O
3Scintillating ceramic, and be applied to medical science X-CT imaging device.Ji Yaming etc. mix 10~40% HfO
2Low temperature cube can be stabilized to sintering temperature 1600-1700 ℃ mutually.Directly adopt the reducing atmosphere sintering to obtain to reach 60% cube phase Gd in the visible region transmitance
2O
3: the Eu scintillating ceramic.
But aforesaid method all makes Gd
2O
3: the scintillation properties variation of Eu, too much LiCl or the Y of mixing
2O
3Reduced the density of material and the ability of absorption ray, reduced the resolving power of detector simultaneously, mixed Y as GE company
2O
3Obtain (Y, Gd)
2O
3Density only is 5.9g/cm
3And mix HfO
2Stablize Gd
2O
3Its twinkling light output is reduced, as mix 5%HfO
2Back UV emissive porwer reduces by 50%, has limited Gd
2O
3Material is in Application for Field such as X-CT and rays safety detection apparatus.
Summary of the invention
The present invention is taking all factors into consideration Gd
2O
3: Eu, Lu
2O
3: Eu and Y
2O
3: on the basis of Eu cost of material and performance, the strong point of the performance of three kinds of materials of performance and the advantage on the price form a kind of new rare earth oxide solid solution ceramic scintillator, the object of the present invention is to provide a kind of ceramic scintillator and preparation method thereof.
The technical scheme that the present invention solves its technical problem employing is:
1, rare earth oxide solid solution ceramic scintillator
The principal constituent of this ceramic scintillator is Gd
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3, 0.1≤x≤0.6,0.1≤y≤0.4,0.01≤z≤0.1 wherein; The crystalline structure of this solid solution ceramic is the vacant fluorite structure of isometric system, and spacer is Ia3.In addition, in order to improve the scintillation properties of this solid solution ceramic,, can add the Nd of 0.001wt%~1wt% as time of persistence and fall time
3+, Tb
3+Or Pr
3+
2, the preparation method of rare earth oxide solid solution ceramic scintillator
This ceramic powder adopts chemical coprecipitation synthetic, and isostatic pressing is pressed into ceramic idiosome, pressureless sintering in vacuum or hydrogen atmosphere then, through cutting, grind and polishing after be prepared into the Gd of desired size
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3Ceramic scintillator.Specifically comprise following processing step:
1) according to the synthetic Gd of institute
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3Pottery is Gd (NO in molar ratio
3)
3: Lu (NO
3)
3: Y (NO
3)
3: Eu (NO
3)
3=x:y:(1-x-y-z): z prepares mixed nitrate solution, in addition according to the needs of synthesize ceramic, can add (0.5~10mol%) Tb (NO
3)
3, Nd (NO
3)
3, or Pr (NO
3)
3, mixing solutions rare earth ion total concn is (0.05~0.9) mol/l.
2) preparation precipitant solution.Employing concentration is that ammoniacal liquor, the concentration of (0.2~5) mol/l is the bicarbonate of ammonia of (0.1~2) mol/l or the mixing solutions of two kinds of solution, any precipitation agent that all can be used as among the three.
3) precipitation agent is titrated in the mixed rare earth nitrates solution gradually, constantly stir, constantly produce white floss precipitation, the pH to 8 of solution~9 o'clock end titration, continue to stir 30 minutes, ageing is filtered, then throw out is used respectively deionized water and absolute ethanol washing each 3 times or more than, drying is 10~48 hours in baking oven, calcining, grinding has obtained nanometer level RE oxide solid solution ceramic powder.Calcining temperature is at 700~1000 ℃, and the time is 1-6 hour.
4) after the powder that obtains after will calcining is crossed 40 mesh sieves, in stainless steel mould~10MPa premolding obtains biscuit, again by 100~400MPa isostatic pressing, obtains the ceramic green of higher density.
5) sintering of crystalline ceramics carries out in vacuum tungsten filament sintering oven or hydrogen furnace, and pottery is placed in the molybdenum crucible.Vacuum tungsten coil furnace vacuum degree of cold state requires to be higher than 10
-3Pa, vacuum tightness preferably reaches 10
-4More than the Pa, with the temperature rise rate of 10~30 ℃/min, sintering temperature is 1600-1900 ℃, is 2-24 hour according to ceramic size soaking time, can obtain Gd
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3Crystalline ceramics.During the hydrogen furnace sintering, keep normal pressure in the stove, sintering temperature is 1600-1900 ℃, is 2-24 hour according to ceramic size soaking time.
6) with the crystalline ceramics that obtains, cut into desired size through interior circle, adopt diamond saw blade, use the alumina lap powder to grind, rubbing paste is a cerium dioxide, can obtain transparent Gd
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3Ceramic scintillator.
Rare earth oxide solid solution ceramic scintillator that the present invention obtains and preparation method thereof has the following advantages:
1) this stupalith is europium ion-doped gadolinium lutetium yttrium oxide sosoloid, can be according to performance requriements and convenient within the specific limits its chemical constitution of regulating of price, to obtain the good ceramic scintillator of cheap scintillation properties, as performances such as luminous intensity, fall time, twilight sunset.
2) at Gd
2O
3, Y
2O
3With Lu
2O
3Market value between greatest differences, under the prerequisite of satisfy using, can improve Gd during the preparation pottery as far as possible
2O
3And Y
2O
3Ratio, thereby reduce the cost of material.
3) adopt single precipitation agent or the coprecipitation method of ammoniacal liquor and bicarbonate of ammonia mixed precipitant and the methods of vacuum sintering such as ammoniacal liquor, bicarbonate of ammonia, technology is simple, and equipment requirements is low, is easy to realize suitability for industrialized production.
4) powder that adopts coprecipitation method to obtain is a nano-powder, and even particle distribution, particle are ball-type, have high sintering activity.
5) emission wavelength of this rare earth oxide solid solution ceramic is positioned at 610nm, the light that totally takes on a red color, and luminous intensity is suitable with commercial CsI (T1) crystal, the luminous intensity height.
6) and Gd
2O
3: Eu compares, and this rare earth oxide solid solution ceramic has higher density, to the absorption and the detectivity height of x ray, has advantage in x X-ray detection X material is used.With Lu
2O
3: Eu compares, the price advantage that this rare earth oxide solid solution ceramic is good, and have less time of persistence.
Therefore, the rare earth oxide solid solution ceramic that the present invention obtained sends ruddiness under ultraviolet excitation or x rays excite, is suitable for as x ray scintillation detecting material or electroluminescent material etc.
Description of drawings
Fig. 1 adopts the Gd of the mixing solutions of ammoniacal liquor and bicarbonate of ammonia as the precipitation agent preparation
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3The XRD figure of powder.
Fig. 2 is the Gd of coprecipitation method preparation
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3The stereoscan photograph of powder.
Fig. 3 is the Gd that utilizes the vaccum sintering process preparation
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3Crystalline ceramics sample photo in kind.
Fig. 4 is the Gd that co-precipitation and vacuum sintering obtain
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3The stereoscan photograph of crystalline ceramics.
Fig. 5 is Gd
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3The XRD figure of crystalline ceramics.
Fig. 6 is Gd
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3The transmittance curve of crystalline ceramics.
Fig. 7 is Gd
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3The fluorescence spectrum of crystalline ceramics.
Fig. 8 is Gd
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3The emmission spectrum of crystalline ceramics under excitation of X-rays.
Embodiment
Embodiment 1
Preparation Gd
1.1Lu
0.4Y
0.4Eu
0.1O
3Pottery is Gd (NO in molar ratio
3)
3: Lu (NO
3)
3: Y (NO
3)
3: Eu (NO
3)
3=0.55:0.2:0.2:0.05 prepares mixed nitrate solution, and mixing solutions rare earth ion total concn is 0.5mol/l.Adopting concentration is that the ammoniacal liquor of 2mol/l and bicarbonate of ammonia mixing solutions that concentration is 0.5mol/l are precipitation agent.Precipitation agent is titrated in the mixed rare earth nitrates solution gradually, constantly stir, constantly produce white floss precipitation, the pH of solution finished titration by 8 o'clock, continue to stir 30 minutes, ageing is filtered, and then throw out is used deionized water and absolute ethanol washing respectively each 3 times, drying is 24 hours in baking oven, calcining, grinding has obtained nano level cube rare earth oxide solid solution ceramic powder, be the XRD figure of this powder as shown in Figure 1, powder granule is subsphaeroidal, uniform particles, SEM figure as shown in Figure 2.Calcining temperature is at 1000 ℃, and the time is 1 hour.
After the powder that obtains was crossed 40 mesh sieves after the calcining, 10MPa premolding obtained biscuit in stainless steel mould, again by the 300MPa isostatic pressing, obtained the ceramic green of higher density.
The sintering of crystalline ceramics carries out at vacuum tungsten filament sintering oven, and pottery is placed in the molybdenum crucible.Vacuum degree of cold state reaches 10
-4Pa, with the temperature rise rate of 10 ℃/min, sintering temperature is 1700 ℃, is 6 hours according to ceramic size soaking time, can obtain Gd
1.1Lu
0.4Y
0.4Eu
0.1O
3Crystalline ceramics, as shown in Figure 3.This pottery is observed under scanning electron microscope, visible crystal grain~10 microns, and crystal boundary is straight, clean, so to optical transparency, as shown in Figure 4.This pottery is done X-ray diffraction, and it is a cube phase crystalline structure as can be known, and is single-phase, does not have other any dephasign, as shown in Figure 5.With the crystalline ceramics that obtains, use the alumina lap powder to grind, rubbing paste is a cerium dioxide.
Test Gd
1.1Lu
0.4Y
0.4Eu
0.1O
3The transmitance of crystalline ceramics, its transmitance can reach 65% near 610 nanometers as can be known, as shown in Figure 6.Test its burst of ultraviolel emmission spectrum, 274 nano-ultraviolet lights can effectively excite as can be known, make its ruddiness that sends 610 nanometers, have good coupling with silicon photoelectric diode, and fluorescence spectrum is seen shown in the accompanying drawing 7.In addition, this pottery sends very strong flicker under excitation of X-rays luminous, and the emission main peak is positioned at 610 nanometers, and is similar with fluorescence spectrum, as shown in Figure 8.
Embodiment 2
Preparation Gd
1.2Lu
0.2Y
0.4Eu
0.2O
3Pottery is Gd (NO in molar ratio
3)
3: Lu (NO
3)
3: Y (NO
3)
3: Eu (NO
3)
3=0.6:0.1:0.2:0.1 prepares mixed nitrate solution, and mixing solutions rare earth ion total concn is 0.5mol/l.Adopting concentration is that the ammoniacal liquor of 2mol/l and bicarbonate of ammonia mixing solutions that concentration is 0.5mol/l are precipitation agent.Precipitation agent is titrated in the mixed rare earth nitrates solution gradually, constantly stirs, constantly produce white floss precipitation, the pH of solution finished titration by 9 o'clock, continued to stir ageing 30 minutes, filter, then throw out is used deionized water and absolute ethanol washing respectively each 3 times, drying is 24 hours in baking oven, calcining, grinding, obtained nano level cube rare earth oxide solid solution ceramic powder, powder granule is subsphaeroidal, uniform particles.Calcining temperature is at 700 ℃, and the time is 6 hours.
After the powder that obtains was crossed 40 mesh sieves after the calcining, 10MPa premolding obtained biscuit in stainless steel mould, again by the 400MPa isostatic pressing, obtained the ceramic green of higher density.
The sintering of crystalline ceramics carries out at vacuum tungsten filament sintering oven, and pottery is placed in the molybdenum crucible.Vacuum degree of cold state reaches 1.0*10
-3Pa, with the temperature rise rate of 10 ℃/min, sintering temperature is 1800 ℃, is 10 hours according to ceramic size soaking time, can obtain Gd
1.2Lu
0.2Y
0.4Eu
0.2O
3Crystalline ceramics.With the crystalline ceramics that obtains, use the alumina lap powder to grind, rubbing paste is a cerium dioxide.This crystalline ceramics is coupled to silicon photoelectric diode can be made into scintillation detector.
Embodiment 3
Preparation Gd
0.2Lu
0.8Y
0.98Eu
0.02O
3Pottery is Gd (NO in molar ratio
3)
3: Lu (NO
3)
3: Y (NO
3)
3: Eu (NO
3)
3=0.1:0.4:0.49:0.01 prepares mixed nitrate solution, and mixing solutions rare earth ion total concn is 0.5mol/l.Adopting concentration is that the ammoniacal liquor of 2mol/l and bicarbonate of ammonia mixing solutions that concentration is 0.5mol/l are precipitation agent.Precipitation agent is titrated in the mixed rare earth nitrates solution gradually, constantly stirs, constantly produce white floss precipitation, the pH of solution finished titration by 9 o'clock, continued to stir ageing 30 minutes, filter, then throw out is used deionized water and absolute ethanol washing respectively each 3 times, drying is 24 hours in baking oven, calcining, grinding, obtained nano level cube rare earth oxide solid solution ceramic powder, powder granule is subsphaeroidal, uniform particles.Calcining temperature is at 800 ℃, and the time is 4 hours.
After the powder that obtains was crossed 40 mesh sieves after the calcining, 10MPa premolding obtained biscuit in stainless steel mould, again by the 100MPa isostatic pressing, obtained the ceramic green of higher density.
The sintering of crystalline ceramics carries out at vacuum tungsten filament sintering oven, and pottery is placed in the molybdenum crucible.Vacuum degree of cold state reaches 6.67*10
-4Pa, with the temperature rise rate of 10 ℃/min, sintering temperature is 1900 ℃, is 2 hours according to ceramic size soaking time, can obtain Gd
0.2Lu
0.8Y
0.98Eu
0.02O
3Crystalline ceramics.With the crystalline ceramics that obtains, use the alumina lap powder to grind, rubbing paste is a cerium dioxide.This crystalline ceramics is coupled to silicon photoelectric diode can be made into scintillation detector.
Embodiment 4
Preparation Gd
1.2Lu
0.2Y
0.4Eu
0.2O
3Pottery is Gd (NO in molar ratio
3)
3: Lu (NO
3)
3: Y (NO
3)
3Eu (NO
3)
3=0.6:0.1:0.2:0.1 prepares mixed nitrate solution, adds Tb (NO in addition
3)
3, accounting for the 0.4wt% of total rare earth (TRE), mixing solutions rare earth ion total concn is 0.5mol/l.Adopting concentration is that the ammoniacal liquor of 2mol/l and bicarbonate of ammonia mixing solutions that concentration is 0.5mol/l are precipitation agent.Precipitation agent is titrated in the mixed rare earth nitrates solution gradually, constantly stirs, constantly produce white floss precipitation, the pH of solution finished titration by 8 o'clock, continued to stir ageing 30 minutes, filter, then throw out is used deionized water and absolute ethanol washing respectively each 3 times, drying is 24 hours in baking oven, calcining, grinding, obtained nano level cube rare earth oxide solid solution ceramic powder, powder granule is subsphaeroidal, uniform particles.Calcining temperature is at 100 ℃, and the time is 2 hours.
After the powder that obtains was crossed 40 mesh sieves after the calcining, 10MPa premolding obtained biscuit in stainless steel mould, again by the 300MPa isostatic pressing, obtained the ceramic green of higher density.
The sintering of crystalline ceramics carries out at hydrogen sintering furnace, and pottery is placed in the molybdenum crucible.With the temperature rise rate of 10 ℃/min, sintering temperature is 1800 ℃, is 6 hours according to ceramic size soaking time, can obtain Gd
1.2Lu
0.2Y
0.4Eu
0.2O
3Crystalline ceramics.With the crystalline ceramics that obtains, use the alumina lap powder to grind, rubbing paste is a cerium dioxide.This crystalline ceramics is coupled to silicon photoelectric diode can be made into scintillation detector.
Claims (7)
1, a kind of rare earth oxide solid solution ceramic scintillator is characterized in that: the principal constituent of this ceramic scintillator is Gd
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3, 0.1≤x≤0.6,0.1≤y≤0.4,0.01≤z≤0.1 wherein; The crystalline structure of this solid solution ceramic is the vacant fluorite structure of isometric system, and spacer is Ia3.
2, a kind of rare earth oxide solid solution ceramic scintillator according to claim 1 is characterized in that: described Gd
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3In also can contain the Nd of 0.001wt%~1wt%
3+, Tb
3+Or Pr
3+
3, the preparation method who is used for the described a kind of rare earth oxide solid solution ceramic scintillator of claim 1, it is characterized in that: this ceramic powder adopts chemical coprecipitation synthetic, isostatic pressing is pressed into ceramic idiosome, pressureless sintering in vacuum or hydrogen atmosphere then, through cutting, grind and polishing after be prepared into the Gd of desired size
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3Ceramic scintillator.
4, the preparation method of a kind of rare earth oxide solid solution ceramic scintillator according to claim 3, it is characterized in that: the chemical coprecipitation of synthetic this ceramic powder adopts ammoniacal liquor, the mixing solutions of bicarbonate of ammonia or ammoniacal liquor and bicarbonate of ammonia is as precipitation agent, precipitation agent is titrated to Gadolinium trinitrate, lutecium nitrate, obtain white floss precipitation in the solution of Yttrium trinitrate and europium nitrate, and constantly stir, the pH to 8 of solution~9 o'clock end titration, continue to stir 30 minutes, ageing, filter, then throw out is used deionized water and absolute ethanol washing respectively, drying, calcining, grinding has obtained nano-powder.Calcining temperature is at 700~1000 ℃, and the time is 1-6 hour.The mol ratio of Gadolinium trinitrate, lutecium nitrate, Yttrium trinitrate and europium nitrate is x:y:(1-x-y-z when wherein preparing nitrate solution): z, 0.1≤x≤0.6 wherein, 0.1≤y≤0.4,0.01≤z≤0.1 is in addition according to the neodymium nitrate that adds 0.001wt%~1wt% in the claim 2, Terbium trinitrate or praseodymium nitrate.
5, the preparation method of a kind of rare earth oxide solid solution ceramic scintillator according to claim 3, it is characterized in that: after the powder that will obtain after will calcining is crossed 40 mesh sieves, in stainless steel mould~10MPa premolding obtains biscuit, again by 100~400MPa isostatic pressing.
6, the preparation method of a kind of rare earth oxide solid solution ceramic scintillator according to claim 3 is characterized in that: the sintering of crystalline ceramics carries out in vacuum tungsten filament sintering oven or hydrogen furnace, and pottery is placed in the molybdenum crucible.Vacuum tungsten coil furnace vacuum degree of cold state requires to be higher than 10
-3Pa, sintering temperature is 1600-1900 ℃, is 2-24 hour according to ceramic size soaking time, can obtain Gd
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3Crystalline ceramics.During the hydrogen furnace sintering, keep normal pressure in the stove, sintering temperature is 1600-1900 ℃, is 2-24 hour according to ceramic size soaking time.
7, the preparation method of a kind of rare earth oxide solid solution ceramic scintillator according to claim 3, it is characterized in that: with the crystalline ceramics that obtains, cut into desired size through interior circle, adopt diamond saw blade, use the alumina lap powder to grind, rubbing paste is a cerium dioxide, can obtain transparent Gd
2xLu
2yY
2 (1-x-y-z)Eu
2zO
3Ceramic scintillator.
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