CN102674838B - Preparation method of Eu<3+> and Ce<3+> co-doped lanthanum yttrium oxide sparkling transparent ceramic material - Google Patents
Preparation method of Eu<3+> and Ce<3+> co-doped lanthanum yttrium oxide sparkling transparent ceramic material Download PDFInfo
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- CN102674838B CN102674838B CN 201210140501 CN201210140501A CN102674838B CN 102674838 B CN102674838 B CN 102674838B CN 201210140501 CN201210140501 CN 201210140501 CN 201210140501 A CN201210140501 A CN 201210140501A CN 102674838 B CN102674838 B CN 102674838B
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Abstract
The invention relates to a preparation method of a Eu<3+> and Ce<3+> co-doped lanthanum yttrium oxide sparkling transparent ceramic material, belonging to the field of special ceramic manufacturing technology. The preparation method comprises the following steps of: taking high-purity Y2O3, Eu2O3, CeO2 and La2O3 powder as raw materials, so that the Eu<3+> and Ce<3+> co-doped lanthanum yttrium oxide sparkling transparent ceramic material can be prepared by adopting a conventional ceramic preparation technology under a lower temperature condition, due to a proper sintering schedule, and a solid phase sintering method. The experimental determination shows that through the hydrogen annealing, the red fluorescent light intensity of the sparkling ceramic can be obviously enhanced. Therefore, the Eu<3+> and Ce<3+> co-doped lanthanum yttrium oxide sparkling transparent ceramic material is wide in application prospect in the field of sparkling material.
Description
Technical field
The present invention relates to a kind of Eu
3+and Ce
3+the preparation method of the lanthanum yttrium oxide twinkling transparent ceramics material of mixing altogether, belong to the special cermacis manufacturing process technology field.
Background technology
Inorganic scintillation material is widely used in nuclear medicine (X-CT, PET), high energy physics, nuclear physics, core uranology, material non-destructive test(ing)(NDT), safety inspection, the fields such as geology detecting.Eu
3+scintillator is because its level structure is simple, and luminous efficiency is high, and fall time is short, and twilight sunset is short, and photo-detector has Spectral matching preferably and the characteristics such as excellent chemistry and thermostability, is widely used.Especially its light output is far longer than the BGO scintillation crystal.Application at present inorganic scintillation material more widely is rare earth ion doped crystalline material, but the crystal growth cycle is long, and utilization ratio is not high, with crystal, compares, it is high that crystalline ceramics has doping content, uniform doping is good, and sintering temperature is low, and the cycle is short, cost is low, the advantages such as quality controllability is strong, and size is large, and freedom shape is large.Therefore transparent ceramic glaring material has caused concern widely.
Y
2o
3belong to isometric system, the free of birefringence phenomenon, thermal conductivity is high, for the twice of yttrium aluminum garnet (YAG) is many, is a kind of good solid flicker substrate material.Therefore, Eu:Y
2o
3be used in widely the fields such as cathode tube, plasma display, three-color fluorescent lamp and Field Emission Display.But due to Y
2o
3fusing point up to 2430 ℃, and the polymorphic transition change of Emission in Cubic to six side's phases can occur near 2280 ℃, thereby be difficult to grow the Y of large size and high optical quality
2o
3monocrystalline.Along with the development of ceramics processing and nanopowder manufacturing system technology, Y
2o
3the sintering temperature of crystalline ceramics can be reduced to 1700 ℃ of left and right.In addition, due to La
2o
3add, can accelerate the eliminating of pore, reduce the crystalline ceramics sintering temperature and effectively suppress ceramic crystalline grain and too grow up, so Eu
3+the yttrium lanthanum oxide transparent ceramics of doping is a kind of scintillation material of excellent property.
In addition, with other lanthanide ions, compare, due to the energy level transformation of track spin and 4f-5d, Ce
3+fluorescence output more efficient.So Ce
3+other lanthanide ions of-Re() material of mixing is altogether studied widely, especially at Ce
3+-Eu
3+in the YAG mixed altogether, Eu
3+light output obviously strengthen.Due at Y
2o
3in matrix, Ce
3+emission wavelength and the Eu of 4f-5d
3+'s
7f
2→
5d
2,
5d
3absorbing wavelength exists significantly overlapping, Ce
3+with Eu
3+between effective energy shift and can obviously improve red emission intensity.Therefore, Eu
3+and Ce
3+mixing altogether the lanthanum yttrium oxide transparent ceramic material has a wide range of applications in the scintillator field.
Summary of the invention
The object of the invention is to adopt domestic high-purity Y
2o
3, Eu
2o
3, CeO
2, La
2o
3nano powder is raw material, adopts traditional ceramics preparation technology, formulates suitable sintering temperature, last under lower temperature condition, adopts solid sintering technology to prepare Ce
3+-Eu
3+the yttrium lanthanum oxide transparent ceramics material of mixing altogether.
A kind of Ce of the present invention
3+-Eu
3+the preparation method of the lanthanum yttrium oxide twinkling transparent ceramics material of mixing altogether is characterized in that it has following technological process and step:
A. adopt high-purity 99.99% Y
2o
3, 99.99%Eu
2o
3, 99.99%CeO
2with 99.99% La
2o
3for raw material, four mol ratio is pressed chemical formula (Ce
0.001eu
0.01y
0.889la
0.1)
2o
3carry out weigh batching;
B. Y that will be good by above-mentioned formulated
2o
3, Eu
2o
3, CeO
2, La
2o
3mixed powder is put into ball grinder and is carried out ball milling, and ratio of grinding media to material is 2:1, and the mass ratio of etoh solvent and powder is 4:1, and the ball grinder rotating speed is 50 rev/mins, and Ball-milling Time is 5h;
C. by ball milling, good powder, in drying in oven, is then calcined mixed powder in retort furnace, 1200 ℃ of insulation 10h, and naturally cooling, obtain (Ce
0.001eu
0.01y
0.889la
0.1)
2o
3powder;
D. again powder is put into to ball grinder and carry out ball milling, ratio of grinding media to material is 2:1, and the mass ratio of etoh solvent and powder is 4:1, and the ball grinder rotating speed is 50 rev/mins, and Ball-milling Time is 5h;
E. by ball milling, good powder, in drying in oven, carries out granulation by powder, crosses 40 mesh sieves;
F. the powder after granulation is dry-pressing formed, depress to sheet specimens in the 200MP isostatic cool pressing subsequently;
G. said sample is placed in vacuum oven, normal pressure-sintered, sintering range 1600-1700 ℃, finally obtain fine and close (Ce in sintering time 40-45 hour
0.001eu
0.01y
0.889la
0.1)
2o
3pottery.
The accompanying drawing explanation
Fig. 1 is (Ce in the present invention
0.001eu
0.01y
0.889la
0.1)
2o
3the excitation spectrum of crystalline ceramics.
Fig. 2 is (Ce in the present invention
0.001eu
0.01y
0.889la
0.1)
2o
3the fluorescence spectrum of crystalline ceramics.
Embodiment
After now specific embodiments of the invention being described in.
The present invention is a kind of Ce
3+-Eu
3+the preparation method of the lanthanum yttrium oxide twinkling transparent ceramics material of mixing altogether is characterized in that it has following technological process and step:
C. adopt high-purity 99.99% Y
2o
3, 99.99%Eu
2o
3, 99.99%CeO
2with 99.99% La
2o
3for raw material, four mol ratio is pressed chemical formula (Ce
0.001eu
0.01y
0.889la
0.1)
2o
3carry out weigh batching;
D. Y that will be good by above-mentioned formulated
2o
3, Eu
2o
3, CeO
2, La
2o
3mixed powder is put into ball grinder and is carried out ball milling, and ratio of grinding media to material is 2:1, and the mass ratio of etoh solvent and powder is 4:1, and the ball grinder rotating speed is 50 rev/mins, and Ball-milling Time is 5h;
C. by ball milling, good powder, in drying in oven, is then calcined mixed powder in retort furnace, 1200 ℃ of insulation 10h, and naturally cooling, obtain (Ce
0.001eu
0.01y
0.889la
0.1)
2o
3powder;
D. again powder is put into to ball grinder and carry out ball milling, ratio of grinding media to material is 2:1, and the mass ratio of etoh solvent and powder is 4:1, and the ball grinder rotating speed is 50 rev/mins, and Ball-milling Time is 5h;
E. by ball milling, good powder, in drying in oven, carries out granulation by powder, crosses 40 mesh sieves;
F. the powder after granulation is dry-pressing formed, depress to sheet specimens in the 200MP isostatic cool pressing subsequently;
G. said sample is placed in vacuum oven, normal pressure-sintered, sintering range 1630-1650 ℃, finally obtain fine and close (Ce in sintering time 40-45 hour
0.001eu
0.01y
0.889la
0.1)
2o
3pottery.
Prepared fine and close (Ce by above-mentioned example
0.001eu
0.01y
0.889la
0.1)
2o
3crystalline ceramics, have good optical property.Material preparation process of the present invention is simple, and low cost of manufacture is conducive to realize industrial scale production.The excitation spectrum of crystalline ceramics sample and fluorescence spectrum detect by spectrophotometer (FP-6300, JASCO, Japan).As shown in Figure 1, after the air anneal, 400 nm, the excitation band at 466 nm and 535 nm places is due to Eu
3+f layer electronics from ground state
7f
0energy level transits to respectively
5l
6,
5d
2,
5d
1cause, the excitation band at 260 nm places may be by Eu
3+-O
2-charge transfer causes.After hydrogen annealing is processed, due to Eu
3+become Eu
2+, so 400 nm, the excitation band at 466 nm and 535 nm places disappears, simultaneously due to Ce
3+increase, the strength increase of the excitation band at 260 nm places.As shown in Figure 2,580nm is by Eu to the fluorescence emission peak group of 650nm
3+excited level
5d
0to ground state level
7f
jthe transition of electron of (J=0,1,2,3) obtains.After hydrogen annealing is processed, due to Ce
3+increase, the red emission intensity at 613nm place significantly increases, Ce
3+with Eu
3+between effectively energy shift and improved Eu
3+flashing intensity.Therefore, Eu
3+and Ce
3+mixing altogether the lanthanum yttrium oxide transparent ceramic material has a wide range of applications in the scintillator field.
Claims (1)
1. an Eu
3+and Ce
3+the preparation method of the lanthanum yttrium oxide twinkling transparent ceramics material of mixing altogether is characterized in that it has following technological process and step:
A. adopt high-purity 99.99% Y
2o
3, 99.99%Eu
2o
3, 99.99%CeO
2with 99.99% La
2o
3for raw material, four mol ratio is pressed chemical formula (Ce
0.001eu
0.01y
0.889la
0.1)
2o
3carry out weigh batching;
B. Y that will be good by above-mentioned formulated
2o
3, Eu
2o
3, CeO
2, La
2o
3mixed powder is put into ball grinder and is carried out ball milling, and ratio of grinding media to material is 2:1, and the mass ratio of etoh solvent and powder is 4:1, and the ball grinder rotating speed is 50 rev/mins, and Ball-milling Time is 5h;
C. by ball milling, good powder, in drying in oven, is then calcined mixed powder in retort furnace, 1200 ℃ of insulation 10h, and naturally cooling, obtain (Ce
0.001eu
0.01y
0.889la
0.1)
2o
3powder;
D. again powder is put into to ball grinder and carry out ball milling, ratio of grinding media to material is 2:1, and the mass ratio of etoh solvent and powder is 4:1, and the ball grinder rotating speed is 50 rev/mins, and Ball-milling Time is 5h;
E. by ball milling, good powder, in drying in oven, carries out granulation by powder, crosses 40 mesh sieves;
F. the powder after granulation is dry-pressing formed, depress to sheet specimens in the 200MPa isostatic cool pressing subsequently;
G. said sample is placed in vacuum oven, normal pressure-sintered, sintering range 1600-1700 ℃, finally obtain fine and close (Ce in sintering time 40-45 hour
0.001eu
0.01y
0.889la
0.1)
2o
3pottery.
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|---|---|---|---|
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| CN102674838B true CN102674838B (en) | 2013-12-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073295B (en) * | 2013-01-17 | 2014-07-30 | 上海大学 | Preparation method of Er3+ and Tm3+ co-doped yttrium lanthanum oxide scintillating material transparent ceramic material |
| CN103073294A (en) * | 2013-01-17 | 2013-05-01 | 上海大学 | Preparation method of Er3+ and Pr3+ co-doped yttrium lanthanum oxide scintillating material transparent ceramic material |
| CN103073293B (en) * | 2013-01-17 | 2014-07-30 | 上海大学 | Preparation method of Er3+ and Nd3+ co-doped yttrium lanthanum oxide scintillating material transparent ceramic material |
| CN104478434B (en) * | 2014-12-08 | 2017-05-31 | 上海大学 | Eu2+/Eu3+:Y1.8‑xLa0.2ZrxO3Crystalline ceramics and preparation method thereof |
| CN112500163A (en) * | 2020-12-24 | 2021-03-16 | 中红外激光研究院(江苏)有限公司 | Preparation method of yttrium oxide transparent ceramic with high visible light transmittance |
| CN114685166A (en) * | 2022-05-05 | 2022-07-01 | 闽都创新实验室 | Scintillation ceramic and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148356A (en) * | 2007-09-13 | 2008-03-26 | 上海大学 | Ce3+ mixed lanthanum yttrium oxide transparent flickering ceramic material and preparation method thereof |
| CN102320833A (en) * | 2011-06-10 | 2012-01-18 | 上海大学 | Preparation method of Eu3+ doped yttrium lanthanum oxide transparent ceramic |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148356A (en) * | 2007-09-13 | 2008-03-26 | 上海大学 | Ce3+ mixed lanthanum yttrium oxide transparent flickering ceramic material and preparation method thereof |
| CN102320833A (en) * | 2011-06-10 | 2012-01-18 | 上海大学 | Preparation method of Eu3+ doped yttrium lanthanum oxide transparent ceramic |
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