CN102674838A - Preparation method of Eu<3+> and Ce<3+> co-doped lanthanum yttrium oxide sparkling transparent ceramic material - Google Patents

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

Eu 3+And Ce 3+Mix lanthanum yttrium oxide twinkling transparent ceramics preparation methods altogether

Technical field

The present invention relates to a kind of Eu ³⁺And Ce ³⁺The lanthanum yttrium oxide twinkling transparent ceramics preparation methods of mixing altogether belongs 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, nuclear uranology, material non-destructive test(ing)(NDT), safety inspection, 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 the short and photo-detector of twilight sunset has characteristics such as Spectral matching preferably and excellent chemistry and thermostability, has obtained application widely.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; Compare with crystal, crystalline ceramics has the doping content height, and uniform doping property is good; Sintering temperature is low, and the cycle is short, and cost is low; Advantages such as quality controllability is strong, and size is big, and freedom shape is big.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 fields such as cathode tube, plasma display, three-color fluorescent lamp and Field Emission Display widely.But because Y ₂O ₃Fusing point up to 2430 ℃, and near 2280 ℃ cube polymorphic transition change of six side's phases in opposite directions can take place, thereby be difficult to grow the Y of large size and high optical quality ₂O ₃Monocrystalline.Along with the development of ceramics processing and nanometer powder-making technique, Y ₂O ₃The sintering temperature of crystalline ceramics can be reduced to about 1700 ℃.In addition, because La ₂O ₃Adding, can quicken the eliminating of pore, reduce the crystalline ceramics sintering temperature and effectively suppress ceramic crystalline grain and too grow up, so Eu ³⁺Adulterated lanthanum yttrium oxide transparent pottery is a kind of scintillation material of excellent property.

In addition, compare, because the energy level of track spin and 4f-5d changes Ce with other lanthanide ions ³⁺Fluorescence output more efficient.So Ce ³⁺The material that-Re (other lanthanide ions) mixes altogether obtains extensive studies, especially at Ce ³⁺-Eu ³⁺Among the YAG that mixes altogether, Eu ³⁺Light output obviously strengthen.Because at Y ₂O ₃In the matrix, Ce ³⁺Emission wavelength and the Eu of 4f-5d ^{3+ 7}F 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 the lanthanum yttrium oxide transparent ceramic material altogether has a wide range of applications in the scintillator field.

Summary of the invention

The objective of the invention is to adopt homemade high-purity Y ₂O ₃, Eu ₂O ₃, CeO ₂, La ₂O ₃Nano powder is a raw material, adopts traditional ceramics preparation technology, formulates suitable sintering temperature, and is last under lower temperature condition, adopts solid sintering technology to prepare Ce ³⁺-Eu ³⁺The lanthanum yttrium oxide transparent stupalith of mixing altogether.

A kind of Ce of the present invention ³⁺-Eu ³⁺The lanthanum yttrium oxide twinkling transparent ceramics preparation methods 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 ₃Be raw material, four mol ratio is pressed chemical formula (Ce _0.001Eu _0.01Y _0.889La _0.1) ₂O ₃Carry out weigh batching;

B. will be by the good Y of 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 ball-to-powder weight ratio 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 the ball milling time is 5h;

C. ball milling is good powder is calcined mixed powder in drying in oven then in retort furnace, 1200 ℃ of insulation 10h, and naturally cooling obtains (Ce _0.001Eu _0.01Y _0.889La _0.1) ₂O ₃Powder;

D. once more powder is put into ball grinder and carry out ball milling, ball-to-powder weight ratio 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 the ball milling time is 5h;

E. ball milling is good powder carries out granulation in drying in oven with powder, crosses 40 mesh sieves;

F. the powder after the granulation is dry-pressing formed, depress to the sheet sample in the 200MP isostatic cool pressing subsequently;

G. said sample is placed in the vacuum oven, normal pressure-sintered, sintering range 1600-1700 ℃, sintering time 40-45 finally obtained fine and close (Ce in individual hour _0.001Eu _0.01Y _0.889La _0.1) ₂O ₃Pottery.

Description of drawings

Fig. 1 is (Ce among the present invention _0.001Eu _0.01Y _0.889La _0.1) ₂O ₃The excitation spectrum of crystalline ceramics.

Fig. 2 is (Ce among the present invention _0.001Eu _0.01Y _0.889La _0.1) ₂O ₃The fluorescence spectrum of crystalline ceramics.

Embodiment

After specific embodiment of the present invention being described at present.

The present invention is a kind of Ce ³⁺-Eu ³⁺The lanthanum yttrium oxide twinkling transparent ceramics preparation methods 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 ₃Be raw material, four mol ratio is pressed chemical formula (Ce _0.001Eu _0.01Y _0.889La _0.1) ₂O ₃Carry out weigh batching;

D. will be by the good Y of 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 ball-to-powder weight ratio 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 the ball milling time is 5h;

C. ball milling is good powder is calcined mixed powder in drying in oven then in retort furnace, 1200 ℃ of insulation 10h, and naturally cooling obtains (Ce _0.001Eu _0.01Y _0.889La _0.1) ₂O ₃Powder;

D. once more powder is put into ball grinder and carry out ball milling, ball-to-powder weight ratio 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 the ball milling time is 5h;

E. ball milling is good powder carries out granulation in drying in oven with powder, crosses 40 mesh sieves;

F. the powder after the granulation is dry-pressing formed, depress to the sheet sample in the 200MP isostatic cool pressing subsequently;

G. said sample is placed in the vacuum oven, normal pressure-sintered, sintering range 1630-1650 ℃, sintering time 40-45 finally obtained fine and close (Ce in individual hour _0.001Eu _0.01Y _0.889La _0.1) ₂O ₃Pottery.

By above-mentioned examples preparation fine and close (Ce _0.001Eu _0.01Y _0.889La _0.1) ₂O ₃Crystalline ceramics has the good optical performance.Material preparation process of the present invention is simple, and low cost of manufacture helps realizing industrial scale production.(FP-6300, JASCO Japan) detect through spectrophotometer for the PLE of crystalline ceramics sample and fluorescence spectrum.As shown in Figure 1, after the air anneal, 400 nm, the excitation band at 466 nm and 535 nm places are because Eu ³⁺F layer electronics from ground state ⁷F ₀Energy level transits to respectively ⁵L ₆, ⁵D ₂, ⁵D ₁Cause that the excitation band at 260 nm places possibly be by Eu ³⁺-O ^2-Charge transfer causes.After hydrogen annealing is handled, because Eu ³⁺Become Eu ²⁺, so 400 nm, the excitation band at 466 nm and 535 nm places disappears, simultaneously because Ce ³⁺Increase, the intensity of the excitation band at 260 nm places increases.Can know that by Fig. 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 handled, because 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⁺The flicker luminous intensity.Therefore, Eu ³⁺And Ce ³⁺Mixing the lanthanum yttrium oxide transparent ceramic material altogether has a wide range of applications in the scintillator field.

Claims (1)

1. Eu ³⁺And Ce ³⁺The lanthanum yttrium oxide twinkling transparent ceramics preparation methods of mixing altogether is characterized in that it has following technological process and step:

Adopt high-purity 99.99% Y ₂O ₃, 99.99%Eu ₂O ₃, 99.99%CeO ₂With 99.99% La ₂O ₃Be raw material, four mol ratio is pressed chemical formula (Ce _0.001Eu _0.01Y _0.889La _0.1) ₂O ₃Carry out weigh batching;

Will be by the good Y of 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 ball-to-powder weight ratio 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 the ball milling time is 5h;

C. ball milling is good powder is calcined mixed powder in drying in oven then in retort furnace, 1200 ℃ of insulation 10h, and naturally cooling obtains (Ce _0.001Eu _0.01Y _0.889La _0.1) ₂O ₃Powder;

D. once more powder is put into ball grinder and carry out ball milling, ball-to-powder weight ratio 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 the ball milling time is 5h;

E. ball milling is good powder carries out granulation in drying in oven with powder, crosses 40 mesh sieves;

F. the powder after the granulation is dry-pressing formed, depress to the sheet sample in the 200MP isostatic cool pressing subsequently;

G. said sample is placed in the vacuum oven, normal pressure-sintered, sintering range 1600-1700 ℃, sintering time 40-45 finally obtained fine and close (Ce in individual hour _0.001Eu _0.01Y _0.889La _0.1) ₂O ₃Pottery.

Images