CN1587196A - High light output quick attenuation flash ceramic and its preparing method - Google Patents
High light output quick attenuation flash ceramic and its preparing method Download PDFInfo
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- CN1587196A CN1587196A CN 200410053427 CN200410053427A CN1587196A CN 1587196 A CN1587196 A CN 1587196A CN 200410053427 CN200410053427 CN 200410053427 CN 200410053427 A CN200410053427 A CN 200410053427A CN 1587196 A CN1587196 A CN 1587196A
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- light output
- high light
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Abstract
The present invention relates to one kind of flash ceramic with high light output and quick attenuation and its preparation process, and belongs to the field of flash ceramic technology. The present invention features that the flash ceramic has the composition of La2Hf2-xTi2xO7, with x being 0-0.1. The present invention has low temperature combustion synthesized nanometer powder as initial powder, adopts no-pressure sintering process in hydrogen and is suitable for industrial production. The transparent flash ceramic has high light output, quick attenuation and high X-ray absorbing capacity.
Description
Technical field
The present invention relates to hafnium acid lanthanum is that matrix, titanic ion are scintillating ceramic of active ions and preparation method thereof, belongs to the scintillating ceramic field.
Background technology
X-CT (X-ray computed tomography) is a kind of important medical diagnositc equipment; X-ray detector is its core, determines its imaging performance.Current X-CT generally adopts scintillator silicon photodiode array coupled solid state detector: scintillation material becomes the energy transformation of the X ray of absorption the visible light of silicon photoelectric diode sensitivity; Visible light converts electric current to by the coupled silicon photodiode array again, and the information translation of again X ray being carried becomes image to show.
X-CT to the performance requriements of scintillator is: (1) high light output; (2) low twilight sunset; (3) high X ray receptivity; (4) low radiation damage; (5) good uniformity; (6) good mechanical processing characteristics; (7) stable chemical performance; (8) the sensitive band district of emission band silicon photoelectricity two utmost points is complementary.
The sweep velocity of the X-CT of current hommization more is faster, and this just requires scintillation material to have fast fall time.
Because imaging is to the homogeneity height of scintillator, the luminous scintillation crystal that mixes is difficult to satisfy its requirement; X-CT adopts the luminous CdWO of intrinsic
4Scintillation crystal, but CdWO
4There is the processor poor performance, shortcoming such as toxic.
Scintillating ceramic becomes a kind of new scintillation material and has obtained in the X-CT field using widely.That eighties of last century GE eighties company has at first developed is transparent (Y, Gd)
2O
3: Eu scintillating ceramic [U.S.P.4421671].(Y, Gd)
2O
3: the Eu scintillating ceramic has the scintillation properties of output of high light and low excellence such as twilight sunset and is widely used in the X-CT detector of commerce.But (Y, Gd)
2O
3: grow (about 1ms) fall time of Eu, can not satisfy the performance requriements of advanced person, rapid scanning X-CT.Gd
2O
2S:Pr, Ce, F scintillating ceramic [Ito H, Yamada H, Yoshida M, et al, Jpn.J.Appl.Phys.1988,27 (8): L1371-1373] has fast fall time (several approximately delicate) becomes second kind of ceramic scintillator that is applied to X-CT.But Gd
2O
2S is a hexagonal structure, can only prepare translucent pottery.
Prepare and a kind ofly have the output of high-density, high light and decay soon and have the scintillating ceramic that cubic structure can be used for high speed X-CT detector and just cause purpose of the present invention.
Summary of the invention
The object of the invention is to adopt in the hydrogen pressureless sintering to prepare a kind of transparent titanium ion doping hafnium acid lanthanum transparent scintillating ceramic.
Titanium ion doping hafnium acid lanthanum scintillating ceramic, its general formula is expressed as: La
2Hf
2-xTi
2xO
70＜x＜0.1.This transparent scintillating ceramic has high light and exports, decays soon and high X ray receptivity.
The powder that the present invention uses is for utilizing glycine and La (NO
3)
3, HfO (NO
3)
2, TiO (NO
3)
2Burning synthetic nanometer (10-100nm) powder.
Titanium ion doping hafnium acid lanthanum transparent scintillating ceramic provided by the invention comprises the thermal treatment of burning synthetic powder, dry-pressing or technologies such as cold isostatic compaction, sintering and annealing thermal treatment.Sintering process is characterised in that:
(1) agglomerating atmosphere is hydrogen;
(2) at 1700-1900 ℃ of insulation 4-20 hour, furnace cooling.
Its annealing process is characterised in that:
(1) annealed atmosphere is air;
(2) the annealed temperature is 1050-1200 ℃;
(3) speed of Sheng Wening is 1-5 ℃/min, the sample furnace cooling.
Adopting glycine is the nanopowder of fuel by the combustion reactions preparation, successfully makes a kind of Ti ion doping La with good transparency first by sintering process under the no press strip spare in the hydrogen
2Hf
2O
7Pottery, the heat treated sample of annealing through polishing has the favorable linearity transmitance at visible light wave range; Ceramic sintered bodies has a cube pyrochlore constitution.The scintillating ceramic that obtains has from the blue light to the green glow that (~ 400-600nm) wide emission peak, its light output is greater than CaWO
4Scintillation crystal, fall time is less than 1 millisecond.
La provided by the invention
2Hf
2O
7: Ti transparent scintillating ceramic characteristics are:
(1) La
2Hf
2O
7: the Ti crystalline ceramics has higher transmittance in its emission wavelength ranges.
(2) La
2Hf
2O
7: the Ti crystalline ceramics has high density (～7.9g/cm
3) and high X ray receptivity.
(3) La
2Hf
2O
7: the light output of Ti transparent scintillating ceramic is better than CaWO
4Scintillation crystal; Its emission band broad (~ 400-600nm), have high detection efficiency.
(4) La
2Hf
2O
7: the Ti transparent scintillating ceramic has fast fall time, satisfies high speed X-CT imaging to the scintillation material requirement of fall time.
Description of drawings
Fig. 1 is that diameter is 1.5cm, and thickness is 1.5mm agglomerating La in the hydrogen of polishing
2Hf
2O
7: the Ti ceramics sample.
Fig. 2 is that diameter is 1.5cm, thickness be 1.5mm through polishing through the heat treated La that anneals
2Hf
2O
7: the Ti ceramics sample.
Fig. 3 thickness be 1.5mm through polishing through the heat treated transparent La that anneals
2Hf
2O
7: the Ti pottery is at the transmittance curve of visible light wave range, and X-coordinate is a wavelength, the ordinate zou transmitance.
Fig. 4 is transparent La
2Hf
2O
7: the X-ray diffraction spectrum of Ti pottery shows that it is the La of purified cube of pyrochlore constitution
2Hf
2O
7Phase.
Fig. 5 is transparent La
2Hf
2O
7: the exciting and emmission spectrum of Ti scintillating ceramic.
Embodiment
Further illustrate substantial characteristics of the present invention and obvious improvement below by embodiment, yet the present invention absolutely not only is confined to described embodiment.
Embodiment 1
0.0199 mole HfO (NO
3)
2, 0.0001 mole of TiO (NO
3)
2, 0.02 mole of La (NO
3)
3Calcine under 800 ℃ of conditions with the powder of 0.054 mole of glycine combustion reactions preparation and to remove residual carbon and organism in 2 hours.Through calcination processing burning synthetic La
2Hf
2O
7Powder is earlier through waiting axial compression, again through the 180MPa isostatic pressing.The goods of isostatic pressing are incubated 6 hours in 1900 ℃ of hydrogen atmospheres.The agglomerating sample was annealed 4 hours under 1150 ℃ of conditions of air atmosphere.
The composition and the performance thereof of the transparent scintillating ceramic that obtains are as follows:
Form: La
2Hf
1.99Ti
0.01O
7
Relative density:＞99.9%
Density (g/cm
3):＞7.8
Crystalline phase (X diffraction analysis): La
2Hf
2O
7
Void content (%):＜0.1
400-800nm wave band maximum transmission (%):＞50
Light output: be better than CaWO
4Scintillation crystal
Embodiment 2
0.0198 mole HfO (NO
3)
2, 0.0002 mole of TiO (NO
3)
2, 0.02 mole of La (NO
3)
3Calcine under 800 ℃ of conditions with the powder of 0.054 mole of glycine combustion reactions preparation and to remove residual carbon and organism in 2 hours.Through calcination processing burning synthetic La
2Hf
2O
7Powder is earlier through waiting axial compression, again through the 180MPa isostatic pressing.The goods of isostatic pressing are incubated 6 hours in 1900 ℃ of hydrogen atmospheres.The agglomerating sample was annealed 4 hours under 1150 ℃ of conditions of air atmosphere.
The composition and the performance thereof of the transparent scintillating ceramic that obtains are as follows:
Form: La
2Hf
1.98Ti
0.02O
7
Relative density:＞99.9%
Density (g/cm
3):＞7.8
Crystalline phase (X diffraction analysis): La
2Hf
2O
7
Void content (%):＜0.1
400-800nm wave band maximum transmission (%):＞50
Light output: be better than CaWO
4Scintillation crystal
Fall time:＜1ms
Embodiment 3
0.0196 mole HfO (NO
3)
2, 0.0004 mole of TiO (NO
3)
2, 0.02 mole of La (NO
3)
3Calcine under 800 ℃ of conditions with the powder of 0.054 mole of glycine combustion reactions preparation and to remove residual carbon and organism in 2 hours.Through calcination processing burning synthetic La
2Hf
2O
7Powder is earlier through waiting axial compression, again through the 180MPa isostatic pressing.The goods of isostatic pressing are incubated 9 hours in 1900 ℃ of hydrogen atmospheres.The agglomerating sample was annealed 2 hours under 1200 ℃ of conditions of air atmosphere.
The composition and the performance thereof of the transparent scintillating ceramic that obtains are as follows:
Form: La
2Hf
1.96Ti
0.04O
7
Relative density:＞99.9%
Density (g/cm
3):＞7.8
Crystalline phase (X diffraction analysis): La
2Hf
2O
7
Void content (%):＜0.1
400-800nm wave band maximum transmission (%):＞50
Light output: be better than CaWO
4Scintillation crystal
Fall time:＜1ms
Embodiment 4
0.0194 mole HfO (NO
3)
2, 0.0006 mole of TiO (NO
3)
2, 0.02 mole of La (NO
3)
3Calcine under 800 ℃ of conditions with the powder of 0.054 mole of glycine combustion reactions preparation and to remove residual carbon and organism in 2 hours.Through calcination processing burning synthetic La
2Hf
2O
7Powder is earlier through waiting axial compression, again through the 180MPa isostatic pressing.The goods of isostatic pressing are incubated 9 hours in 1900 ℃ of hydrogen atmospheres.The agglomerating sample was annealed 2 hours under 1200 ℃ of conditions of air atmosphere.
The composition and the performance thereof of the transparent scintillating ceramic that obtains are as follows:
Form: La
2Hf
1.94Ti
0.05O
7
Relative density:＞99.9%
Density (g/cm
3):＞7.8
Crystalline phase (X diffraction analysis): La
2Hf
2O
7
Void content (%):＜0.1
400-800nm wave band maximum transmission (%):＞50
Light output: with CaWO
4Scintillation crystal is suitable
Fall time:＜1ms
Claims (6)
1, the fast decay of a kind of high light output scintillating ceramic is characterized in that group of ceramics becomes La
2Hf
2-xTi
2xO
70＜x＜0.1 wherein.
2, by the preparation method of the fast decay of the described a kind of high light output of claim 1 scintillating ceramic, comprise moulding, sintering process and annealing heat treatment process, it is characterized in that:
(1) adopts burning synthesis of nano Ti
4+Doping La
2Hf
2O
7Powder is as raw material;
(2) furnace cooling behind the heat preservation sintering in hydrogen of the raw material after the moulding;
(3) the agglomerating sample is annealed under the air atmosphere condition.
3, by the preparation method of the fast decay of the described a kind of high light output of claim 2 scintillating ceramic, it is characterized in that moulding process can adopt dry-pressing formed or isostatic pressing.
4, press the preparation method of the fast decay of the described a kind of high light output of claim 2 scintillating ceramic, sintering condition is 1700-1900 ℃ and is incubated 4-20 hour down.
5, by the preparation method of the fast decay of the described a kind of high light output of claim 2 scintillating ceramic, annealing conditions is 1050-1200 ℃ of annealing 2-10 hour.
6, by the preparation method of the fast decay of the described a kind of high light output of claim 2 scintillating ceramic, the powder that the present invention uses is for utilizing glycine and La (NO
3)
3, HfO (NO
3)
2, TiO (NO
3)
2Burning synthetic nanopowder.
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|---|---|---|---|
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|---|---|---|---|
| CNB2004100534274A CN100358834C (en) | 2004-08-04 | 2004-08-04 | High light output quick attenuation flash ceramic and its preparing method |
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|---|---|
| CN1587196A true CN1587196A (en) | 2005-03-02 |
| CN100358834C CN100358834C (en) | 2008-01-02 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1992599A1 (en) | 2007-05-08 | 2008-11-19 | Schott AG | Optoceramics, optical elements manufactured thereof and their use as imaging optics |
| EP2246317A1 (en) | 2009-03-31 | 2010-11-03 | Schott AG | Passive optoceramics with cubic crystal structure, process for producing the same and their use |
| CN102838352A (en) * | 2005-12-13 | 2012-12-26 | 通用电气公司 | Polycrystalline transparent ceramic articles and method of making same |
| US8872119B2 (en) | 2008-12-30 | 2014-10-28 | Saint-Gobain Ceramics & Plastics, Inc. | Ceramic scintillator body and scintillation device |
| US8877093B2 (en) | 2008-12-30 | 2014-11-04 | Saint-Gobain Ceramics & Plastics, Inc. | Ceramic scintillator body and scintillation device |
| CN107473707A (en) * | 2017-09-13 | 2017-12-15 | 景德镇陶瓷大学 | A kind of crowded mud method luminescent ceramic pug composition and preparation method thereof |
| CN110105954A (en) * | 2019-05-24 | 2019-08-09 | 厦门大学 | A kind of near-infrared light-emitting material and preparation method thereof |
| CN114195656A (en) * | 2021-11-29 | 2022-03-18 | 华南理工大学 | Large-area high-transmittance metal halide scintillating ceramic and preparation method thereof |
Families Citing this family (1)
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|---|---|---|---|---|
| CN111978087B (en) * | 2019-05-22 | 2022-04-15 | 北京理工大学 | Composite material and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5120328A (en) * | 1988-01-27 | 1992-06-09 | The Dow Chemical Company | Dense, self-reinforced silicon nitride ceramic prepared by pressureless or low pressure gas sintering |
| GB9018409D0 (en) * | 1990-08-22 | 1990-10-03 | Ici Plc | Catalysts |
| DE4033388C3 (en) * | 1990-10-20 | 1998-01-29 | Bosch Gmbh Robert | Layer system for gas sensors and method for its production |
| DE69204992T2 (en) * | 1991-02-19 | 1996-02-08 | Dow Chemical Co | SELF-ARMED SILICON NITRIDE CERAMIC WITH CRYSTALLINE GRAIN LIMIT PHASE AND METHOD FOR THE PRODUCTION THEREOF. |
| DE4427021C2 (en) * | 1994-07-29 | 1996-05-30 | Siemens Ag | Fluorescent with reduced afterglow |
| DE4427022A1 (en) * | 1994-07-29 | 1996-02-01 | Siemens Ag | Rare earth oxysulphide fluorescent substance used in radiation detectors |
-
2004
- 2004-08-04 CN CNB2004100534274A patent/CN100358834C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838352A (en) * | 2005-12-13 | 2012-12-26 | 通用电气公司 | Polycrystalline transparent ceramic articles and method of making same |
| EP1992599A1 (en) | 2007-05-08 | 2008-11-19 | Schott AG | Optoceramics, optical elements manufactured thereof and their use as imaging optics |
| DE102007022048A1 (en) | 2007-05-08 | 2008-11-20 | Schott Ag | Optoceramics, optical elements produced therefrom or their use and imaging optics |
| US7710656B2 (en) | 2007-05-08 | 2010-05-04 | Schott Ag | Optoceramics, optical elements manufactured thereof and their use as well as imaging optics |
| CN101343173B (en) * | 2007-05-08 | 2013-09-11 | 肖特公开股份有限公司 | Optoceramics, optical elements manufactured thereof and their use as imaging optics |
| US8872119B2 (en) | 2008-12-30 | 2014-10-28 | Saint-Gobain Ceramics & Plastics, Inc. | Ceramic scintillator body and scintillation device |
| US8877093B2 (en) | 2008-12-30 | 2014-11-04 | Saint-Gobain Ceramics & Plastics, Inc. | Ceramic scintillator body and scintillation device |
| EP2246317A1 (en) | 2009-03-31 | 2010-11-03 | Schott AG | Passive optoceramics with cubic crystal structure, process for producing the same and their use |
| US8343884B2 (en) | 2009-03-31 | 2013-01-01 | Schott Ag | Passive optoceramics with cubic crystal structure, process for manufacturing the same and their uses |
| CN107473707A (en) * | 2017-09-13 | 2017-12-15 | 景德镇陶瓷大学 | A kind of crowded mud method luminescent ceramic pug composition and preparation method thereof |
| CN110105954A (en) * | 2019-05-24 | 2019-08-09 | 厦门大学 | A kind of near-infrared light-emitting material and preparation method thereof |
| CN114195656A (en) * | 2021-11-29 | 2022-03-18 | 华南理工大学 | Large-area high-transmittance metal halide scintillating ceramic and preparation method thereof |
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|---|---|
| CN100358834C (en) | 2008-01-02 |
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| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Shanghai Debao Seal Co., Ltd. Assignor: Shanghai Silicates Institute, the Chinese Academy of Sciences Contract fulfillment period: 2008.2.1 to 2013.2.1 contract change Contract record no.: 2009310000096 Denomination of invention: High light output quick attenuation flash ceramic and its preparing method Granted publication date: 20080102 License type: Exclusive license Record date: 2009.6.16 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.2.1 TO 2013.2.1; CHANGE OF CONTRACT Name of requester: JOINT POWER SHANGHAI SEALS CO.,LTD. Effective date: 20090616 |
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Granted publication date: 20080102 Termination date: 20130804 |