CN104177092A - Method for preparing transparent luminescent ceramic - Google Patents
Method for preparing transparent luminescent ceramic Download PDFInfo
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- CN104177092A CN104177092A CN201310188444.8A CN201310188444A CN104177092A CN 104177092 A CN104177092 A CN 104177092A CN 201310188444 A CN201310188444 A CN 201310188444A CN 104177092 A CN104177092 A CN 104177092A
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- sintering
- ion
- ceramic
- luminescent
- transparent
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Abstract
The invention discloses a method for preparing transparent luminescent ceramic. The method includes the steps of burdening, preparing a blank, sintering and annealing, the burdening step is characterized in that composition raw materials are weighed according to the stoichiometric ratio of the general formula of the transparent luminescent ceramic, are ball-milled and are mixed. A compound with the structural general formula of RX is used simultaneously as a sintering aid and a luminescent activated ion composition raw material, wherein R represents the luminescent ion, and X represents a volatile anion. The method can effectively avoid the introduction of other heterogeneous impurities in order to avoid the influences of the introduction of defects on the carrier transfer process, so the transparent luminescent ceramic with high purity and high optical quality is obtained in order to meet the requirements of the performances of LED luminescent materials, high energy flash detection materials and laser gain medium materials, and has an application prospect and practical values.
Description
Technical field
The present invention relates to a kind of preparation method of transparent luminescent ceramic, belong to optical ceramics technical field of material.
Background technology
Luminescent material is excited after (ray, high energy particle, electron beam, external electric field etc.) when certain material, and material will be in excited state, and the energy of excited state can discharge by the form of light or heat.If the energy of this part is to be positioned at visible, ultraviolet or near infrared electromagnetic radiation, this process is referred to as luminescence process.Rare earth ion has the incomparable spectral quality of general element because of its special electron structure, rare earth luminous nearly cover whole fields of solid luminescence, rare earth luminescent material has many advantages: photoluminescent band is narrow, purity of color is high, bright in luster; Light absorpting ability is strong, and efficiency of conversion is high; Emission wavelength range of distribution field width; Fluorescence lifetime reaches 6 orders of magnitude from crossing millisecond nanosecond; Physics and chemistry stable in properties, high temperature resistant, can bear great-power electronic bundle, high-energy radiation and the effect of UV-light by force.These excellent performances just, become rare earth compound to seek the main study subject of advanced luminescent material.At present, rare earth luminescent material is widely used in laser, and the field such as detection and record of illumination, demonstration, video picture, medical radiology image, radiation field has formed very large industrial production and consumption market scale, and other new technique field expansion of forward.
Crystalline ceramics, from the sixties in last century, has also passed through semicentennial development, is successively developed into transparent laser ceramic, transparent scintillating ceramic, transparent optical pottery etc.Particularly to nineteen ninety-five, by [Journal of the American Ceramic Society such as Ikesue, 1995.78 (4): p.1033-1040.] taking high-purity yttrium oxide and aluminum oxide as raw material, through isostatic pressing, adopt high-temperature solid phase reaction method to prepare YAG and the Nd:YAG pottery of highly transparent and realized Laser output.At present, crystalline ceramics prepared by solid state reaction sintering technology adopts out-phase sintering aid with acceleration of sintering more, MgO, SiO
2deng being widely adopted as sintering aid [Journal of Alloys and Compounds, 2010.502 (1): p.225-230.], but this positively charged ion sintering aid is as heterogeneous impurity, bring new out-phase cation element, after sintering, can remain in ceramic sintered bodies, thereby cannot get rid of, ceramic optics and luminescent properties be exerted an influence.Document [Journal of the American Ceramic Society, 2012.95 (7): p.2130-2132.], reported the impact of heterogeneous sintering aid for the flicker of crystalline ceramics, luminous or even laser military service performance.Research shows, owing to having added heterogeneous sintering aid, residual impurity atoms can produce great negative impact to ceramic scintillation properties, the introducing of impurity element can form defect center, compete with luminescence process, and can capture the current carrier transporting, thereby reduce luminous efficiency and the scintillation properties of luminescence center.
Summary of the invention
For the problems referred to above and the defect of prior art existence, the object of this invention is to provide a kind of method of the transparent luminescent ceramic that can prepare high-purity high optical quality that there is no out-phase impurity.
For achieving the above object, the technical solution used in the present invention is as follows:
Prepare a method for transparent luminescent ceramic, comprise batching, prepare biscuit, sintering and anneal step, described batching is the each constitutive material that takes stoichiometric ratio according to the composition general formula of prepared transparent luminescent ceramic, carries out ball milling and mixes; It is characterized in that: the compound using general structure as RX is simultaneously as the constitutive material of sintering aid and activation ion, and R wherein represents light emitting ionic, and X wherein represents volatile negatively charged ion.
As a kind of preferred version, described R is that rare earth ion is or/and transition metal ion.
As further preferred version, described R is selected from Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Cr
4+, Ti
4+and Mn
4+at least one in ion.
As a kind of preferred version, described X is selected from F
-, Cl
-, Br
-, I
-, O
2-, S
2-, N
3-, P
3-in at least one.
As a kind of preferred version, the preparation of biscuit adopts at least one in dry pressing, isostatic cool pressing method, colloidal formation method, slip casting, gel injection method, electrophoretic deposition.
As a kind of preferred version, described sintering adopts at least one in vacuum sintering, atmosphere sintering, hot pressed sintering.
As further preferred version, described hot pressed sintering atmosphere is the mixed atmosphere of nitrogen atmosphere or hydrogen and air.
As further preferred version, described sintering temperature is 1450～1900 DEG C, and sintering time is 5～50 hours.
As a kind of preferred version, described anneal is carried out in air or in oxygen.
As further preferred version, described annealing temperature is 1000～1650 DEG C, and annealing time is 5～50 hours.
Transparent luminescent ceramic of the present invention includes but not limited to transparent laser ceramic, transparent scintillating ceramic, transparent optical pottery, for example: can be RE for disclosed structural formula in Chinese patent CN200610025536.4
3xlu
3(1-x) Al
5o
12luetcium aluminum garnet-base transparent ceramic, also can be for disclosed structural formula in Chinese patent application CN200910047340.9 is 3mR, 3nR ': (A
1-m-n-xa '
x)
3(B
yc
1-y)
5o
12the transparent scintillating ceramic of garnet structure.
Compared with prior art, the present invention has following beneficial effect:
The present invention first the compound using general structure as RX simultaneously as the constitutive material of sintering aid and activation ion, R wherein represents light emitting ionic, X wherein represents volatile negatively charged ion, makes light emitting ionic enter lattice by solid solution on the one hand, becomes luminescence center; The ionic radius difference of utilizing on the other hand negatively charged ion, produces lattice distortion by sintering, promotes ion diffusive migration, and acceleration of sintering, then gets rid of negatively charged ion outside ceramic body completely in the sintering later stage; Can effectively avoid the introducing of other out-phase impurity, thereby avoid introducing defect and carrier transport process is exerted an influence, can obtain high-purity transparent luminescent ceramic with high light quality, to meet the performance requriements of LED luminescent material, high energy flash detection material and gain medium material, there is application prospect and practical value.
Brief description of the drawings
Fig. 1 is the photo in kind of embodiment 1 prepared transparent scintillating ceramic;
Fig. 2 is the transmittance curve of embodiment 1 prepared transparent scintillating ceramic;
Fig. 3 is X-ray diffraction (XRD) spectrogram of embodiment 1 prepared transparent scintillating ceramic;
Fig. 4 is the surface topography map (SEM photo) of the prepared transparent scintillating ceramic of embodiment 1 after polish etch;
Fig. 5 is the excitation-emission curve of embodiment 1 prepared transparent scintillating ceramic;
Fig. 6 is the X ray luminous intensity figure of embodiment 1 prepared transparent scintillating ceramic.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only for the present invention is described but not limit the scope of the invention.
Embodiment 1: preparation Pr:Lu
3al
5o
12transparent scintillating ceramic
Adopt commercially available high pure raw material: by (Pr
0.005lu
0.9995)
3al
5o
12stoichiometric ratio take Al
2o
3(99.99%), Lu
2o
3(99.99%), PrF
3(99.99%) respectively form powder raw material, adopt water or ethanol to do ball-milling medium, with high-purity Al
2o
3ball does ball-milling medium, with rotational speed of ball-mill ball milling 5～24h of 100～350rpm; After slurry drying is sieved, adopt cold isostatic compaction technology (pressure is not less than 150MPa) to be pressed into biscuit; By biscuit sintering under vacuum condition: be first incubated 1～5 hour at 1500～1650 DEG C, to accelerate negatively charged ion diffusive migration speed, promote solid state reaction, then be incubated 5～50 hours at 1700～1850 DEG C, negatively charged ion is excreted, obtain high-purity ceramic of compact; Then in air at 1000～1650 DEG C anneal 5～50 hours, excrete the oxygen room of introducing to compensate negatively charged ion, finally obtain the Pr:Lu of high-purity compact
3al
5o
12transparent scintillating ceramic.
Fig. 1 is the photo in kind of the obtained pottery of the present embodiment, and Fig. 2 is the transmittance curve of the obtained pottery of the present embodiment, from Fig. 1 and Fig. 2: the obtained pottery of the present embodiment is transparent at visible light wave range, and transmitance can reach more than 70%.
Fig. 3 is X-ray diffraction (XRD) spectrogram of the obtained pottery of the present embodiment, as seen from Figure 3: the obtained pottery of the present embodiment has garnet phase structure.
Fig. 4 is the surface topography map (SEM photo) of the obtained pottery of the present embodiment after polish etch, as seen from Figure 4: the obtained pottery of the present embodiment has uniform crystal grain and distributes.
Fig. 5 is the excitation-emission curve of the obtained pottery of the present embodiment, as seen from Figure 5: the obtained pottery of the present embodiment exists emission peak at 313nm place, is Pr
3+the feature 5d-4f emission peak of ion.
Fig. 6 is the X ray luminous intensity figure of the obtained pottery of the present embodiment, as seen from Figure 6: the luminous quantum efficiency of the obtained pottery of the present embodiment is high, is the more than 50 times of BGO.
Embodiment 2: preparation Nd:YAG transparent laser ceramic
Adopt commercially available high pure raw material: by (Nd
0.01y
0.99)
3al
5o
12stoichiometric ratio take Al
2o
3(99.99%), Y
2o
3(99.99%), NdF
3(99.99%) respectively form powder raw material, adopt water or ethanol to do ball-milling medium, with high-purity Al
2o
3ball does ball-milling medium, with rotational speed of ball-mill ball milling 5～24h of 100～350rpm; After slurry drying is sieved, adopt cold isostatic compaction technology (pressure is not less than 150MPa) to be pressed into biscuit; Biscuit is incubated to 5～50 hours under vacuum condition at 1700～1850 DEG C, then in air at 1000～1650 DEG C anneal 5～50 hours, obtain the Nd:YAG transparent laser ceramic of high-purity compact.
Visible in sum: the compound while of the present invention using general structure as RX is as the constitutive material of sintering aid and activation ion, R wherein represents light emitting ionic, X wherein represents volatile negatively charged ion, makes light emitting ionic enter lattice by solid solution on the one hand, becomes luminescence center; The ionic radius difference of utilizing on the other hand negatively charged ion, produces lattice distortion by sintering, promotes ion diffusive migration, and acceleration of sintering, then gets rid of negatively charged ion outside ceramic body completely in the sintering later stage; Can effectively avoid the introducing of other out-phase impurity, thereby avoid introducing defect and carrier transport process is exerted an influence, can obtain high-purity transparent luminescent ceramic with high light quality, there is application prospect and practical value.
Finally be necessary described herein: above embodiment, only for technical scheme of the present invention is described in more detail, can not be interpreted as limiting the scope of the invention; Some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (10)
1. prepare a method for transparent luminescent ceramic, comprise batching, prepare biscuit, sintering and anneal step, described batching is the each constitutive material that takes stoichiometric ratio according to the composition general formula of prepared transparent luminescent ceramic, carries out ball milling and mixes; It is characterized in that: the compound using general structure as RX is simultaneously as the constitutive material of sintering aid and activation ion, and R wherein represents light emitting ionic, and X wherein represents volatile negatively charged ion.
2. the method for claim 1, is characterized in that: described R is that rare earth ion is or/and transition metal ion.
3. method as claimed in claim 2, is characterized in that: described R is selected from Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Cr
4+, Ti
4+and Mn
4+at least one in ion.
4. the method for claim 1, is characterized in that: described X is selected from F
-, Cl
-, Br
-, I
-, O
2-, S
2-, N
3-, P
3-in at least one.
5. the method for claim 1, is characterized in that: the preparation of biscuit adopts at least one in dry pressing, isostatic cool pressing method, colloidal formation method, slip casting, gel injection method, electrophoretic deposition.
6. the method for claim 1, is characterized in that: described sintering adopts at least one in vacuum sintering, atmosphere sintering, hot pressed sintering.
7. method as claimed in claim 6, is characterized in that: described hot pressed sintering atmosphere is the mixed atmosphere of nitrogen atmosphere or hydrogen and air.
8. method as claimed in claim 6, is characterized in that: described sintering temperature is 1450～1900 DEG C, and sintering time is 5～50 hours.
9. the method for claim 1, is characterized in that: described anneal is carried out in air or in oxygen.
10. method as claimed in claim 9, is characterized in that: described annealing temperature is 1000～1650 DEG C, and annealing time is 5～50 hours.
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|---|---|---|---|
| CN201310188444.8A CN104177092A (en) | 2013-05-20 | 2013-05-20 | Method for preparing transparent luminescent ceramic |
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|---|---|---|---|
| CN201310188444.8A CN104177092A (en) | 2013-05-20 | 2013-05-20 | Method for preparing transparent luminescent ceramic |
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Family
ID=51958477
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316373A (en) * | 2016-07-29 | 2017-01-11 | 江苏罗化新材料有限公司 | Preparing method for high power illuminant fluoride florescent and crystalline ceramics |
| CN113548894A (en) * | 2021-07-15 | 2021-10-26 | 中国科学院上海硅酸盐研究所 | Ytterbium-yttria up-conversion luminescent transparent ceramic and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514100A (en) * | 2009-03-10 | 2009-08-26 | 中国科学院上海硅酸盐研究所 | Twinkling transparent ceramics system with garnet structure and preparation method thereof |
| CN102826850A (en) * | 2012-08-20 | 2012-12-19 | 长春理工大学 | Barium fluoride up-conversion transparent ceramic and preparation method thereof |
-
2013
- 2013-05-20 CN CN201310188444.8A patent/CN104177092A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514100A (en) * | 2009-03-10 | 2009-08-26 | 中国科学院上海硅酸盐研究所 | Twinkling transparent ceramics system with garnet structure and preparation method thereof |
| CN102826850A (en) * | 2012-08-20 | 2012-12-19 | 长春理工大学 | Barium fluoride up-conversion transparent ceramic and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄毅华: "Nd3+，La3+共掺杂氧化钇透明陶瓷的制备及其性能", 《无机化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316373A (en) * | 2016-07-29 | 2017-01-11 | 江苏罗化新材料有限公司 | Preparing method for high power illuminant fluoride florescent and crystalline ceramics |
| CN113548894A (en) * | 2021-07-15 | 2021-10-26 | 中国科学院上海硅酸盐研究所 | Ytterbium-yttria up-conversion luminescent transparent ceramic and preparation method thereof |
| CN113548894B (en) * | 2021-07-15 | 2022-09-06 | 中国科学院上海硅酸盐研究所 | Ytterbium-yttria up-conversion luminescent transparent ceramic and preparation method thereof |
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Application publication date: 20141203 |