CN107418576A - Rear-earth-doped monoclinic system gadolinium siliate salt fluorescent powder and preparation method thereof - Google Patents
Rear-earth-doped monoclinic system gadolinium siliate salt fluorescent powder and preparation method thereof Download PDFInfo
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- CN107418576A CN107418576A CN201710554453.2A CN201710554453A CN107418576A CN 107418576 A CN107418576 A CN 107418576A CN 201710554453 A CN201710554453 A CN 201710554453A CN 107418576 A CN107418576 A CN 107418576A
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- C—CHEMISTRY; METALLURGY
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7792—Aluminates
Abstract
A kind of rear-earth-doped monoclinic system gadolinium siliate salt fluorescent powder, its chemical expression are as follows：Gd2‑xSiO5：xRE；In formula RE be tri- kinds of elements of Eu, Tb, Sm in any one, x be RE substitute Gd mole, 0.01<x<0.1.Preparation method, as follows：Raw material is stoichiometrically weighed, adds 3 ~ 7wt%BaF2Grinding is uniform, is put into corundum crucible, and capping is put into calcination in heating furnace, and programming rate is 5 ~ 10 DEG C/min, and calcination temperature is 1450 ~ 1500 DEG C, and soaking time is 2 ~ 3.5 hours；Natural cooling is taken out, and fluorescent powder is obtained after grinding.Fluorescent powder luminous intensity prepared by the present invention is big, technical process is simple and easy.
Description
Technical field
The invention belongs to luminescent powder preparation field, more particularly to rare-earth activated gadolinium siliate salt fluorescent powder and preparation side
Method.
Background technology
Monoclinic system Y2SiO5（YSO）、Lu2SiO5(LSO) crystalline material is traditional optical substrates, and doping Ce has height
The advantages that light output, high Radiation Hardness, low-refraction (internal reflection loss is small), medium/high density and effective atomic number, general it can answer
For application fields such as oil well detection, nuclear medical imaging (PET) and high-energy physics nuclear physics；It can be used as after doping Yb excellent
Wide range emitting laser；Er, Yb codope light available for the infrared upper conversion to visible ray, and quantum-cutting effect is extremely bright
It is aobvious.YSO, LSO, GSO vitreum are prepared using conventional melt cooling technology and also show the splendid transparency（Li Jing, it is highly crystalline
The Study on Preparation Technology Central South University of degree transparent glass-ceramics, 2011）.Due to YSO, LSO show good heat-proof quality and
Corrosion resisting property under hot conditions, its thin-film material can be used for thermal barrier coating（Byung-Koog Jang, et al. Surface
& Coatings Technology 2016,308 :24–30; Jia Liu,et al. Journal of the European
Ceramic Society 2013,33: 3419–3428; Zhilin Tian, Journal of the European
Ceramic Society 2015,35:1923–1932; Zhilin Tian, Journal of the European
Ceramic Society 2016,36: 189–202）.It is less to powder morphology YSO, LSO correlative study, and concentrate on Eu3+、
Tb3+、Ce3+、Sm3+、Tm3+（X.M. Han, et al. Solid State Sciences 2004,6：349–355; Y. Liu,
et al. Optical Materials 2004,25: 243–250）Research after doping.Jiaguo Wang et al. have found
RE2SiO5X1 types be present in (R=Y, La-Lu)（Low-temperature phase, P21/C）With X2 types (high-temperature-phase, C2/C), group when prepared by sol-gel process
Divide and temperature influences greatly, and for+3 ~+4 valency changeable valence rare earth ions on crystalline phase（Such as Tb）It is difficult to keep+trivalent, it is necessary to using weak
Reducing atmosphere（Jiaguo Wang. Materials Research Bulletin 2001,36：1855–1861）.
Due to (Y1-xGdx)2SiO5（YGSO）、(Lu1-xGdx)2SiO5(LGSO) crystal can also show good optics base
Volume property, people begin to focus on Gd2SiO5（GSO）Optical substrates material.Czochralski method prepares GSO:Its scintillation crystal of Ce（It is situated between bright
The artificial lens journals such as print, 2005,34: 136-143）, light output is that more than twice of BGO crystal, optical attenuation are about BGO crystalline substances
Body 1/7, higher Radiation Hardness, low-refraction and big density and effective atomic number etc., be widely used in oil well detection,
The application field such as nuclear medical imaging (PET) and high-energy physics nuclear physics；GSO:Yb is used as wide range laser（Ning Kaijie, etc. people
Work crystal journal, 2011,40:817-827）Also superperformance is shown；And to GSO:Er, Yb crystalline material are also showed on good
Convert illumination effect（In the rear-earth-doped laser crystals of Han Lin radiationless mechanism research and its influence to ionoluminescence property,
Nankai University, 2009）.It is less in GSO research accumulation in general, YSO and LSO is come from mostly, and focus mostly in crystal, glass
Glass, ceramic material, the research of its powder body material is relatively weak, and rare earth ion doped species also focuses on Eu ions.Such as：Using
Bridgman methods（Chen Yonghu, nuclear technology, 2002,25:788-792）And sol-gal process（Bing Yan, Colloids and
Surfaces A: Physicochem. Eng. Aspects 287 (2006) 158–162）It is prepared for Gd2SiO5:Eu3+It is high
Vacuum VUV excites high-efficiency fluorescence powder, and (PDP) and non-mercury florescent lamp are shown for plasma flat；Sun Haiying etc. uses high temperature
Solid phase method is with Gd2O3、SiO2、Eu2O3For raw material BaF2This red fluorescence powder is also successfully prepared for fluxing agent（Sun Haiying, Changchun
Polytechnics's journal（Natural science edition）, 2013,36：87-89）；The high temperature solid-state method H such as Song Jialan3SiO3、Y2O3、Gd2O3、
Eu2O3Gd is prepared for raw material1.95-xYxSiO5:Eu red fluorescence powders（Luminous journal, 2000,21:145-149）.
The content of the invention
The purpose of the present invention is to propose to a kind of rear-earth-doped monoclinic system gadolinium siliate salt fluorescent powder and preparation method thereof.
The chemical expression of rear-earth-doped monoclinic system gadolinium siliate salt fluorescent powder of the present invention is as follows：
Gd2-xSiO5：xRE
In formula RE be tri- kinds of elements of Eu, Tb, Sm in any one, x be RE substitute Gd mole, 0.01<x<0.1.When RE is
During Eu, lower transmitting red fluorescence is excited in 277nm, 396nm, 466nm (main peak value is 620nm).When RE is Tb, 247nm,
277nm, 315nm excite lower transmitting green fluorescence (main peak value is 548nm).When RE is Sm, excites and issue in 292nm, 402nm
Penetrate pink fluorescence (main peak value is 602nm).
The preparation method of a kind of rear-earth-doped monoclinic system gadolinium siliate salt fluorescent powder of the present invention, by following step
Suddenly：Raw material is stoichiometrically weighed, adds 3 ~ 7wt% BaF2Grinding is uniform, is put into corundum crucible, and capping is put into heating furnace
Middle calcination, programming rate are 5 ~ 10 DEG C/min, and calcination temperature is 1450 ~ 1500 DEG C, and soaking time is 2 ~ 3.5 hours；Naturally it is cold
But take out, fluorescent powder is obtained after grinding.
The present invention uses solid sintering technology under weakly reducing atmosphere to prepare fluorescent powder, and raw materials used is rare earth oxide
（99.95%）, silicon monoxide（99.0%, analysis is pure）, its weakly reducing atmosphere provides by silicon monoxide.
Fluorescent powder luminous intensity prepared by the present invention is big, technical process is simple and easy.
Brief description of the drawings
Gd prepared by Fig. 1 embodiments 12SiO5Powder XRD spectrum, abscissa are 2 θ（0）, ordinate is intensity (a.u.).
Gd prepared by Fig. 2 embodiments 2,32-xSiO5：XEu red fluorescence powders excite and launched fluorescence spectrum, and abscissa is
Wavelength（nm）, ordinate is luminous intensity (a.u.).
Gd prepared by Fig. 3 embodiments 4,52-xSiO5：XTb Green phosphors excite and launched fluorescence spectrum, and abscissa is
Wavelength（nm）, ordinate is luminous intensity (a.u.).
Gd prepared by Fig. 4 embodiments 6,72-xSiO5：XSm pink colour fluorescent powders excite and launched fluorescence spectrum, and abscissa is
Wavelength（nm）, ordinate is luminous intensity (a.u.).
Embodiment
The present invention will be further described with the following Examples.
Embodiment 1.
36.26g gadolinium oxides, 4.2g silicon monoxides are taken, adds 3wt% BaF2Grinding is uniform, is put into corundum crucible, is capped
Calcination in heating furnace is put into, programming rate is 5 ~ 10 DEG C/min, and calcination temperature is 1450 DEG C, and soaking time is 3 hours；Naturally it is cold
But take out, Gd is obtained after grinding2SiO5Powder.Fig. 1 is the XRD of powder.
Embodiment 2.
35.90g gadolinium oxides, 4.2g silicon monoxides are taken, 0.35 europium oxide, adds 4wt% BaF2Grinding is uniform, is put into corundum
In crucible, capping is put into calcination in heating furnace, and programming rate is 5 ~ 10 DEG C/min, and calcination temperature is 1500 DEG C, soaking time 2
Hour；Natural cooling is taken out, and Gd is obtained after grinding1.98SiO5:0.02Eu powders.Fig. 2 be fluorescent material 277nm, 396nm,
466nm excites lower transmitting red fluorescence (main peak value is 620nm).
Embodiment 3.
34.81g gadolinium oxides, 4.2g silicon monoxides are taken, 1.41 europium oxides, adds 5wt% BaF2Grinding is uniform, is put into corundum
In crucible, capping is put into calcination in heating furnace, and programming rate is 5 ~ 10 DEG C/min, and calcination temperature is 1500 DEG C, soaking time 2
Hour；Natural cooling is taken out, and Gd is obtained after grinding1.92SiO5:0.08Eu powders.Fig. 2 be fluorescent material 277nm, 396nm,
466nm excites lower transmitting red fluorescence (main peak value is 620nm).
Embodiment 4.
36.14g gadolinium oxides, 4.2g silicon monoxides are taken, 0.2 terbium oxide, adds 6wt% BaF2Grinding is uniform, is put into corundum
In crucible, capping is put into calcination in heating furnace, and programming rate is 5 ~ 10 DEG C/min, and calcination temperature is 1450 DEG C, and soaking time is
3.5 hour；Natural cooling is taken out, and Gd is obtained after grinding1.99SiO5:0.01Tb powders.Fig. 3 be fluorescent material 247nm, 277nm,
315nm excites lower transmitting green fluorescence (main peak value is 548nm).
Embodiment 5.
34.99g gadolinium oxides, 4.2g silicon monoxides are taken, 1.41 terbium oxides, adds 3wt% BaF2Grinding is uniform, is put into corundum
In crucible, capping is put into calcination in heating furnace, and programming rate is 5 ~ 10 DEG C/min, and calcination temperature is 1450 DEG C, and soaking time is
3.5 hour；Natural cooling is taken out, and Gd is obtained after grinding1.93SiO5:0.07Tb powders.Fig. 3 be fluorescent material 247nm, 277nm,
315nm excites lower transmitting green fluorescence (main peak value is 548nm).
Embodiment 6.
35.72g gadolinium oxides, 4.2g silicon monoxides are taken, 0.52 samarium oxide, adds 5wt% BaF2Grinding is uniform, is put into corundum
In crucible, capping is put into calcination in heating furnace, and programming rate is 5 ~ 10 DEG C/min, and calcination temperature is 1450 DEG C, soaking time 3
Hour；Natural cooling is taken out, and Gd is obtained after grinding1.97SiO5:0.03Sm powders.Fig. 4 is that fluorescent material excites in 292nm, 402nm
The lower pink fluorescence of transmitting (main peak value is 602nm).
Embodiment 7.
35.17g gadolinium oxides, 4.2g silicon monoxides are taken, 1.05 samarium oxides, adds 5wt% BaF2Grinding is uniform, is put into corundum
In crucible, capping is put into calcination in heating furnace, and programming rate is 5 ~ 10 DEG C/min, and calcination temperature is 1450 DEG C, soaking time 3
Hour；Natural cooling is taken out, and Gd is obtained after grinding1.94SiO5:0.06Sm powders.Fig. 4 is that fluorescent material excites in 292nm, 402nm
The lower pink fluorescence of transmitting (main peak value is 602nm).
Stoichiometry/technological parameter of each embodiment of table/luminescent properties contrast
Claims (3)
- A kind of 1. rear-earth-doped monoclinic system gadolinium siliate salt fluorescent powder, it is characterized in that chemical expression is as follows：Gd2-xSiO5：xREIn formula RE be tri- kinds of elements of Eu, Tb, Sm in any one, x be RE substitute Gd mole, 0.01<x<0.1.
- 2. a kind of preparation method of rear-earth-doped monoclinic system gadolinium siliate salt fluorescent powder described in claim 1, it is characterized in that As follows：Raw material is stoichiometrically weighed, adds 3 ~ 7wt% BaF2Grinding is uniform, is put into corundum crucible, capping is put Enter calcination in heating furnace, programming rate is 5 ~ 10 DEG C/min, and calcination temperature is 1450 ~ 1500 DEG C, and soaking time is 2 ~ 3.5 small When；Natural cooling is taken out, and fluorescent powder is obtained after grinding.
- 3. a kind of preparation method of rear-earth-doped monoclinic system gadolinium siliate salt fluorescent powder according to claim 2, it is special Sign is that raw material is rare earth oxide and silicon monoxide.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230582A (en) * | 1998-03-26 | 1999-10-06 | 中国科学院长春物理研究所 | Fluorescent nanometer rare earth oxide powder and its preparation |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230582A (en) * | 1998-03-26 | 1999-10-06 | 中国科学院长春物理研究所 | Fluorescent nanometer rare earth oxide powder and its preparation |
Non-Patent Citations (2)
| Title |
|---|
| 孙海鹰 等: "Gd2SiO5：Eu3+红色荧光粉的制备与发光性能的研究", 《长春理工大学学报（自然科学版）》 * |
| 李建宇: "《稀土发光材料及其应用》", 31 October 2003, 化学工业出版社 * |
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Application publication date: 20171201 |