CN101629078B - Method for preparing cubic shape green luminescent material of lanthanum zirconate doped with cerium and terbium - Google Patents
Method for preparing cubic shape green luminescent material of lanthanum zirconate doped with cerium and terbium Download PDFInfo
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- CN101629078B CN101629078B CN2009101021470A CN200910102147A CN101629078B CN 101629078 B CN101629078 B CN 101629078B CN 2009101021470 A CN2009101021470 A CN 2009101021470A CN 200910102147 A CN200910102147 A CN 200910102147A CN 101629078 B CN101629078 B CN 101629078B
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Abstract
The invention discloses a method for preparing a cubic shape green luminescent material of lanthanum zirconate doped with cerium and terbium. The method comprises the following steps: dissolving lanthanum nitrate, cerium nitrate and terbium nitrate in deionized water according to the mole ratio and stirring; adding PVP into the solution, controlling the concentration of the mass percent of the PVP at 0.25-1% and stirring; adding zirconium acetate into the solution, controlling the mole number of the zirconium acetate and the mole number of the total rare earth cation to be equivalent, adding a sodium hydroxide solution drops by drops to obtain a white precipitate and controlling the pH value of the solution at 6-9; putting the solution into a high-pressure kettle, taking the filling degree at 80% and processing for 6-40 hours at 180-220 DEG C; and centrifugalizing and drying the processed solution to obtain the cubic shape green luminescent material of lanthanum zirconate doped with cerium and the terbium.
Description
Technical field
The present invention relates to a kind of preparation method of cubic shape green luminescent material of lanthanum zirconate doped with cerium and terbium.
Background technology
Rare earth zirconate (Re
2Zr
2O
7) purposes is very extensive, and have a lot of special performances, have HMP, macroion electroconductibility, high chemical stability, high catalytic activity etc. like the zirconic acid lanthanum as a kind of functional materials.
The zirconic acid lanthanum is as thermal barrier coating, because very low thermal conductivity, higher chemicalstability and the series of advantages of working as with the yttria-stabilized zirconia ceramic phase such as hot expansibility, at present by broad research.Use this thermal barrier coating can improve its working temperature such as, internal combustion turbine, improve motor power, reduce oil consumption, prolongs life, the simplified design complexity reduces the requirement of body material etc.The zirconic acid lanthanum still is a kind of good catalyzer, is widely used in the photochemical catalysis aspect.Its matrix as embedded photoluminescent material comes into one's own, but, but correlative study is also less.
Rare earth zirconic acid lanthanum has advantages such as higher thermostability, low heat conductivity, sintering temperature be relatively low as the matrix of luminescent material.The preparation method of common rare earth luminescent material has: high temperature solid-phase sintering method, coprecipitation method, sol-gel method, hydrothermal method etc.Wherein simple, the product advantages of good crystallization of hydrothermal method technology, product purity are higher, and temperature of reaction is relatively low.So far, also less relatively about the zirconic acid lanthanum as the research of luminescent material matrix, also more single to the research of its preparation, mainly be main [AiyuZhang, et al, Systematic research on RE with the sol-gel method
2Zr
2O7 (RE=La, Nd, Eu and Y) nanocrystals:Preparation, structure and photoluminescence characterization, Solid State Sciences, 10 (2008) 74-81], hydrothermal method is synthetic relatively seldom.
Summary of the invention
The object of the present invention is to provide a kind of cubic lanthanum zirconate doped with cerium and terbium (La
2Zr
2O
7: Ce, the Tb) preparation method of green luminescent material adopts hydro-thermal technology, through adding the auxiliary of PVP tensio-active agent, has realized the synthetic of cubic shape green luminescent material of lanthanum zirconate doped with cerium and terbium.
The step of the technical scheme that the present invention adopts is following:
1) Lanthanum trinitrate, cerous nitrate, Terbium trinitrate are dissolved in the deionized water, the mole number of control cerous nitrate is 1%～5% of a total rare earth cation mole number, and the mole number of control Terbium trinitrate is 5%～8% of a total rare earth cation mole number, stirs;
2) in above-mentioned solution, add PVP, the mass percent concentration of control PVP is 0.25%～1%, stirs;
3) in above-mentioned solution, add the acetic acid zirconium, the mole number of acetic acid zirconium equates with above-mentioned total rare earth cation mole number, stirs;
4) dropwise add sodium hydroxide solution and generate white precipitate, the pH value of control solution is 6～9, continues to stir;
5) with the above-mentioned solution autoclave of packing into, adopt hydro-thermal technology, the solution centrifugal of handling well, drying obtain cubic shape green luminescent material of lanthanum zirconate doped with cerium and terbium.
Said hydro-thermal technology, temperature are controlled to be 180～220 ℃, and the treatment time is 6～40 hours.
The beneficial effect that the present invention has is:
The present invention is to be reactant with Lanthanum trinitrate, cerous nitrate, Terbium trinitrate and acetic acid zirconium; Add the PVP tensio-active agent; Sodium hydroxide, synthesizes granule-morphology and is cubic green luminescent material of lanthanum zirconate doped with cerium and terbium through hydro-thermal technology as mineralizer under 180～220 ℃.The more traditional high temperature solid-phase sintering method of its synthesis temperature has remarkable reduction.It has certain significance to exploring rare earth zirconate as the research of luminescent material matrix.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 products therefrom.
Fig. 2 is the stereoscan photograph of embodiment 1 products therefrom.
Fig. 3 embodiment 1 products therefrom pl-emmission spectrum.
Fig. 4 implements the stereoscan photograph of Comparative Examples 1 products therefrom.
Embodiment
Embodiment 1:
Get 1.1691 gram Lanthanum trinitrate (La (NO respectively
3)
36H
2O), 0.0651 gram cerous nitrate (Ce (NO
3)
36H
2O), 0.068 gram Terbium trinitrate (Tb (NO
3)
36H
2O) be dissolved in 40 ml deionized water, the volumetric molar concentration of Lanthanum trinitrate, cerous nitrate, Terbium trinitrate is respectively 0.0675 mol, 0.0038 mol, 0.0038 mol; In above-mentioned solution, add PVP (Vinylpyrrolidone polymer K30) 0.1 gram, the mass percent concentration of PVP is 0.25%, stirs.Get 0.465 milliliter of acetic acid zirconium (Yutai County reaches fine chemistry industry clearly) and be dissolved in 40 ml deionized water, the volumetric molar concentration of acetic acid zirconium is 0.079 mol, and 40 milliliters of zirconium acetate solutions are dropwise added above-mentioned nitrate mixed solution, stirs.In above-mentioned mixing solutions, dropwise add sodium hydroxide under the whipped state, to white precipitate regeneration not.Regulator solution pH is 6, continues to stir 0.5 hour.Put into the teflon-lined autoclave to the above-mentioned solution for preparing, compactedness is 80%, and the liner volume is 100 milliliters.This solution was handled 20 hours down at 180 ℃, the solution centrifugal of handling well, drying, obtained required product.Fig. 1 is the XRD figure spectrum of this routine products therefrom, each diffraction peak position and La among the figure
2Zr
2O
7Standard card (JCPDSNO.71-2363) unanimity, the variation that does not cause structure of mixing of Ce, Tb is described.Fig. 2 is its stereoscan photograph, can know and see La
2Zr
2O
7: Ce, Tb are cubic, about 1～2 micron of its length.Fig. 3 is its pl-emmission spectrum, has sharp-pointed green emission spectrum in 545 nanometers.
Embodiment 2:
Get 1.5761 gram Lanthanum trinitrate (La (NO respectively
3)
36H
2O), 0.01736 gram cerous nitrate (Ce (NO
3)
36H
2O), 0.1450 gram Terbium trinitrate (Tb (NO
3)
36H
2O) be dissolved in 40 ml deionized water, Lanthanum trinitrate, cerous nitrate, Terbium trinitrate volumetric molar concentration are respectively 0.1 mol, 0.001 mol, 0.008 mol; In above-mentioned solution, add PVP (Vinylpyrrolidone polymer K30) 0.2 gram, the mass percent concentration of PVP is 0.5%, stirs.Get acetic acid zirconium (Yutai County reaches fine chemistry industry clearly) and be dissolved in 40 ml deionized water for 0.66 milliliter, the volumetric molar concentration of acetic acid zirconium is 0.113 mol, and 40 milliliters of zirconium acetate solutions are dropwise added above-mentioned nitrate mixed solution, stirs.Whipped state dropwise adds sodium hydroxide in above-mentioned mixing solutions, to white precipitate regeneration not.Regulator solution pH is 7, continues to stir 0.5 hour.Put into the teflon-lined autoclave to the above-mentioned solution for preparing, compactedness is 80%, and the liner volume is 100 milliliters.This solution was handled 6 hours down at 220 ℃, the solution centrifugal of handling well, drying, obtained required product.
Embodiment 3:
Get 3.464 gram Lanthanum trinitrate (La (NO respectively
3)
36H
2O), 0.0771 gram cerous nitrate (Ce (NO
3)
36H
2O), 0.3221 gram Terbium trinitrate (Tb (NO
3)
36H
2O) be dissolved in 40 ml deionized water, Lanthanum trinitrate, cerous nitrate, Terbium trinitrate volumetric molar concentration are respectively 0.2 mol, 0.004 mol, 0.017 mol; In above-mentioned solution, add PVP (Vinylpyrrolidone polymer K30) 0.4 gram, the mass percent concentration of PVP is 1%, stirs.Get acetic acid zirconium (Yutai reaches fine chemistry industry clearly) and be dissolved in 40 ml deionized water for 1.32 milliliters, the volumetric molar concentration of acetic acid zirconium is 0.225 mol, and 40 milliliters of zirconium acetate solutions are dropwise added above-mentioned nitrate mixed solution, stirs.Whipped state dropwise adds sodium hydroxide in above-mentioned mixing solutions, to white precipitate regeneration not.Regulator solution pH is 9, continues to stir 0.5 hour.Put into the teflon-lined autoclave to the above-mentioned solution for preparing, compactedness is 80%, and the liner volume is 100 milliliters.This solution was handled 40 hours down at 200 ℃, the solution centrifugal of handling well, drying, obtained required product.
The comparative example 1:
Get 1.1691 gram Lanthanum trinitrate (La (NO respectively
3)
36H
2O), 0.0651 gram cerous nitrate (Ce (NO
3)
36H
2O), 0.068 gram Terbium trinitrate (Tb (NO
3)
36H
2O) be dissolved in 40 ml deionized water, Lanthanum trinitrate, cerous nitrate, Terbium trinitrate volumetric molar concentration are respectively 0.0675 mol, 0.0038 mol, 0.0038 mol, stir.Get 0.465 milliliter of acetic acid zirconium and be dissolved in 40 ml deionized water, the volumetric molar concentration of acetic acid zirconium is 0.079 mol, and 40 milliliters of zirconium acetate solutions are dropwise added above-mentioned nitrate soln, stirs.Whipped state dropwise adds sodium hydroxide in above-mentioned mixing solutions, to white precipitate regeneration not.Regulator solution pH is 6, continues to stir 0.5 hour.Put into the teflon-lined autoclave to the above-mentioned solution for preparing, compactedness is 80%, and the liner volume is 100 milliliters.This solution was handled 20 hours down at 180 ℃, the solution centrifugal of handling well, drying, obtained required product.Fig. 4 is its stereoscan photograph, can know and see La
2Zr
2O
7: Ce, Tb are long bar-shaped, about 10 microns of its length, and about 1 micron of diameter, better dispersed.
Claims (1)
1. the preparation method of a cubic shape green luminescent material of lanthanum zirconate doped with cerium and terbium is characterized in that the step of this method is following:
1) Lanthanum trinitrate, cerous nitrate, Terbium trinitrate are dissolved in the deionized water, the mole number of control cerous nitrate is 1%～5% of a total rare earth cation mole number, and the mole number of control Terbium trinitrate is 5%～8% of a total rare earth cation mole number, stirs;
2) in above-mentioned solution, add PVP, the mass percent concentration of control PVP is 0.25%～1%, stirs;
3) in above-mentioned solution, add the acetic acid zirconium, the mole number of acetic acid zirconium equates with above-mentioned total rare earth cation mole number, stirs;
4) dropwise add sodium hydroxide solution and generate white precipitate, the pH value of control solution is 6～9, continues to stir;
5) with the above-mentioned solution autoclave of packing into, adopt hydro-thermal technology, the solution centrifugal of handling well, drying obtain cubic shape green luminescent material of lanthanum zirconate doped with cerium and terbium; Said hydro-thermal technology, temperature are controlled to be 180～220 ℃, and the treatment time is 6～40 hours.
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| CN102719778B (en) * | 2012-06-27 | 2014-04-02 | 中国地质大学（武汉） | Nanostructured cerium-doped lanthanum zirconate spherical powder for thermal spraying and preparation method thereof |
| CN107267148A (en) * | 2017-07-26 | 2017-10-20 | 齐齐哈尔大学 | A kind of terbium ion doping zirconic acid lanthanum fluorescent material and preparation method thereof |
| CN108659839A (en) * | 2017-11-21 | 2018-10-16 | 杭州显庆科技有限公司 | Phosphor is applied to optical anti-counterfeiting label material |
| CN108690611B (en) * | 2018-06-26 | 2021-05-04 | 浙江理工大学 | Terbium-doped gadolinium zirconate and preparation method thereof |
| CN109455760A (en) * | 2018-12-29 | 2019-03-12 | 中国建筑材料科学研究总院有限公司 | A kind of rear-earth-doped zirconates mesoporous material and preparation method thereof |
| CN110803926B (en) * | 2019-11-07 | 2022-02-11 | 兰州工业学院 | Preparation method of micro-doped high-surface-area nano zirconium dioxide powder |
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| CN1539914A (en) * | 2003-10-23 | 2004-10-27 | 北京有色金属研究总院 | Red luminescent powder in use for LED, preparing method and electric light source produced |
| CN1760326A (en) * | 2004-10-11 | 2006-04-19 | 北京有色金属研究总院 | Phosphor powder of composite oxide in use for white light LED and fabricated electric light source |
| US20080245663A1 (en) * | 2004-05-13 | 2008-10-09 | Berland Brian S | Novel Proton Conducting Materials And Devices Incorporating Them |
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| CN1539914A (en) * | 2003-10-23 | 2004-10-27 | 北京有色金属研究总院 | Red luminescent powder in use for LED, preparing method and electric light source produced |
| US20080245663A1 (en) * | 2004-05-13 | 2008-10-09 | Berland Brian S | Novel Proton Conducting Materials And Devices Incorporating Them |
| CN1760326A (en) * | 2004-10-11 | 2006-04-19 | 北京有色金属研究总院 | Phosphor powder of composite oxide in use for white light LED and fabricated electric light source |
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Inventor after: Gao Linhui Inventor after: Du Pingfan Inventor after: Wang Longcheng Inventor after: Luo Haoding Inventor after: Ju Cheng Inventor after: An Yue Inventor after: Zhu Hongliang Inventor after: Jin Dalai Inventor after: Wang Naiyan Inventor after: Yao Kuihong Inventor after: Chen Jianjun Inventor before: Gao Linhui Inventor before: An Yue Inventor before: Zhu Hongliang Inventor before: Jin Dalai Inventor before: Wang Naiyan Inventor before: Yao Kuihong Inventor before: Chen Jianjun Inventor before: Du Pingfan Inventor before: Wang Longcheng |
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Free format text: CORRECT: INVENTOR; FROM: GAO LINHUI AN YUE ZHU HONGLIANG JIN DALAI WANG NAIYAN YAO KUIHONG CHEN JIANJUN DU PINGFAN WANG LONGCHENG TO: GAO LINHUI LUO HAODING JU SHENG AN YUE ZHU HONGLIANG JIN DALAI WANG NAIYAN YAO KUIHONG CHEN JIANJUN DU PINGFAN WANG LONGCHENG |
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Granted publication date: 20121114 Termination date: 20130817 |