CN102391865A - Preparation method for doping gadolinium oxide nano-powders - Google Patents
Preparation method for doping gadolinium oxide nano-powders Download PDFInfo
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- CN102391865A CN102391865A CN2011102837093A CN201110283709A CN102391865A CN 102391865 A CN102391865 A CN 102391865A CN 2011102837093 A CN2011102837093 A CN 2011102837093A CN 201110283709 A CN201110283709 A CN 201110283709A CN 102391865 A CN102391865 A CN 102391865A
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Abstract
The invention provides a preparation method for doping gadolinium oxide nano-powders, which is based on coprecipitation hydro-thermal reaction and achieves simple process and lower cost. In the preparation method, urea can release ammonia uniformly under hydrothermal condition, the ammonia and rareearth ions such as gadolinium, activating agent erbium, sensitizing agent ytterbium and the like can generate high-quality precursors, and the high-quality precursors are calcined so as to obtain the doping gadolinium oxide up-conversion luminous nano-powders; and the prepared doping gadolinium oxide nano-powders are in a crystalline state and have high purity, and particle size is about 40 nm.
Description
Technical field
The invention belongs to field of material preparation, relate in particular to a kind of preparation method of up-conversion luminescence doping gadolinium sesquioxide nano-powder.
Background technology
Rare earth doped oxide fluorescent powder is of many uses in fields such as projection TV and FPD, and it is high, subsphaeroidal that high-quality fluorescent material should satisfy thing phase purity, and nothing is reunited, particle is little, requirements such as narrow diameter distribution.Rare earth oxide is common fluorescent material matrix, and wherein gadolinium sesquioxide has the visible region and do not have the energy level absorption, and specific refractory power is high, is prone to realize the rare earth ion doped excellent properties that waits, and is the rare earth luminescent material matrix of widespread use.The doping gadolinium sesquioxide also is applied to up-conversion luminescent material, because of its unique luminescent properties (long wavelength light excites down and sends short-wavelength light), has obtained widespread use in fields such as solid statelaser, transmitter, solar cell, 3 D stereo demonstrations.Above-mentioned important application, the preparation of high quality gadolinium sesquioxide powder is a key link.The product of different powder compound methods has different granule-morphologies and specific surface area, has determined final material properties.The present synthesis by solid state reaction of preparation gadolinium sesquioxide powder, its technology is simple, be easy to produce in batches, but has following point: be prone to cause particle to become in big, the process of lapping during high-temperature calcination and be prone to introduce impurity, be prone to exist second to equate dephasign.The wet-chemical synthesis method mainly contains: the precipitator method, sol-gel method etc., its product have advantages such as chemical constitution is accurate, uniform component distribution.
Because it has wide application prospects; Both at home and abroad the scientific worker has carried out the research that chemical method prepares the gadolinium sesquioxide nano-powder: the old long-pending sun of Shanghai Inst. of Silicate, Chinese Academy of Sciences etc. are precipitation agent with the mixture of ammoniacal liquor and bicarbonate of ammonia, prepared even particle distribution, had a yttrium oxide nano-powder (Chinese patent 03129648.3) of reunion basically.It is nanocrystalline that Sweden Optoqrit AB etc. has prepared the gadolinium sesquioxide of the 1-15 nm that glycol ether applies, can be applicable to selectivity and organize fields such as nuclear magnetic resonance (Chinese patent 200580030876.X).Shanghai Baoshan Iron & Steel Co., Ltd, Lee of Central South University are salty big etc. to adopt sol-gel method, through simple roasting, has prepared the Yttria/titanium dioxide nano composite material (Chinese patent 200610024966.4) with higher catalytic capability.Shenyang Institute of Chemical Technology Ma Weimin etc. has prepared good dispersivity, almost spherical, the size europium-doped yttrium oxide gadolinium luminescent powder (Chinese patent 200810010900.9) in 10-20 nm scope through microemulsion method.The Li Lings of Ji'nan University etc. introduce tensio-active agent, and ruthenium ion solution and basic soln react at normal temperatures and pressures, and granularity is tiny evenly, good dispersivity, and production unit requires simple, cost low (Chinese patent 01129722.0).Shanghai Inst. of Silicate, Chinese Academy of Sciences Yi Huang China etc. are the precipitation from homogeneous solution agent with urea, prepare sphere, monodispersed 50-400 nm yttrium oxide powder (Chinese patent 200910198286.8) through calcining; Behind cold isostatic compaction,, prepared doped yttrium oxide base transparent ceramic (Chinese patent 200910198283.4) with doping quasi-nano yttrium powder through low-temperature sintering, vacuum intensification sintering.
The hydrothermal method reactive behavior is high, and synthetic particles dispersed degree is good, percent crystallinity is high, is a kind of Perfected process for preparing nano-powder.Coprecipitation method is that the precipitation agent introduced discharges precipitating ion down at certain reaction conditions and accomplishes coprecipitation process. overcome direct precipitation method and prepared shortcomings such as the reactant mixing that exists in the powder is inhomogeneous, can obtain that particle diameter is little, the powder body material of narrow diameter distribution.Therefore the preparation method who develops a kind of hydro-thermal reaction based on co-precipitation, simpler, the lower-cost doping gadolinium sesquioxide of technology nano-powder has important practice value.
Summary of the invention
The purpose of this invention is to provide a kind of method of improving Hydrothermal Preparation high quality doping gadolinium sesquioxide nano-powder.The present invention adopts following technical scheme:
1.A kind of preparation method of the gadolinium sesquioxide nano-powder that mixes is a raw material with gadolinium salt, inorganic salt of rare earth, is coprecipitator with urea, under hydrothermal condition, generates presoma, makes doping gadolinium sesquioxide nano-powder through calcining.
Preparing method according to item 1 described doping gadolinium sesquioxide nano-powder is characterized in that: described gadolinium salt is selected Gadolinium trichloride or Gadolinium trinitrate for use; Described inorganic salt of rare earth is selected Ytterbium trichloride or ytterbium nitrate or Erbium trichloride or Erbium trinitrate for use.
Preparing method according to item 1 described doping gadolinium sesquioxide nano-powder is characterized in that: the mol ratio of described rare earth ion and gadolinium ion is that 0.1:4 is to 1:4.
Preparing method according to item 1 described doping gadolinium sesquioxide nano-powder is characterized in that: the mol ratio of described urea and gadolinium ion is about 10:1-5:1.
Preparing method according to item 1 described doping gadolinium sesquioxide nano-powder is characterized in that: the temperature of described hydro-thermal reaction is controlled in 120-180 degree centigrade, and the reaction times was controlled in 1-10 hour.
Preparing method according to item 1 described doping gadolinium sesquioxide nano-powder is characterized in that: the incinerating temperature is controlled in 500-1000 degree centigrade, and the reaction times was controlled in 1-10 hour.
Compared with prior art, the present invention has following advantage: water react, technology are simple, cost is lower, and the gadolinium sesquioxide nano-powder of preparation is high, the about 40nm particle diameter of crystal form, purity, is up-conversion luminescent material.
Description of drawings
Fig. 1 median size is the er-doped of 39 nm, the transmission electron microscope TEM figure of ytterbium gadolinium sesquioxide powder; Fig. 2 median size is the er-doped of 39 nm, the x-ray diffractogram of powder of ytterbium gadolinium sesquioxide powder; Fig. 3 median size is that figure (980 nm excite) is penetrated in the er-doped of 39 nm, the up-conversion luminescence of ytterbium gadolinium sesquioxide powder.
Embodiment
Instance 1: be dissolved in 8.0 ml deionized waters to 0.5 g urea, add 8.0 ml GdCl again
3The aqueous solution (0.2 M), 4.0 ml YbCl
3The aqueous solution (0.1 M), 4.0 ml ErCl
3After the aqueous solution (0.01 M) stirs; Solution is transferred in the withstand voltage reaction kettle of stainless steel of 40 ml, and after 10 hours, the gained white precipitate is through spinning 140 ℃ of reactions; Wash secondary respectively with deionized water and absolute ethyl alcohol; Through vacuum-drying, calcined 10 hours, and obtained white powder for 800 ℃.Fig. 1 is its transmission electron microscope picture, can know that it is the nano-powder that median size is about 39 nm; Fig. 2 is its X-ray diffractogram, can know that it is the gadolinium sesquioxide of high-purity thing phase; Fig. 3 median size is the er-doped of 39 nm, the up-conversion luminescence spectrogram of ytterbium gadolinium sesquioxide nano-powder, and rubescent look high light shows the doping that has realized erbium, ytterbium ion.
Instance 2: be dissolved in 8.0 ml deionized waters to 0.5 g urea, add 8.0 ml GdCl again
3The aqueous solution (0.2 M), 4.0 ml YbCl
3The aqueous solution (0.1 M), 4.0 ml ErCl
3After the aqueous solution (0.01 M) stirs; Solution is transferred in the withstand voltage reaction kettle of stainless steel of 40 ml, and after 10 hours, the gained white precipitate is through spinning 150 ℃ of reactions; Wash secondary respectively with deionized water and absolute ethyl alcohol; Through vacuum-drying, calcined 10 hours, and obtained white powder for 800 ℃.Through transmission electron microscope and powder x-ray diffraction analysis, be the doping gadolinium sesquioxide powder of about 73 nm of median size.
Instance 3: be dissolved in 8.0 ml deionized waters to 0.5 g urea, add 8.0 ml Gd (NO again
3)
3The aqueous solution (0.2 M), 4.0 ml Yb (NO
3)
3The aqueous solution (0.1 M) and 4.0 ml Er (NO
3)
3The aqueous solution (0.01 M), after stirring, solution is transferred in the withstand voltage reaction kettle of stainless steel of 40 ml; 150 ℃ the reaction 5 hours after; The gained white precipitate washs secondary respectively with deionized water and absolute ethyl alcohol, through vacuum-drying through spinning; Calcined 10 hours, and obtained white powder for 700 ℃.Through transmission electron microscope and powder x-ray diffraction analysis, be the doping gadolinium sesquioxide powder of about 65 nm of median size.
Instance 4: be dissolved in 8.0 ml deionized waters to 0.8 g urea, add 8.0 ml Gd Cl again
3The aqueous solution (0.2 M), after stirring, solution is transferred in the withstand voltage reaction kettle of stainless steel of 40 ml; After 8 hours, the gained white precipitate washs secondary through spinning respectively with deionized water and absolute ethyl alcohol 150 ℃ of reactions; Through vacuum-drying, calcined 5 hours, and obtained white powder for 700 ℃.Through transmission electron microscope and powder x-ray diffraction analysis, be the gadolinium sesquioxide powder of about 50 nm of median size.
Claims (6)
1. the preparation method of gadolinium sesquioxide nano-powder that mixes is a raw material with gadolinium salt, inorganic salt of rare earth, is coprecipitator with urea, under hydrothermal condition, generates presoma, makes doping gadolinium sesquioxide nano-powder through calcining.
2. the preparation method of doping gadolinium sesquioxide nano-powder according to claim 1 is characterized in that: described gadolinium salt is selected Gadolinium trichloride or Gadolinium trinitrate for use; Described inorganic salt of rare earth is selected Ytterbium trichloride or ytterbium nitrate or Erbium trichloride or Erbium trinitrate for use.
3. the preparation method of doping gadolinium sesquioxide nano-powder according to claim 1 is characterized in that: the mol ratio of described rare earth ion and gadolinium ion is that 0.1:4 is to 1:4.
4. the preparation method of doping gadolinium sesquioxide nano-powder according to claim 1 is characterized in that: the mol ratio of described urea and gadolinium ion is about 10:1-5:1.
5. the preparation method of doping gadolinium sesquioxide nano-powder according to claim 1 is characterized in that: the temperature of described hydro-thermal reaction is controlled in 120-180 degree centigrade, and the reaction times was controlled in 1-10 hour.
6. the preparation method of doping gadolinium sesquioxide nano-powder according to claim 1 is characterized in that: the incinerating temperature is controlled in 500-1000 degree centigrade, and the reaction times was controlled in 1-10 hour.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058724A (en) * | 2012-09-22 | 2013-04-24 | 包头市京瑞新材料有限公司 | Preparation method of large-particle gadolinium oxide |
| CN103359685A (en) * | 2013-07-02 | 2013-10-23 | 中山大学 | Positioning and doping method for nanomaterial |
| CN103421503A (en) * | 2012-05-16 | 2013-12-04 | 海洋王照明科技股份有限公司 | Holmium and ytterbium doped gadolinium oxide salt up-conversion luminescent material and preparation method and application thereof |
| CN103432598A (en) * | 2013-09-05 | 2013-12-11 | 中山大学 | Preparation method of nano rear earth doped gadolinium oxide bi-modal contrast medium |
| CN104781729A (en) * | 2012-09-17 | 2015-07-15 | 麦考瑞大学 | Enhancing upconversion luminescence in rare-earth doped particles |
| CN106753373A (en) * | 2016-11-30 | 2017-05-31 | 青岛科技大学 | A kind of ytterbium thulium codope gadolinium oxide upper conversion fluorescent nano particle and preparation method thereof |
| CN113481008A (en) * | 2021-03-30 | 2021-10-08 | 中山大学 | Plasmon-enhanced up-conversion luminescent nanoparticles and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421503A (en) * | 2012-05-16 | 2013-12-04 | 海洋王照明科技股份有限公司 | Holmium and ytterbium doped gadolinium oxide salt up-conversion luminescent material and preparation method and application thereof |
| CN104781729A (en) * | 2012-09-17 | 2015-07-15 | 麦考瑞大学 | Enhancing upconversion luminescence in rare-earth doped particles |
| CN103058724A (en) * | 2012-09-22 | 2013-04-24 | 包头市京瑞新材料有限公司 | Preparation method of large-particle gadolinium oxide |
| CN103058724B (en) * | 2012-09-22 | 2014-12-03 | 包头市京瑞新材料有限公司 | Preparation method of large-particle gadolinium oxide |
| CN103359685A (en) * | 2013-07-02 | 2013-10-23 | 中山大学 | Positioning and doping method for nanomaterial |
| CN103359685B (en) * | 2013-07-02 | 2016-04-13 | 中山大学 | A kind of location doping method of nano material |
| CN103432598A (en) * | 2013-09-05 | 2013-12-11 | 中山大学 | Preparation method of nano rear earth doped gadolinium oxide bi-modal contrast medium |
| CN103432598B (en) * | 2013-09-05 | 2015-04-15 | 中山大学 | Preparation method of nano rear earth doped gadolinium oxide bi-modal contrast medium |
| CN106753373A (en) * | 2016-11-30 | 2017-05-31 | 青岛科技大学 | A kind of ytterbium thulium codope gadolinium oxide upper conversion fluorescent nano particle and preparation method thereof |
| CN113481008A (en) * | 2021-03-30 | 2021-10-08 | 中山大学 | Plasmon-enhanced up-conversion luminescent nanoparticles and preparation method and application thereof |
| CN113481008B (en) * | 2021-03-30 | 2022-06-03 | 中山大学 | Plasmon-enhanced up-conversion luminescent nanoparticles and preparation method and application thereof |
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Application publication date: 20120328 |