CN1230490C - Method for preparing rare earth oxide group nanometer luminescent powder - Google Patents

Method for preparing rare earth oxide group nanometer luminescent powder Download PDF

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CN1230490C
CN1230490C CNB031508367A CN03150836A CN1230490C CN 1230490 C CN1230490 C CN 1230490C CN B031508367 A CNB031508367 A CN B031508367A CN 03150836 A CN03150836 A CN 03150836A CN 1230490 C CN1230490 C CN 1230490C
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rare earth
earth oxide
powder
edta
citric acid
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CN1523077A (en
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刘庆峰
刘茜
罗岚
沈彩
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C01B13/185—Preparing mixtures of oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
    • C01B13/363—Mixtures of oxides or hydroxides by precipitation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides

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Abstract

The present invention relates to a process for preparing nanometer rare earth oxide light emitting powder by using a sol gelatinizing method. The nanometer rare earth oxide light emitting powder can be obtained at low temperature by using the raw materials and the technological conditions of the present invention. The rare earth oxides has the chemical general formula of Ln2O3: Re, wherein Ln is one or any two of Y, Gd and Lu; Re is one of Ce, Pr, Nd, Sm, Eu, Tb, Dy and Yb, or specific two or three (Eu/Pr, Pr/ Ce, Eu/Tb, Eu/Pr/Ce and Ce/Tb) of Ce, Pr, Nd, Sm, Eu, Tb, Dy and Yb, and the molar ratio is 0.1 to 10%. In the present invention, citric acid or EDTA is used as a complexing agent, ethylene glycol is used as a polymerizing auxiliary agent and dispersing agent, the complexing agent interacts with the polymerizing auxiliary agent so as to form sol, and precursor powder is gelatinized; the precursor powder is calcined at the temperature of 500 to 850 DEG C so as to obtain the light emitting powder with the particle sizes of 20 to 80 nm. The present invention is characterized in that the heat treatment temperature of the powder is low, the particle sizes of the synthesized powder are small and even, and the light emitting activating ions (Re) are evenly distributed.

Description

The preparation method of rare earth oxide base nano-luminescent powder body
Technical field
The present invention relates to the preparation method of rear-earth-doped nanometer rare earth oxide luminescent powder.
Background technology
Rare earth oxide base luminescent powder is a kind of important functional material, plays crucial effect in widely used negative ray screen, electroluminescent and field emission display field.With respect to the micron order luminescent powder that generally uses on the market at present, the relative luminous intensity of nanoscale luminescent powder significantly improves, and the phenomenon that on luminescent spectrum, also exists the spectrum peak to move, cause the change of photoresponse, thereby widened the application prospect of luminescent powder.At present, the method for preparing the rare earth oxide luminescent powder is a lot, and as high temperature solid phase synthesis, oxalate coprecipitation method etc., but the luminescent powder that these methods obtain is micron order.Chinese patent 98106748.4 discloses a kind of urea homogeneous precipitation method that utilizes, and perhaps homogeneous precipitation method combines with sonochemical method and prepares the method for fluorescent nanometer rare earth oxide powder.Utilize the precipitation agent concentration in the hydrolytic action control solution of urea, precipitation agent concentration is increased lentamente, and make the precipitation in the solution be in quasi-balanced state, add the effect of ultrasonic cavitation, precipitation can generate in whole solution equably.Utilize this method can obtain luminescent powder about 70nm, but this method still can't be avoided the ununiformity of the different caused luminescent powder set of dispense ratios of each constituent element settling rate in the mixed system, and the thermal treatment temp of powder need be more than 900 ℃, the processing unit more complicated, production cost is higher.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of collosol and gel to prepare the novel method of nanometer rare earth oxide luminescent powder.The characteristics of this method are that the powder thermal treatment temp is low, and technology is simple, can realize activation ionic atom level uniform mixing.
The chemical general formula of nanometer rare earth oxide powder of the present invention is:
Ln 2O 3:Re
Wherein Ln is a kind of or any two kinds compound among Y, Gd, the Lu, and Re is a kind of or specific several (Eu/Pr, Pr/Ce among Ce, Pr, Nd, Sm, Eu, Tb, Dy, the Yb, Eu/Tb, Eu/Pr/Ce, Ce/Tb) compound, its molar content is 0.1～10%.
It is main raw material that the present invention selects cheap and nontoxic rare earth oxide for use, adopt the complexing agent of citric acid or ethylenediamine tetraacetic acid (EDTA) (EDTA) metal ion, ethylene glycol is as reagent and additive in polymerization, utilize the polymerization of citric acid or EDTA and ethylene glycol to form colloidal sol, the amount of control complexing agent, reagent and additive in polymerization is controlled in the ideal scope particle diameter of luminescent powder.Adopt manufacture method of the present invention, the particle diameter of nano-oxide luminescent powder is in 20～80nm scope.
The present invention mainly may further comprise the steps:
A, with rare earth oxide mixture (Ln 2O 3With Re 2O 3) be dissolved in the concentrated nitric acid, add lemon
Lemon acid or ethylenediamine tetraacetic acid (EDTA) (EDTA) and ethylene glycol, regulating the pH value is 2～8 scopes, obtains settled solution.
B, under water bath condition, controlled temperature is 65～80 ℃ of scopes, continuously stirring obtains colloidal sol;
C, under water bath condition, controlled temperature is 70～90 ℃ of scopes, control pressure is at 0.6～1 normal atmosphere, heating obtains gel continuously;
D, gel are at 100～200 ℃ of dry forerunner's powder that obtain;
E, obtain the nano-oxide luminescent materials in the calcining of 500～850 ℃ temperature ranges, temperature rise rate is per hour 150～600 ℃.
It is characterized in that the mol ratio of citric acid or EDTA and metal ion is (0.33～10): 1, the mol ratio of ethylene glycol and citric acid or EDTA is 0.5～16: 1.Wherein citric acid and EDTA have equal effect.Citric acid or EDTA and complexing of metal ion form settled solution, and the mutual polymerization of acid of lemon rubber or EDTA and ethylene glycol forms colloidal sol and further gelationization.Ethylene glycol is as reagent and additive in polymerization and dispersion agent.
Description of drawings
Fig. 1 is Gd 2O 3: the TEM photo of Eu nano luminescent material, median size are 50nm
Fig. 2 is Gd 2O 3: the emmission spectrum spectrogram of Eu nano luminescent material, X-coordinate are wavelength (nm), and ordinate zou is an intensity.
Embodiment
Following example is in order further more specifically to illustrate the characteristics and the advantage of technological process of the present invention.
Embodiment 1
Take by weighing 3.625g gadolinium sesquioxide (Gd 2O 3) and 0.130g europium sesquioxide (Eu 2O 3), with an amount of concentrated nitric acid heating for dissolving; Take by weighing the 42g citric acid, use deionized water dissolving, join in the nitrate solution and stir; PH value with the ammoniacal liquor regulator solution is 7, obtains settled solution; Add 49.66g ethylene glycol again, formed colloidal sol in 2 hours in 70 ℃ of continuously stirring; Elevated temperature to 85 ℃ heating formed the transparence gel in 6 hours.Gel is put into the box-type furnace that is preheated to 150 ℃ after dry 2 hours, and obtaining particle diameter in two hours through 600 ℃ of thermal treatments is Gd about 50nm 2O 3: Eu nano luminescent material (Fig. 1).This powder is a cube phase structure through X-ray analysis, the strong ruddiness of emission under 254nm UV-light and excitation of X-rays.Wherein 254nm excites down spectrum as shown in Figure 2.
Embodiment 2
Take by weighing 3.625g gadolinium sesquioxide (Gd 2O 3) and 0.130g europium sesquioxide (Eu 2O 3), with an amount of concentrated nitric acid heating for dissolving; Take by weighing the 11g citric acid, use deionized water dissolving, join in the nitrate solution and stir; PH value with the ammoniacal liquor regulator solution is 7, obtains settled solution; Add 2g ethylene glycol again, formed colloidal sol in 2 hours in 70 ℃ of continuously stirring; Elevated temperature to 85 ℃ heating formed the transparence gel in 6 hours.Gel is put into the box-type furnace that is preheated to 110 ℃ after dry 2 hours, and obtaining particle diameter in two hours through 600 ℃ of thermal treatments is Gd about 80nm 2O 3: the Eu nano luminescent material.This powder is single monocline phase structure through X-ray analysis, and emission peak is at the 621nm place under the exciting of 254nm UV-light.
Embodiment 3
Take by weighing 2.258g gadolinium sesquioxide (Y 2O 3) and 0.1044g Sm 2O 3, all the other conditions can obtain Y with embodiment 1 2O 3: the Sm nano-luminescent powder body.Its luminescence peak is at 609nm.
Embodiment 4
Take by weighing 3.625g gadolinium sesquioxide (Gd 2O 3) and 0.341g Pr 6O 11, all the other conditions can obtain monocline phase Gd with embodiment 2 2O 3: the Pr nano-luminescent powder body.Its luminescence peak is green glow at 510nm.
Embodiment 5
Take by weighing 84g citric acid and 198g ethylene glycol, all the other conditions can obtain the Gd that particle diameter is 20～30nm with embodiment 1 2O 3: the Eu luminescent powder
Embodiment 6
Take by weighing the 117.2g ethylenediamine tetraacetic acid (EDTA), all the other conditions can obtain the Gd that particle diameter is 40nm with embodiment 1 2O 3: the Eu luminescent powder
Embodiment 7
Take by weighing 3.98g Lu 2O 3, all the other conditions can be prepared Lu with embodiment 1 2O 3: Eu red light Nano luminescent material.Diameter of particle is about 45nm.
Embodiment 8
Take by weighing 1.45g Gd 2O 3, 1.355g Y 2O 3With 0.130g Eu 2O 3, 0.002g Pr 6O 11, all the other conditions are with embodiment 1, can prepare compound (Y, Gd) 2O 3: Eu, Pr red light Nano material.
Wherein embodiment 1,2,5,6 is a class Comparative Examples, chooses identical Ln 2O 3And Re 2O 3Proportioning, and the consumption and the kind of change complexing agent and dispersion agent contrast the crystalline structure of obtained powder and the difference of the size distribution and the characteristics of luminescence.
Embodiment 1,3,7 and embodiment 2,4 and embodiment 1,8 are respectively another kind of Comparative Examples, choose different Ln 2O 3And Re 2O 3Kind, and keep the same complexing agent and the kind and the consumption of dispersion agent, with the difference of contrast development powder.
During important reduced parameter and difference are listed in the table below:
Implement Ln 2O 3 Re Complexing agent Ethylene glycol Calcining temperature Particle diameter Glow peak
Lemon EDTA
1 Gd 2O 3 Eu 2O 3 42g 49.66g 600 50nm 611nm
2 Gd 2O 3 Eu 2O 3 11g 2g 600 80nm 621nm
3 Y 2O 3 Sm 2O 3 42g 49.66g 600 50nm 609nm
4 Gd 2O 3 Pr 6O 11 11g 2g 600 80nm 510nm
5 Gd 2O 3 Eu 2O 3 84g 198g 600 20～30nm 611nm
6 Gd 2O 3 Eu 2O 3 117.2g 49.66g 600 40nm 611nm
7 Lu 2O 3 Eu 2O 3 42g 49.66g 600 45nm 609nm
8 Gd 2O 3 /Y 2O 3 Eu 2O 3 /Pr 6O 11 42g 49.66g 600 50nm 611nm

Claims (3)

1. the preparation method of a nanometer rare earth oxide luminescent powder is characterized in that comprising the steps:
(1) with Ln 2O 3: the rare earth oxide mixture of Re is dissolved in the concentrated nitric acid, adds citric acid or EDTA, and ethylene glycol, and regulating the pH value is 2～8 scopes, makes settled solution; Ln is a kind of or any two kinds compound among Y, Gd, the Lu, and Re is a kind of or specific several among Ce, Pr, Nd, Sm, Tb, Eu, Dy, the Yb, and its molar content is 0.1-10%;
(2) under water bath condition, controlled temperature is 65～80 ℃ of scopes, and continuously stirring makes colloidal sol;
(3) under water bath condition, controlled temperature is 70～90 ℃ of scopes, and control pressure is at 0.6～1 normal atmosphere, and heating obtains gel continuously;
(4) gel is at 100～200 ℃ of dry forerunner's powder that obtain;
(5) at 500～850 ℃ temperature range calcining acquisition nano-oxide luminescent material, the calcination process temperature rise rate is per hour 150～600 ℃;
Specific several of wherein said Re are meant among Eu/Pr, Pr/Ce, Eu/Tb, Ce/Tb or the Eu/Pr/Ce a kind of;
The mol ratio of wherein said citric acid or EDTA and metal ion is 0.33～10: 1, and the mol ratio of ethylene glycol and citric acid or EDTA is 0.5～16: 1.
2. the preparation method of nanometer rare earth oxide luminescent powder according to claim 1, it is characterized in that citric acid or EDTA and complexing of metal ion form settled solution, the mutual polymerization of citric acid or EDTA and ethylene glycol forms colloidal sol and further gelationization, and ethylene glycol is as reagent and additive in polymerization and dispersion agent.
3. the preparation method of nanometer rare earth oxide luminescent powder according to claim 1, the sub-Ah of its feature in the preparation the nanometer rare earth oxide diameter of particle at 20～80nm.
CNB031508367A 2003-09-05 2003-09-05 Method for preparing rare earth oxide group nanometer luminescent powder Expired - Fee Related CN1230490C (en)

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CN100445347C (en) * 2005-09-28 2008-12-24 同济大学 Gadolinium tantalate transparent illuminating film and preparing process thereof
EP2194025A1 (en) 2008-12-05 2010-06-09 Koninklijke Philips Electronics N.V. Monodisperse nanoparticles and their application
CN101962544B (en) * 2009-07-24 2014-02-05 海洋王照明科技股份有限公司 Oxide light-emitting material capable of emitting ultraviolet lights and preparation method thereof
CN101984015B (en) * 2010-09-29 2013-07-17 南京工业大学 Preparation of (Y) by microwave radiation
CN101979460B (en) * 2010-09-30 2013-10-02 广东炜林纳功能材料有限公司 Method for preparing microwave-assisted non ball milling rare-earth superfine powder
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CN104124317B (en) * 2013-04-25 2017-10-17 浙江大学 A kind of inorganic electroluminescence infrared light-emitting device of neodymium-doped and preparation method thereof
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