CN101619218B - Preparation method of Sm ion-activated superfine red fluorescent powder - Google Patents

Preparation method of Sm ion-activated superfine red fluorescent powder Download PDF

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CN101619218B
CN101619218B CN 200910063402 CN200910063402A CN101619218B CN 101619218 B CN101619218 B CN 101619218B CN 200910063402 CN200910063402 CN 200910063402 CN 200910063402 A CN200910063402 A CN 200910063402A CN 101619218 B CN101619218 B CN 101619218B
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fluorescent powder
red fluorescent
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fused salt
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CN101619218A (en
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梁玉军
刘蓉
李永周
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China University of Geosciences
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China University of Geosciences
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Abstract

The invention discloses Sm ion-activated superfine red fluorescent powder and a preparation method thereof. The structural formula of the fluorescent powder is Ln1-xSmxVO4, wherein Ln is at least one of Y, Gd, Yb and Lu, and x is larger than or equal to 0.001 and is smaller than or equal to 0.1. The preparation method comprises the following steps: weighing simple substances, oxides or corresponding salt of Ln and simple substances, oxides or corresponding salt of Sm according to the stoichiometric ratio of the structural formula; using ammonium metavanadate as raw material, and using the mixture which is formed by mixing one or more kinds of NaNO3, KNO3 and LiNO3 according to arbitrary mass ratio as molten salt; uniformly mixing and grinding the raw material with the molten salt according to the proportion; burning the mixture at 350-500 DEG C, and washing, filtering and baking the mixture; and then, obtaining the Sm ion-activated superfine red fluorescent powder. The Sm ion-activated superfine red fluorescent powder has fine fluorescent powder particles, has stronger absorption capacity within the range of 225-350nm, emits bright red light, has abundant raw materials of products and simple preparation technology, and can be produced at lower temperature.

Description

The preparation method of the superfine red fluorescent powder that a kind of Sm is ion-activated
Technical field
The present invention relates to the preparation method of the ion-activated superfine red fluorescent powder of a kind of Sm.
Background technology
Nineteen sixty-five, Levine and Palilla develop rare-earth ion activated Yttrium Orthovanadate, and from then on, rare-earth ion activated fluorescent material is greatly developed.It mainly is used as cathode ray fluorescence power, high-pressure mercury lamp phosphor and XRF powder, and it also has potential using value on pure flat display equipment.Wherein the rare earth activators ion of red fluorescence powder utilization mainly is Eu 3+, such as YVO 4: Eu 3+, Y 2O 3: Eu 3+Deng.But up to the present, the fluorescent material of doing activator preparation with the Sm ion of report all produces orange emission, and the fluorescent material that can produce red emission there is not yet report.
Traditional high temperature solid-state method to what mostly adopt synthesizing of rare earth ion doped luminescent material at present, sol-gel method that also has combustion synthesis method, spray method, hydrothermal method, microwave irradiation, polyvalent alcohol method in addition and study now often etc.Although the crystal mass of traditional high temperature solid-state method crystallite is good, few surface defects, luminous efficiency is high, and its synthesis temperature is high, and the large and skewness of particle size is difficult to obtain spheroidal particle; Study to get sol-gel method the most widely for present investigator, its advantage is the product good uniformity that makes, active ions can be evenly distributed in the parent lattice, purity is high, banded emission peak narrows, can improve relative luminous intensity and the relative quantum efficient of twinkler, compare the high temperature solid-state method calcining temperature low, can save the energy, but it also exists very important shortcoming simultaneously: operation is loaded down with trivial details, and is wayward, if matrix is residual, then can reduce luminous intensity, used alkoxide is harmful.
Molten-salt growth method is a kind of softening synthesis method, usually adopt one or several low-melting salts as reaction medium, there is liquid phase to occur in the building-up process, reactant has certain solubleness in fused salt, greatly accelerated the rate of diffusion of ion, makes reactant realize that in liquid phase atomic scale mixes, thereby be converted into solid-liquid reaction by solid-solid reaction, reaction adopts suitable solvent that salt is dissolved after finishing, and can obtain synthetic product behind washing, filtering and drying.The modern synthetic method of this method and other relatively has an operating procedure simple, does not need other specific equipment, synthesis temperature is low, and synthesis cycle is short, and synthetic powder chemical composition is even, crystal morphology good, phase purity advantages of higher, in addition, salt is easily separated, and is also reusable.But not yet occur at present adopting molten-salt growth method to prepare the report of the ion-activated superfine red fluorescent powder of Sm.
Summary of the invention
The object of the invention is to remedy the deficiencies in the prior art, ion-activated superfine red fluorescent powder of a kind of Sm and preparation method thereof is provided, this red fluorescence powder has stronger absorption in 225 ~ 350 nm scopes, send bright ruddiness, this product abundant raw materials simultaneously, preparation technology is simple, can produce under lower temperature.
The technical scheme that realizes the object of the invention is: the superfine red fluorescent powder that a kind of Sm is ion-activated, its structural formula is: Ln 1-xSm xVO 4, wherein, Ln is at least a among Y, Gd, Yb or the Lu, 0.001≤x≤0.1.
The particle diameter of above-mentioned red fluorescence powder is 20nm ~ 800nm.
It is the optical excitation of 225nm ~ 350nm that above-mentioned red fluorescence powder is subjected to wavelength, the ruddiness of emission take 647nm and 602nm as predominant wavelength.
The present invention also provides the above-mentioned Sm preparation method of ion-activated superfine red fluorescent powder, may further comprise the steps:
(1) according to the structural formula Ln of red fluorescence powder 1-xSm xVO 4, wherein, Ln is at least a among Y, Gd, Yb or the Lu, 0.001≤x≤0.1 take by weighing the simple substance, oxide compound of Ln or simple substance, oxide compound or the corresponding salt of corresponding salt and Sm by the stoichiometric ratio of this structural formula, and ammonium meta-vanadate is as raw material;
(2) with NaNO 3, KNO 3Or LiNO 3In any or several mixture that mixes by any mass ratio as fused salt, in the ratio of raw material Rare Earth Ion and the amount of substance of fused salt be the ratio of 1:1 ~ 10 with raw material with fused salt mixes and fully grinding, obtain presoma;
(3) presoma was carried out calcination in 1 ~ 10 hour in 350 ℃ ~ 500 ℃ insulations, calcination cools to product with the furnace room temperature after finishing, fully wash with deionized water and to remove unreacted fused salt and impurity in the product, refilter, dry, namely obtain the ion-activated superfine red fluorescent powder of Sm.
Fully wash with deionized water in the above-mentioned steps (3) and remove in the product behind the unreacted fused salt and impurity, with absolute ethanol washing 2 ~ 3 times, and then filter, oven dry.
Bake out temperature is 70 ℃ ~ 150 ℃ in the above-mentioned steps (3).
Compared with prior art, the advantage that the present invention has is: the present invention adopts molten-salt growth method to synthesize the ion-activated superfine red fluorescent powder of Sm, and its CIE coordinate range is: CIE X=(0.624 ~ 0.627), CIE Y=(0.372 ~ 0.375) is in the pure red range, and this fluorescent material high color purity is described; Utilizing emitted light spectrogram by it illustrates that the brightness of this fluorescent material is high.Required rare earth starting material both can be simple substance, oxide compound, can also be the various salts of rare earth element, and synthetic method were very simple, can produce under the cold condition.
Description of drawings
Fig. 1 is embodiment 1 gained fluorescent material Y 0.98Sm 0.02VO 4XRD figure;
Fig. 2 is embodiment 1 gained fluorescent material Y 0.98Sm 0.02VO 4The exciting light spectrogram;
Fig. 3 is embodiment 1 gained fluorescent material Y 0.98Sm 0.02VO 4The utilizing emitted light spectrogram.
Embodiment
Embodiment 1
Take by weighing Y 2O 34.154g, Sm 2O 30.129g, ammonium meta-vanadate 4.301g and SODIUMNITRATE 9.400g.First with the Y that weighs up 2O 3, Sm 2O 3Place agate mortar to grind with ammonium meta-vanadate it is mixed, the SODIUMNITRATE that then adds as fused salt continues to make presoma after the grinding evenly.Presoma is placed crucible with cover, then put it in the retort furnace, carried out calcination in 5 hours in 500 ℃ of insulations, after calcination finishes, treat that sample cools to room temperature with the furnace, then take out with deionized water wash and remove unreacted fused salt and impurity, and reunite to prevent from producing at drying course with absolute ethanol washing 2 ~ 3 times, refilter, in 70 ℃ of drying and processings, namely get the finished product.
Fig. 1 is the XRD powder diagram of the present embodiment products obtained therefrom, can find out the Y that has successfully synthesized pure phase with molten-salt growth method by the fluorescence spectrum figure with standard card PDF/JCPDS 17-0341 contrast and Fig. 2, Fig. 3 0.98Sm 0.02VO 4, the use of fused salt does not bring any impurity phase to product.The median size of this fluorescent material is 126 nm, its excitation spectrum (λ Em=602 nm) and emmission spectrum (λ Ex=256 nm) see Fig. 2 and Fig. 3, as can be seen from the figure, this fluorescent material can effectively be excited by the UV-light of 225 ~ 350 nm wave bands and launch peak wavelength and be positioned at 602 nm and 647 nm; Its chromaticity coordinates is: CIE X=0.624, CIE Y=0.373; Sample emission general performance is bright ruddiness.
Embodiment 2
Take by weighing Gd 2O 36.663g, Sm 2O 30.129g, ammonium meta-vanadate 4.301g and SODIUMNITRATE 9.400g.First with the Gd that weighs up 2O 3, Sm 2O 3Place agate mortar to grind with ammonium meta-vanadate it is mixed, the SODIUMNITRATE that then adds as fused salt continues to make presoma after the grinding evenly.Presoma is placed crucible with cover, then put it in the retort furnace, carried out calcination in 5 hours in 350 ℃ of insulations, after calcination finishes, sample cools to room temperature with the furnace, then takes out with deionized water wash and removes unreacted fused salt and impurity, and reunite to prevent from producing at drying course with absolute ethanol washing 2 ~ 3 times, refilter, in 90 ℃ of drying and processings, obtain the finished product.
By the method identical with embodiment 1 product is carried out XRD analysis, confirm that this product is the ion-activated superfine red fluorescent powder Gd of Sm 0.98Sm 0.02VO 4, its median size is 45nm; Its chromaticity coordinates is: CIE X=0.626, CIE Y=0.375; Sample emission general performance is bright ruddiness.
Embodiment 3
Take by weighing Y 2O 32.490g, Gd 2O 32.665g, Sm 2O 30.129g, ammonium meta-vanadate 4.301g and SODIUMNITRATE 9.400g.First with the Y that weighs up 2O 3, Gd 2O 3, Sm 2O 3, ammonium meta-vanadate places agate mortar to grind it is mixed, then add to make presoma after SODIUMNITRATE as fused salt continues to grind evenly.Presoma is placed crucible with cover, then put it in the retort furnace, carried out calcination in 3 hours in 500 ℃ of insulations, after calcination finishes, sample cools to room temperature with the furnace, then takes out with deionized water wash and removes unreacted fused salt and impurity, and reunite to prevent from producing at drying course with absolute ethanol washing 2 ~ 3 times, refilter, in 110 ℃ of drying and processings, obtain the finished product.
By the method identical with embodiment 1 product is carried out XRD analysis, confirm that this product is the ion-activated superfine red fluorescent powder Y of Sm 0.588Gd 0.392Sm 0.02VO 4, its median size is 216 nm; Its chromaticity coordinates is: CIE X=0.627, CIE Y=0.372; Sample emission general performance is bright ruddiness.
Embodiment 4
Take by weighing Y 2O 31.671g, Lu 2O 32.945g, Sm 2O 30.129g, ammonium meta-vanadate 4.301g and SODIUMNITRATE 9.400g.First with the Y that weighs up 2O 3, Lu 2O 3, Sm 2O 3, ammonium meta-vanadate places agate mortar to grind it is mixed, then add to make presoma after SODIUMNITRATE as fused salt continues to grind evenly.Presoma is placed crucible with cover, then put it in the retort furnace, carried out calcination in 8 hours in 450 ℃ of insulations, after calcination finishes, sample cools to room temperature with the furnace, then takes out with deionized water wash and removes unreacted fused salt and impurity, and reunite to prevent from producing at drying course with absolute ethanol washing 2 ~ 3 times, refilter, in 120 ℃ of drying and processings, obtain the finished product.
By the method identical with embodiment 1 product is carried out XRD analysis, confirm that this product is the ion-activated superfine red fluorescent powder Y of Sm 0.49Lu 0.49Sm 0.02VO 4, its median size is 114 nm; Its chromaticity coordinates is: CIE X=0.627, CIE Y=0.372; Sample emission general performance is bright ruddiness.
Embodiment 5
Take by weighing Yb 2O 31.671g, Gd 2O 32.682g, Sm 2O 30.129g, ammonium meta-vanadate 4.301g and SODIUMNITRATE 9.400g.First with the Yb that weighs up 2O 3, Gd 2O 3, Sm 2O 3, ammonium meta-vanadate places agate mortar to grind it is mixed, then add to make presoma after SODIUMNITRATE as fused salt continues to grind evenly.Presoma is placed crucible with cover, put it in the retort furnace, carried out calcination in 10 hours in 400 ℃ of insulations, after calcination finishes, sample cools to room temperature with the furnace, then takes out with deionized water wash and removes unreacted fused salt and impurity, and reunite to prevent from producing at drying course with absolute ethanol washing 2 ~ 3 times, refilter, in 150 ℃ of drying and processings, obtain the finished product.
By the method identical with embodiment 1 product is carried out XRD analysis, confirm that this product is the ion-activated superfine red fluorescent powder Yb of Sm 0.49Gd 0.49Sm 0.02VO 4, its median size is 740 nm; Its chromaticity coordinates is: CIE X=0.625, CIE Y=0.374; Sample emission general performance is bright ruddiness.
Among the present invention when fused salt be to appoint in the above-mentioned nitrate when appointing several mixtures in several mixtures or the above-mentioned villaumite, its blending ratio can be any mass ratio, can not exert an influence to the optical property of product.

Claims (3)

1. the preparation method of the ion-activated superfine red fluorescent powder of a Sm is characterized in that may further comprise the steps:
(1) according to the structural formula Ln of red fluorescence powder 1-xSm xVO 4, wherein, Ln is at least a among Y, Gd, Yb or the Lu, 0.001≤x≤0.1 take by weighing the simple substance, oxide compound of Ln or simple substance, oxide compound or the corresponding salt of corresponding salt and Sm by the stoichiometric ratio of this structural formula, and ammonium meta-vanadate is as raw material;
(2) with NaNO 3, KNO 3Or LiNO 3In any or several mixture that mixes by any mass ratio as fused salt, in the ratio of raw material Rare Earth Ion and the amount of substance of fused salt be the ratio of 1:1 ~ 10 with raw material with fused salt mixes and fully grinding, obtain presoma;
(3) presoma was carried out calcination in 1 ~ 10 hour in 350 ℃ ~ 500 ℃ insulations, calcination cools to product with the furnace room temperature after finishing, fully wash with deionized water and to remove unreacted fused salt and impurity in the product, refilter, dry, namely obtain the ion-activated superfine red fluorescent powder of Sm, the structural formula of this red fluorescence powder is: Ln 1-xSm xVO 4, wherein, Ln is at least a among Y, Gd, Yb or the Lu, 0.001≤x≤0.1; The particle diameter of described red fluorescence powder is 20nm ~ 800nm; It is the ultraviolet excitation of 225nm ~ 350nm wave band that described red fluorescence powder is subjected to wavelength, the ruddiness of emission take 647nm and 602nm as predominant wavelength.
2. the preparation method of the ion-activated superfine red fluorescent powder of Sm according to claim 1, it is characterized in that: fully wash with deionized water in the step (3) and remove in the product behind the unreacted fused salt and impurity, with absolute ethanol washing 2 ~ 3 times, and then filter, oven dry.
3. the preparation method of the ion-activated superfine red fluorescent powder of Sm according to claim 2, it is characterized in that: bake out temperature is 70 ℃ ~ 150 ℃ in the step (3).
CN 200910063402 2009-07-31 2009-07-31 Preparation method of Sm ion-activated superfine red fluorescent powder Expired - Fee Related CN101619218B (en)

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