CN101429431B - Microwave excitation low-temperature liquid-phase combustion synthesis process for producing rare earth activated nano-self-luminescence powder - Google Patents
Microwave excitation low-temperature liquid-phase combustion synthesis process for producing rare earth activated nano-self-luminescence powder Download PDFInfo
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- CN101429431B CN101429431B CN2008101365500A CN200810136550A CN101429431B CN 101429431 B CN101429431 B CN 101429431B CN 2008101365500 A CN2008101365500 A CN 2008101365500A CN 200810136550 A CN200810136550 A CN 200810136550A CN 101429431 B CN101429431 B CN 101429431B
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Abstract
The invention relates to a method for preparing rare earth activation self-luminescence nano luminescent powder by microwave excitation liquid phase combustion synthesis, which belongs to the field of luminescent material. In the method, materials(such as aluminate, silicate and oxide) with stable chemical property are optimized as substrate materials, rare earth elements(such as Eu, Tb, Y, Gd, and Er) with 4f electronic configuration are used as activator and sensitizer, and proper amount of auxiliary agent is also added; and by adopting the microwave excitation low-temperature liquid phase combustion synthesis method, the high-efficiency nano self-luminescent material with various luminescent colors of green, blue green, deep blue, blue purple, yellow, yellow green, red, orange red colors and the like. The method has the characteristics of simple process, quick reaction, low ignition temperature and unnecessary addition of reducing atmosphere for protection, and the combustion synthesis reaction can be completed in a few minutes, and the size of the prepared luminescent powder crystal grain is controlled in the range of between 40 and 60mm; and the luminescent powder synthesized by the method is clean, perfect in crystallization and high in luminous efficiency, and can be directly used without ball mill crushing and post treatment. Therefore, the method has the advantages of reliability, energy conservation, high efficiency, environmental protection, and the suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of microwave excitation liquid-phase combustion synthetic preparation method of rare earth activated nano-self-luminescence powder, belong to field of light emitting materials.
Technical background
Adopt traditional high temperature solid-state method synthetic because present commercial fluorescent material is general, need the high temperature more than 1600 ℃ to react for a long time, not only energy consumption is big, cost is high, and product easy-sintering and particle are thick under this high temperature, need ball mill pulverizing, thereby cause crystalline form to be destroyed and the luminescent properties of grievous injury fluorescent material.Test is fixed factually, and the fluorescent material brightness after grinding has only original about 1/4th.Therefore, in order to solve existing issue, the research and development of low temperature synthesis technique have become and have pressed for.
Because nanoparticle has small-size effect, surface effects, quantum size effect and macro quanta tunnel effect etc. and makes it present optics and the electrology characteristic that conventional material does not possess at aspects such as light, electricity, magnetic.Little the arriving in the nano level scope of particle size when fluorescent material matrix, wherein the luminous and kinetic property of adulterated active ions will change, thereby influences its photoabsorption, excites the life-span, character such as transmission ofenergy, photo-quantum efficiency and concentration quenching and improve the performance of fluorescent material.
Wet chemistry method is just becoming the focus of various countries material supply section scholar research as a kind of method for preparing the superfine nano powder.This method is because raw material reacts in solution, thereby component can reach the uniform mixing on molecule, the ionic level, and synthesis temperature is low, and composition is accurately control easily.
Common wet chemistry method comprises coprecipitation method, Sol-gel method (sol-gel method), hydrothermal synthesis method, liquid-phase combustion method etc.Coprecipitation method and Sol-gel method complex process, production cycle are long, the process influence factor is many.In recent years, microwave excitation liquid-phase combustion method is as a kind of nano-powder method for preparing fast and efficiently, can be used to that synthetic crystallization is good, narrow diameter distribution, pattern is controlled and purity is high nano-powder.
Summary of the invention
The object of the invention is to propose a kind of novel process for preparing rare-earth activated luminous nano-phosphor, thereby the low cost of developing, is easy to industrialization and the good preparation luminous fluorescent material novel method of product property.The main characteristics of this method are to adopt microwave excitation low-temperature liquid-phase combustion synthesis of nano fluorescent material.
Microwave is as a kind of rapidly and effectively type of heating, and enormous function has been brought into play in the aspect quickening chemical reaction, improve the quality of products etc., and the increasingly extensive synthetic field that is used for novel material.Compare with the routine heating, microwave heating does not need the conduction and the convection current of heat, make medium molecule reach active state in short period of time at the utmost point, the motion and the collision of aggravation molecule, fast reaction speed shortens reaction time greatly, and because of inside and outside heating simultaneously, system is heated evenly, and does not have thermograde in synthetic reaction process, thereby guarantees the homogeneity of sintetics.
Microwave excited liquid phase medium of the present invention is the mixing solutions that metal nitrate, urea (or glycine) and an amount of additive are formed.Metal nitrate, urea (or glycine, kappa amine), the reactant formed such as additive (in right amount) reaches the uniform mixing of atom level in the aqueous solution, guaranteed that rare-earth ion activated dose is evenly distributed in the parent lattice, thereby can obtain highly efficient fluorescent material.
With pack into reaction unit and insert and carry out the microwave excitation low-temperature combustion synthesis reaction in the microwave equipment of mixed uniformly solution.Microwave excitation equipment adopts single mold microwave radiation design, and its microwave intensity is constant, can produce lasting microwave field, makes sample be subjected to the isostatic microwave radiation, changes energy intensity by the output rating of regulating sustained wave.By infrared temperature controller accurate temperature controlling.The microwave excitation frequency is 2.45GHz, and microwave power is 500-1000W, and the reaction times is 5-10 minute.
Preparation method's of the present invention step is:
Luminous fluorescent material can be taken from one or several of following chemical formula: Sr
2MgSi
2O
7: (Eu
2+, Dy
3+), Y
2O
3: (Eu
3+, Ca
2+, Ti
4+), SrAl
2O
4: (Eu
2+, Dy
3+);
(1), presses chemical formula Sr
2MgSi
2O
7: (Eu
2+, Dy
3+), Y
2O
3: (Eu
3+, Ca
2+, Ti
4+), SrAl
2O
4: (Eu
2+, Dy
3+) take by weighing the rare earth oxide of corresponding mole number spectroscopically pure level, the metal nitrate of analytical pure level;
(2), with the rare earth oxide dilute nitric acid dissolution, all the other samples that will take by weighing are then put into wherein, add deionized water at last and stir, and fully dissolve until raw material, obtain nitrate solution;
(3), add organic-fuel, the mol ratio of organic-fuel and nitrate is 1.2-1.5;
(4), add following one or more compounds: additive, fusing assistant, morphology control agent;
(5), the solution with step (4) gained carries out the microwave excitation low-temperature combustion synthesis reaction;
(6) pass through infrared temperature control in 550-600 ℃, combustion synthesis reaction 5-10min, obtaining grain-size is the luminous nano-phosphor of 40-60nm.
Organic-fuel described in the above-mentioned steps (3) comprises: urea, glycine, kappa amine.
The matrix crystalline phase of luminous fluorescent material is single thing phase, and its grain-size is not more than 60nm.
The microwave reaction condition is: microwave frequency is 2.45GHz, and microwave power is 800W, and the reaction times is 5-10 minute, and temperature is controlled in 550-600 ℃.
Compared with prior art, utilize microwave excitation low-temperature burning synthetizing phosphor powder that following characteristics are arranged:
(1) microwave is whole, inner heating, and reactant is heated evenly, and heat-up rate is fast, shortens the reaction times greatly, has efficient, energy-conservation advantage;
(2) the synthetic product is pure, crystallization is good, luminous efficiency is high, and the excitation spectrum of product, emmission spectrum meet service requirements fully;
(3) the product particle does not need ball mill pulverizing and aftertreatment directly to use for spherical, size are 40-60nm;
(4) production technique is simple, and the production efficiency height is easy to realize industrialization.Because reaction does not then need the outside that any energy is provided again in case light, whole combustion processes relies on self liberated heat complete automatically and quickly fully.Therefore, adopt the microwave excitation low-temperature combustion synthesis technology, can realize the low cost preparation of the rare-earth activated luminous nano-phosphor highly pure, that crystallization is good, luminous efficiency is high.
Description of drawings
Fig. 1 is the SrAl of preparation
2O
4: (Eu, Dy) XRD figure of fluorescent material spectrum shows that product is a pure phase;
Fig. 2 is the FE-SEM picture of the fluorescent material of preparation, and visible particle is spherical, size 40-60nm;
Fig. 3 is the SrAl of preparation
2O
4: (as seen it excites main peak to be positioned at about 340nm for Eu, the Dy) excitation spectrum of fluorescent material, and excitation peak is peak, a broadband (230-400nm), thereby illustrating that fluorescent material can effectively be excited in quite wide excitation wavelength range produces luminescence phenomenon;
Fig. 4 is the SrAl of preparation
2O
4: (Eu, the Dy) emmission spectrum of fluorescent material, emission peak are about 450nm.
Embodiment
Further illustrate the present invention in the mode of embodiment below, but not only be confined to embodiment.
Embodiment 1
With Sr (NO
3)
2, Al (NO
3)
39H
2O, Ba (NO
3)
2And Eu
2O
3(spectroscopically pure), Dy
2O
3The nitrate solution of (spectroscopically pure) mixes by a certain percentage, adds an amount of additive again, places the porcelain crucible, adds proper amount of deionized water and constantly stirring at last, fully dissolves until raw material, obtains mixed uniformly clear solution.
Solution inserted carry out the microwave excitation low-temperature combustion synthesis reaction in the microwave equipment.By infrared temperature controller accurate temperature controlling in 550 ℃.The microwave excitation frequency is 2.45GHz, and microwave power is 800W, and the reaction times is 10 minutes.After reaction finishes, promptly get spumescence powder product.Product is through the X-ray powder diffraction analysis, and the result shows that product is a pure phase, as shown in Figure 1.The field emission scanning electron microscope picture of product shows that particle is spherical, and is of a size of about 50nm as shown in Figure 2.
Embodiment 2
Initial feed Eu
2O
3, Dy
2O
3Be spectroscopically pure, Sr (NO
3)
2, Al (NO
3)
39H
2O, Ba (NO
3)
2And CO (NH
2)
2Be analytical pure, and to take by weighing mass ratio be 1% H
3BO
3, AlF
3Be additive.
Press SrAl
2O
4: (Eu, Dy) stoichiometric accurately take by weighing mentioned reagent with analytical balance.
In beaker, at first use concentrated nitric acid (analytical pure) with Eu
2O
3, Dy
2O
3Fully dissolving will take by weighing Sr (NO then
3)
2, Al (NO
3)
39H
2O, Ba (NO
3)
2And CO (NH
2)
2Put into wherein.Add proper amount of deionized water and constantly stirring at last, fully dissolve, obtain mixed uniformly clear solution until raw material.
Solution inserted carry out the microwave excitation low-temperature combustion synthesis reaction in the microwave equipment.By infrared temperature controller accurate temperature controlling in 600 ℃.The microwave excitation frequency is 2.45GHz, and microwave power is 800W, and the reaction times is 10 minutes.After reaction finishes, promptly get spumescence white powder product.The product that obtains is through the spectrum property test, its excitation spectrum as shown in Figure 3, as seen it excites main peak to be positioned at about 340nm, and excitation peak is peak, a broadband (230-400nm), thereby illustrating that fluorescent material can effectively be excited in quite wide excitation wavelength range produces luminescence phenomenon; Its emmission spectrum as shown in Figure 4, its emission peak is about 450nm.
Claims (4)
1. microwave excitation low-temperature liquid-phase combustion synthesis of nano luminous fluorescent material SrAl
2O
4: (Eu
2+, Dy
3+) the preparation method, it is characterized in that:
Its preparation process is:
(1), presses chemical formula SrAl
2O
4: (Eu
2+, Dy
3+) take by weighing the rare earth oxide of corresponding mole number spectroscopically pure level, the metal nitrate of analytical pure level;
(2), with the rare earth oxide dilute nitric acid dissolution, all the other samples that will take by weighing are then put into wherein, add deionized water at last and stir, and fully dissolve until raw material, obtain nitrate solution;
(3), add organic-fuel, the mol ratio of organic-fuel and nitrate is 1.2-1.5;
(4), add following one or more compounds: additive, fusing assistant, morphology control agent;
(5), the solution with step (4) gained carries out the microwave excitation low-temperature combustion synthesis reaction;
(6), by infrared temperature control in 550-600 ℃, combustion synthesis reaction 5-10 minute, obtaining grain-size was the luminous nano-phosphor of 40-60nm.
2. according to the described preparation method of right 1, it is characterized in that: the organic-fuel described in the above-mentioned steps (3) is: urea, glycine, kappa amine.
3. according to the described preparation method of right 1, it is characterized in that: the matrix crystalline phase of luminous fluorescent material is single thing phase, and its grain-size is 40-60nm.
4. according to the described method of right 1, it is characterized in that: the microwave reaction condition is: microwave frequency is 2.45GHz, and microwave power is 800W, and the reaction times is 5-10 minute, and temperature is controlled in 550-600 ℃.
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|---|---|---|---|
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