CN101250410B - Cerium and ferrous lithium aluminate codoped light-conversion fluorescent powder and preparation method thereof - Google Patents
Cerium and ferrous lithium aluminate codoped light-conversion fluorescent powder and preparation method thereof Download PDFInfo
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- CN101250410B CN101250410B CN2008100304181A CN200810030418A CN101250410B CN 101250410 B CN101250410 B CN 101250410B CN 2008100304181 A CN2008100304181 A CN 2008100304181A CN 200810030418 A CN200810030418 A CN 200810030418A CN 101250410 B CN101250410 B CN 101250410B
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Abstract
The invention discloses a light-conversion fluorescent powder of lithium aluminate which co-dopes cerium Ce and iron Fe and the process for preparation, the light-conversion fluorescent powder can effectively converses ultraviolet light into red light or close to infrared light, which can be used in agricultural light conversion, artificial plant illumination lighting apparatus, television remotecontrollers, night vision devices, and medical cares and the like. The fluorescent powder utilizes normal lithium aluminate to be substrate, utilizes Fe3+and Ce3+ to be activating agent, utilizes Fe3+and Ce3+ to be doping agent, light-conversion fluorescent powder which is needed is prepared through dissolving in nitric acid, mixing and reacting in high temperature, the chemical composition formula is LiAlO2:xFe, yCe, wherein x and y are molar ration between Fe and Ce ions and LiAlo2 molecule, and permissible values of x and y are all 0.1-5%.
Description
Technical field
The present invention relates to a kind of light-conversion fluorescent powder of mixing cerium, ferrous lithium aluminate altogether and preparation method thereof.This luminescent phosphor can be incorporated into to improve in the film changes optical efficiency, is used for various agricultural installations, also can be used as the lamp powder and makes fluorescent-lamp-use in fields such as medical treatment.
Background technology
Studies show that, increase the exposure intensity to farm crop ruddiness and blue light, can impel crop growth and volume increase, the plant-growth luminescent lamp is the agricultural science and technology that therefore grows up, and it is very useful aspect growing seedlings in the farm crop room temperature.On the other hand, how converting green glow in the sunlight and UV-light to ruddiness and blue light, is the important scientific and technological problem that makes full use of sun power development efficient ecological agricultural.Embedded photoluminescent material has the light transition function, studies show that in a large number, embedded photoluminescent material is mixed the plastic sheeting for farm use of blowing out in the plastics as auxiliary agent can convert ruddiness and blue light to effectively with green glow in the daylight or UV-light.The embedded photoluminescent material that is applied in the plastic film is called light-converting agent, and the plastic film that has added light-converting agent is called light-converting film.The farmland is tested and shown, and is luxuriant with crop root prosperity, the cauline leaf of light-converting film cultivation, and can increasing both production and income and the quality that improves agricultural-food.
As far back as 1976, Japanese agriculture utilized technical study association just once to report the polyvinyl chloride film of mixing blue-fluorescence, red fluorescence auxiliary agent with the light line options.1979, reported and used rhodamine 6G to make the film that yellow green light is converted to blood orange light.Nineteen eighty-two, Japanese mountain is added people such as winning a man of virtue and ability and the rare-earth fluorescent compound is added to is made luminescence polymer in the polystyrene.1987, people such as Tanaka mixed coumarins and benzo fluorescent bleaches and make blue light film 10 in the polyvinyl chloride resin] .1985, people such as Russian Golodkova.L.N join the rare-earth fluorescent compound in the resins such as PVC, PE and make greenhouse film.
China's research in this respect starts from later 1980s, looks back the development process of optical transfer agricultural film during the last ten years, and the domestic as can be known research to light-converting agent, optical transfer agricultural film is very active; Its booth experimental scale constantly enlarges, and crop varieties is on the increase, and from culture of ginseng, raising rice seedlings, vegetable melon and fruit are planted flower culture all in test, and have all obtained gratifying effect.The commercialization production of light-converting agent, light conversion matrix materiel and optical transfer agricultural film and market competition thereof progressively form.
In all kinds of agricultural light-converting films, light-converting agent is a core.Become one of research focus of current luminescent material.Relevant patent also continues to bring out.Announced multi-kernel rare-earth light-converting powder that UV-light is converted to ruddiness and preparation method thereof as patent " multi-kernel rare-earth light-converting powder, its preparation method and application thereof " (publication number CN1338500).Patent " nano bionic attitude rare-earth light conversion agent and nano bionic attitude Light Transform Farm Film Doped with Rare Earth and preparation method thereof " (publication number CN1648172) and for example, this patent disclosure a kind of coated with rare-earth light conversion agent preparation technology, with the inorganic particles is base nuclear, with the rare earth gel is that the nano rare earth particle is a coating layer, adopts the rare-earth light-converting material of the method for electroless plating at inorganic particles surface coating one deck nano thickness.
Existing relate to [as JP11263971, JP8293285, CN1448463, the JP7268318] of patent with the light-conversion fluorescent powder of the lithium aluminate of singly mixing iron.This material can be used to prepare special fluorescent luminaire fluorescent material.The lithium aluminate of mixing iron also can convert UV-light to ruddiness as fluorescent material, as sun power ultraviolet light-converting agent, makes plant strengthen the utilization ratio of sunlight.Regrettably, it is but not very good that the lithium aluminate of mixing iron changes optical efficiency.How to improve the commentaries on classics optical efficiency of this class material, become one of key problem of this class investigation of materials.Change the optical efficiency raising in order to make, we have creatively carried out the ion sensitized experimental study of series of rare earth, attempt to improve the commentaries on classics optical efficiency of such material.By the analysis and the test of system, found the ultraviolet sensitizing effect of cerium to iron ion.The commentaries on classics optical efficiency that the lithium aluminate commentaries on classics optical efficiency that cerium, iron ion are mixed is altogether relatively singly mixed the lithium aluminate of iron can double many.Thereby the lithium aluminate fluorescent material that makes cerium, iron ion mix altogether becomes more effective sun power ultraviolet light-converting agent, strengthens the utilization ratio of plant to sunlight; As a kind of high-efficiency fluorescence powder, the lamp powder that also can be used as luminescent lamp is used for plant illumination or medical treatment etc.
Synthetic a lot of methods arranged, usually solid-phase synthesis, sol-gel method, coprecipitation method etc. are arranged for the lithium niobate powder.Both preparation process complexity of back, cost is expensive, and reaction time is longer, has by product after the reaction in addition.Consider the unique of this material Application Areas and mass, the security of producing, these methods are just not too suitable.
Summary of the invention
The object of the present invention is to provide a kind of light-conversion fluorescent powder of mixing cerium, ferrous lithium aluminate altogether and preparation method thereof.
The objective of the invention is to realize by following approach: a kind of light-conversion fluorescent powder of mixing cerium, ferrous lithium aluminate altogether, the chemical constitution formula of this light-conversion fluorescent powder are LiAlO
2: xFe, yCe, wherein x and y are respectively adulterated iron Fe ion, cerium Ce ion and LiAlO
2The mol ratio of molecule, the permissible value scope of x and y is all 0.1%～5%.The emission wavelength ranges of this light-conversion fluorescent powder is 630～850nm.
A kind of preparation method who mixes the light-conversion fluorescent powder of cerium, ferrous lithium aluminate altogether prepares according to following steps:
A. the ratio in described light-conversion fluorescent powder chemical constitution formula takes by weighing nine water aluminum nitrate Al (NO
3)
39H
2O, Quilonum Retard Li
2CO
3, Iron trichloride hexahydrate FeCl
36H
2O cerium oxide CeO
2
B. the method for using nitric acid dissolve is with above-mentioned raw materials and fusing assistant boric acid H
3BO
3After mixing, clarification;
C. with the clear soln evaporation, become solid, in 400～500 ℃ muffle furnace, it is decomposed to oxide compound then;
D. take out oxide compound and ground about 1 hour, be put at last in the muffle furnace and naturally cool to room temperature 1000～1100 ℃ of calcinings after 10～11 hours and get finished product.
The content of described boric acid with LiAlO
2The molar ratio computing of molecule, it is worth less than 5%.
The present invention has following advantage compared with prior art:
(1) light-conversion fluorescent powder of this invention preparation is compared with the corresponding fluorescent material of singly mixing iron.The equality strength ultraviolet source excites down luminous intensity to significantly improve, and more can effectively absorb the UV-light in the sunlight and be converted to ruddiness and near infrared light;
(2) emission wavelength of the light-conversion fluorescent powder of the preparation of this invention can be used for artificial plant fluorescent light tool, TV remote controller, night vision device and medical applications etc. at 630-850nm;
(3) matrix at high temperature has good chemistry, thermostability and mechanical stability.Good with the other materials consistency, fabulous anti-Radiation Characteristics is especially arranged;
(4) present existing agricultural booth generally uses film, and this light conversion agent can mix in the plastics film, helps the popularization of this light-conversion fluorescent powder.As solid-phase synthesis its disadvantageous one side is arranged also, long as the time cycle, need to grind, time consumption and energy consumption, we make it the preparation method of thorough mixing reaction by a kind of nitric acid dissolve reactant of using, and have improved preparation efficiency greatly.
Description of drawings
Below in conjunction with accompanying drawing the present invention is described in further detail:
Fig. 1 is embodiment 1 preparation doped with cerium ionic concentration is 2%, the concentration of iron is 1% light-conversion fluorescent powder emmission spectrum figure;
Fig. 2 is embodiment 2 preparation doped with cerium ionic concentration are 5%, the concentration of iron is 1% light-conversion fluorescent powder emmission spectrum figure;
Fig. 3 is embodiment 3 preparation doped with cerium ionic concentration are 2%, the concentration of iron ion is 5% light-conversion fluorescent powder emmission spectrum figure;
Fig. 4 is embodiment 4 preparation doped with cerium ionic concentration are 0.5%, the concentration of iron ion is 1.5% light-conversion fluorescent powder emmission spectrum figure.
Embodiment
The chemical constitution formula of the light-conversion fluorescent powder that the present invention announced is LiAlO
2: xFe, yCe, wherein x and y are respectively iron Fe ion, cerium Ce ion and LiAlO
2The mol ratio of molecule, the permissible value scope of x and y is all 0.1～5%.The emission wavelength ranges of this light-conversion fluorescent powder is 630～850nm.
Following four embodiment of concrete preparation method's reference of this light-conversion fluorescent powder:
Embodiment one:
Chemical formula LiAlO according to sample
2: 1%Fe.2%Ce takes by weighing Li respectively
2CO
32.218g, Al (NO
3)
39H
2O22.508g, FeCl
36H
2O 0.162g, CeO
20.207g, H
3BO
30.015g, after with sour dissolved method above-mentioned raw materials being mixed, it is evaporated to solid, in 400～500 ℃ muffle furnace, it is decomposed to oxide compound then; Take out oxide compound and ground about 1 hour, be put at last in the muffle furnace and calcined 9 hours, naturally cool to room temperature, obtain light-conversion fluorescent powder at 1000 ℃.
Fig. 1 is the LiAlO of present embodiment preparation
2: 1%Fe 2%Ce light-conversion fluorescent powder emmission spectrum, the solid line among the figure are that the concentration of mixing cerium is 2%, the concentration of iron is 1%, and as a comparison, dotted line provides is that the concentration of mixing cerium is 0%, the concentration of iron is 1%.As shown in Figure 1, the luminous intensity of the light-conversion fluorescent powder of present embodiment preparation is not mix 1.8 times of sample of cerium ion, and this fluorescent material more can effectively convert UV-light to absorbable ruddiness of plant and near infrared light, and its centre wavelength is 742nm.
Embodiment 2:
Chemical formula LiAlO according to sample
2: 1%Fe.5%Ce takes by weighing Li respectively
2CO
31.109g, Al (NO
3)
39H
2O11.254g, FeCl
36H
2O 0.081g, CeO
20.258g, H
3BO
30.008g, after with sour dissolved method above-mentioned raw materials being mixed, it is evaporated to solid, in 400～500 ℃ muffle furnace, it is decomposed to oxide compound then; Take out oxide compound and ground about 1 hour, be put at last in the muffle furnace and calcined 11 hours, naturally cool to room temperature, obtain light-conversion fluorescent powder at 1100 ℃.
Fig. 2 is the LiAlO of present embodiment preparation
2: 1%Fe 5%Ce light-conversion fluorescent powder emmission spectrum.Solid line among the figure is that the concentration of mixing cerium is 5%, the concentration of iron is 1%, and as a comparison, dotted line provides is that the concentration of mixing cerium is 0%, the concentration of iron is 1%.As shown in Figure 2, the luminous intensity of the light-conversion fluorescent powder of present embodiment preparation is not mix 1.2 times of cerium ion sample, and this fluorescent material more can effectively convert UV-light to absorbable ruddiness of plant and near infrared light, and its centre wavelength is 742nm.
Embodiment 3:
Chemical formula LiAlO according to sample
2: 5%Fe, 2%Ce takes by weighing Li respectively
2CO
31.479g, Al (NO
3)
39H
2O15.005g, FeCl
36H
2O 0.541g, CeO
20.138g, H
3BO
30.010g, after with sour dissolved method above-mentioned raw materials being mixed, it is evaporated to solid, in 400～500 ℃ muffle furnace, it is decomposed to oxide compound then; Take out oxide compound and ground about 1 hour, be put at last in the muffle furnace, naturally cool to room temperature, obtain light-conversion fluorescent powder 1050 ℃ of calcinings 10 hours.
Fig. 3 is the LiAlO of present embodiment preparation
2: 5%Fe.2%Ce light-conversion fluorescent powder emmission spectrum, the solid line among the figure are that doping iron ionic concentration is 5%, the concentration of cerium ion is 2%, and as a comparison, dotted line provides is that the concentration of mixing cerium ion is 0%, and concentration of iron is 5%.As shown in Figure 3, the luminous intensity of the light-conversion fluorescent powder of present embodiment preparation is not mix 2.1 times of cerium ion sample, and this fluorescent material more can effectively convert UV-light to absorbable ruddiness of plant and near infrared light, and its centre wavelength is 742nm.
Embodiment 4:
Chemical formula LiAlO according to sample
2: 1.5%Fe, 0.5%Ce takes by weighing Li respectively
2CO
31.331g, Al (NO
3)
39H
2O 13.505g, FeCl
36H
2O 0.146g, CeO
20.031g, H
3BO
30.009g, after with sour dissolved method above-mentioned raw materials being mixed, it is evaporated to solid, in 400～500 ℃ muffle furnace, it is decomposed to oxide compound then; Take out oxide compound and ground about 1 hour, be put at last in the muffle furnace and calcined 10 hours, naturally cool to room temperature, obtain light-conversion fluorescent powder at 1100 ℃.
Fig. 4 is the LiAlO of present embodiment preparation
2: 1.5%Fe.0.5%Ce light-conversion fluorescent powder emmission spectrum, the solid line among the figure are that the concentration of mixing iron is 1.5%, the concentration of cerium ion is 0.5%, and as a comparison, dotted line provides is to mix that concentration of iron is 1.5%, the concentration of cerium ion is 0%.As shown in Figure 4, the luminous intensity of the light-conversion fluorescent powder of present embodiment preparation is not mix 1.3 times of cerium ion sample, and this fluorescent material more can effectively convert UV-light to absorbable ruddiness of plant and near infrared light, and its centre wavelength is 742nm.
Claims (4)
1. light-conversion fluorescent powder of mixing cerium, ferrous lithium aluminate altogether, the chemical constitution formula that it is characterized in that this light-conversion fluorescent powder is LiAlO
2: xFe, yCe, wherein x and y are respectively adulterated iron Fe ion, cerium Ce ion and LiAlO
2The mol ratio of molecule, the permissible value scope of x and y is all 0.1%～5%.
2. the light-conversion fluorescent powder of mixing cerium, ferrous lithium aluminate altogether as claimed in claim 1, the scope that it is characterized in that the emission wavelength of this light-conversion fluorescent powder is 630～850nm.
3. preparation method who mixes the light-conversion fluorescent powder of cerium, ferrous lithium aluminate altogether, it is characterized in that: the light-conversion fluorescent powder of mixing cerium, ferrous lithium aluminate altogether prepares according to following steps:
A. the ratio in the described light-conversion fluorescent powder chemical constitution formula of claim 1 takes by weighing nine water aluminum nitrate Al (NO
3)
39H
2O, Quilonum Retard Li
2CO
3, Iron trichloride hexahydrate FeCl
36H
2O and cerium oxide CeO
2
B. the method for using nitric acid dissolve is with above-mentioned raw materials and fusing assistant boric acid H
3BO
3Mix clarification;
C. with the clear soln evaporation, become solid, in 400～500 ℃ muffle furnace, it is decomposed to oxide compound then;
D. take out oxide compound and ground about 1 hour, be put at last and naturally cool to room temperature 1000～1100 ℃ of calcinings after 10～11 hours in the muffle furnace and get finished product.
4. a kind of preparation method who mixes the light-conversion fluorescent powder of cerium, ferrous lithium aluminate altogether as claimed in claim 3 is characterized in that: as the content of fusing assistant boric acid with LiAlO
2The molar ratio computing of molecule, it is worth less than 5%.
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| CN101250410B true CN101250410B (en) | 2010-06-16 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311285A (en) * | 2001-02-22 | 2001-09-05 | 陈维伦 | Formula of rare-earth trichromatic fluorescent powder for plant tissue cultivation |
| EP1588991A1 (en) * | 2003-01-20 | 2005-10-26 | Ube Industries, Ltd. | Ceramic composite material for optical conversion and use thereof |
-
2008
- 2008-01-03 CN CN2008100304181A patent/CN101250410B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311285A (en) * | 2001-02-22 | 2001-09-05 | 陈维伦 | Formula of rare-earth trichromatic fluorescent powder for plant tissue cultivation |
| EP1588991A1 (en) * | 2003-01-20 | 2005-10-26 | Ube Industries, Ltd. | Ceramic composite material for optical conversion and use thereof |
Non-Patent Citations (10)
| Title |
|---|
| J. Jimenez-Becerril et al..Synthesis and characterization of y-LiAlO2.Journal of Nuclear Materials185 1991.1991,185(1991),304-307. |
| J.Jimenez-Becerril et al..Synthesis and characterization of y-LiAlO2.Journal of Nuclear Materials185 1991.1991,185(1991),304-307. * |
| 李飞 等.燃烧合成制备α-LiAlO2偏铝酸锂粉体.材料科学与工程20 3.2002,20(3),313-316. |
| 李飞等.燃烧合成制备α-LiAlO2偏铝酸锂粉体.材料科学与工程20 3.2002,20(3),313-316. * |
| 杨雪峰等.铕激活的铝酸锂发光性能研究.传感技术学报19 5.2006,19(5),1775-1777. |
| 杨雪峰等.铕激活的铝酸锂发光性能研究.传感技术学报19 5.2006,19(5),1775-1777. * |
| 林化新等.氯化物法制备MCFC隔膜用α- LiAlO2 细料的研究.硅酸盐学报27 4.1999,27(4),452-460. |
| 林化新等.氯化物法制备MCFC隔膜用α- LiAlO2 细料的研究.硅酸盐学报27 4.1999,27(4),452-460. * |
| 陈刚等.LiAlO2细粉料的制备及反应机理研究.无机化学学报18 2.2002,18(2),219-223. |
| 陈刚等.LiAlO2细粉料的制备及反应机理研究.无机化学学报18 2.2002,18(2),219-223. * |
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