CN102965103A - Superfine rare earth magnesium silicate strontium fluorescent powder and preparation technology thereof - Google Patents
Superfine rare earth magnesium silicate strontium fluorescent powder and preparation technology thereof Download PDFInfo
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- CN102965103A CN102965103A CN 201210524072 CN201210524072A CN102965103A CN 102965103 A CN102965103 A CN 102965103A CN 201210524072 CN201210524072 CN 201210524072 CN 201210524072 A CN201210524072 A CN 201210524072A CN 102965103 A CN102965103 A CN 102965103A
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Abstract
The invention relates to a superfine rare earth magnesium silicate strontium fluorescent powder and a preparation technology thereof. The superfine rare earth magnesium silicate strontium fluorescent powder is characterized in that the fluorescent power takes Sr2MgSi2O7 as a matrix, and Eu<2+> and Dy<3+> rare earth ions as activating agents, a crystal structure is a tetragonal system akermanite structure, the grain size of the powder is less than 5mu m, and the powder can emit blue visible lights with the wavelength of about 470nm after irradiated by ultraviolet or visible lights for 1-10 minutes, and the afterglow service life of the powder reaches above 5 hours. The fluorescent powder is nontoxic, harmless and free of radioactive contamination and has no adverse effect on human bodies and the environment. The main preparation processes of the superfine fluorescent power are as follows: a rare earth magnesium silicate strontium precursor and xerogel are prepared through a sol-gel technology, and then a rare earth magnesium silicate luminescent material is obtained through high-temperature roasting, and the superfine fluorescent powder with the grain size of less than 5mu m is obtained by smashing and grinding the luminescent material.
Description
Technical field
The present invention relates to the rare earth long-afterglow luminescent material preparation field, specifically a kind of ultra-fine (＜5 μ m) rare earth Magnesium Silicate q-agent strontium long afterglow luminescent powder body and technology of preparing thereof.
Background technology
Long after glow luminous material is commonly called as luminescent powder, and this material can be luminous lastingly in dark surrounds after the light (such as ultraviolet ray or visible light etc.) of specific wavelength excites.Because their energy-accumulating luminous behavior can be used for making luminous paint, luminescent plastics, luminescent fibre, luminescent paper etc., be used widely in fields such as building dress is drilled, military installations, communications and transportation, fire-fighting emergent.The long after glow luminous material that uses at present mainly contains three major types: a class is traditional sulfide series long after glow luminous material, and a class is the aluminates system long after glow luminous material, and the 3rd class is the silicate systems long after glow luminous material.Compare with traditional sulfide long-afterglow material, the aluminates system long after glow luminous material has the after-glow brightness height, the advantage that twilight sunset is long, and can not produce harm to HUMAN HEALTH and environment.But this class material water tolerance is relatively poor, needs to carry out physical chemistry modifying at particle surface, to improve its stability.These shortcomings for the aluminates system material, the researchist has carried out the research of silicate systems long after glow luminous material, such luminescent material has good chemical stability, water-fast dissolubility and thermostability, low price, cost is low, and the exciting light wide ranges has covered from the ultraviolet to the visible region, and twilight sunset presents from blue light luminous to gold-tinted continually varying multiple color.
The preparation of long after glow luminous material mainly is to be undertaken by high temperature solid state reaction at present, after soon the chemical pure raw material mixes, and calcination under the reducing atmosphere in high temperature kiln, and then obtain luminescent powder after the process fine grinding.The luminescent powder particle that obtains by above-mentioned technique is thicker, and generally more than 10 μ m, and sintering temperature is high, the block hardness that forms behind the sintering is large, and the luminescent properties that grinds energetically powder causes larger infringement.Because particle diameter is relatively large, can not use the higher occasion of fineness requirement at some, has greatly limited application and the development of silicate luminescent material.
Summary of the invention
The present invention is directed to the deficiency in the above-mentioned background technology, under the prerequisite that guarantees the luminescent material afterglow property, adopt sol-gel technique and high-temperature calcination to prepare grain diameter less than the superfine rare-earth Magnesium Silicate q-agent strontium luminescent powder of 5 μ m, this powder has that particle diameter is little, narrow diameter distribution, luminous quantum efficiency is high, the twilight sunset life-span is long characteristics.
The present invention is achieved through the following technical solutions.Luminescent material is with Magnesium Silicate q-agent strontium (Sr
2MgSi
2O
7) be the matrix crystalline phase, Eu
2+, Dy
3+Rare earth ion is as activator (luminescence center), prepare rare earth Magnesium Silicate q-agent strontium presoma and xerogel by sol-gel technique, then obtain rare earth Magnesium Silicate q-agent strontium luminescent material by high-temperature roasting, finally obtain particle diameter less than the ultra-fine luminescent powder of 5 μ m by grinding.Its chemical constitution formula is Sr
2-x-yMgSi
2O
7: Eu
2+ x, Dy
3+ y, B
3+ z, the additional proportion of moiety is: Eu
2+Add-on be equivalent to Sr
2+1～4mol%, Dy
3+Add-on be equivalent to Sr
2+1～4mol%, B
3+Add-on be equivalent to Sr
2+5～20mol%
Below the invention will be further described, concrete steps are as follows:
(1) according to the accurate weighing strontium nitrate of above-mentioned chemical constitution, magnesium nitrate hexahydrate, boric acid, europium sesquioxide and dysprosium oxide, then strontium nitrate, magnesium nitrate hexahydrate and boric acid are dissolved in the appropriate amount of deionized water, europium sesquioxide, dysprosium oxide are dissolved in the certain density salpeter solution, again above-mentioned two kinds of solution are mixed, obtain nitrate solution;
(2) measure the tetraethoxy of certain volume according to chemical constitution, and it is dissolved in an amount of dehydrated alcohol, the solution that obtains is mixed with step 1 gained nitrate solution, and place on the constant temperature blender with magnetic force and stir;
(3) using concentrated nitric acid regulator solution pH value is 1, and the temperature that constant temperature blender with magnetic force is set is 50～80 ℃, makes the continuous hydrolytic condensation of tetraethoxy, and moisture is evaporated to solution and becomes viscosity colloidal sol, and is finally converted into thick gel.Place 80～120 ℃ of thermostatic drying chambers to carry out drying the gel that obtains, obtain the white powder xerogel;
(4) xerogel was being carried out double sintering 3～6 hours under the weakly reducing atmosphere in 1000～1150 ℃ of High Temperature Furnaces Heating Apparatuss, after the taking-up cooling, grinding sieves can obtain particle diameter less than the superfine rare-earth Magnesium Silicate q-agent strontium long afterglow luminescent powder body of 5 μ m.
Superfine rare-earth long persistence luminescent silicate material of the present invention, its crystalline structure are the akermanite structure of tetragonal system, and chemical constitution is Sr
2MgSi
2O
7: Eu
2+, Dy
3+, through the irradiation of Uv and visible light 1～10min, can send the blue visible light that wavelength is 470nm, the twilight sunset life-span reached more than 5 hours.This superfine powder has good dispersiveness and homogeneity (narrow diameter distribution), can mix in printing ink, the paint, method by silk screen printing or air brushing forms printed matter with certain illumination effect, lamp box advertisement picture etc., also can in spinning process, add and form the noctilucence yarn and make various adornments etc., these products produce blue afterglow effect in dark surrounds after the irradiation of natural light or fluorescent lamp excites.
Embodiment
The present invention is described in more detail below in conjunction with embodiment, but the present invention is not limited to these embodiments.
Embodiment one
By mole% weighing 4.106g Sr (NO
3)
2, 2.564g Mg (NO
3)
26H
2O, 0.062g H
3BO
3, 0.018g Eu
2O
3, 0.037g Dy
2O
3, 4.167g (C
2H
5O)
4Si.With Sr (NO
3)
2, Mg (NO
3)
26H
2O, H
3BO
3Be dissolved in the 30ml deionized water; With Eu
2O
3, Dy
2O
3Be dissolved in 30ml HNO
3Solution; With (C
2H
5O)
4Si is dissolved in the 25ml dehydrated alcohol.Above-mentioned three kinds of solution are mixed, and the control amount of water makes overall solution volume about 100ml, adds hydrolyst HNO in solution
3Regulator solution pH value is 1, then solution is placed on the constant temperature blender with magnetic force and stirs, and it is 80 ℃ that whipping temp is set, and makes it fully mix and be hydrolyzed condensation reaction.After the solution moisture content testing evaporation forms thick wet gel, put it in 80 ℃ of thermostatic drying chambers and dry, obtain loosely organized white powder xerogel.The xerogel that obtains is put into the corundum boat, place High Temperature Furnaces Heating Apparatus calcination 3h under 1050 ℃ of reducing atmospheres, namely obtain Sr
2MgSi
2O
7: Eu
2+, Dy
3+Blue long afterflow luminescent material.
Embodiment two
By mole% weighing 4.106g Sr (NO
3)
2, 2.564g Mg (NO
3)
26H
2O, 0.093g H
3BO
3, 0.035g Eu
2O
3, 0.075g Dy
2O
3, 4.167g (C
2H
5O)
4Si.With Sr (NO
3)
2, Mg (NO
3)
26H
2O, H
3BO
3Be dissolved in the 30ml deionized water; With Eu
2O
3, Dy
2O
3Be dissolved in 30ml HNO
3Solution; With (C
2H
5O)
4Si is dissolved in the 25ml dehydrated alcohol.Above-mentioned three kinds of solution are mixed, and the control amount of water makes overall solution volume about 120ml, adds hydrolyst HNO in solution
3Regulator solution pH value is 1, then solution is placed on the constant temperature blender with magnetic force and stirs, and it is 80 ℃ that whipping temp is set, and makes it fully mix and be hydrolyzed condensation reaction.After the solution moisture content testing evaporation forms thick wet gel, put it in 100 ℃ of thermostatic drying chambers and dry, obtain loosely organized white powder xerogel.The xerogel that obtains is put into the corundum boat, place High Temperature Furnaces Heating Apparatus calcination 4h under 1100 ℃ of reducing atmospheres, namely obtain Sr
2MgSi
2O
7: Eu
2+, Dy
3+Blue long afterflow luminescent material.
Embodiment three
By mole% weighing 4.106g Sr (NO
3)
2, 2.564g Mg (NO
3)
26H
2O, 0.124g H
3BO
3, 0.070g Eu
2O
3, 0.075g Dy
2O
3, 4.167g (C
2H
5O)
4Si.With Sr (NO
3)
2, Mg (NO
3)
26H
2O, H
3BO
3Be dissolved in the 30ml deionized water; With Eu
2O
3, Dy
2O
3Be dissolved in 30ml HNO
3Solution; With (C
2H
5O)
4Si is dissolved in the 25ml dehydrated alcohol.Above-mentioned three kinds of solution are mixed, the control amount of water makes overall solution volume about 150ml, adding hydrolyst HNO3 regulator solution pH value in the solution is 1, then solution is placed on the constant temperature blender with magnetic force and stir, it is 80 ℃ that whipping temp is set, and makes it fully mix and be hydrolyzed condensation reaction.After the solution moisture content testing evaporation forms thick wet gel, put it in 120 ℃ of thermostatic drying chambers and dry, obtain loosely organized white powder xerogel.The xerogel that obtains is put into the corundum boat, place High Temperature Furnaces Heating Apparatus calcination 6h under 1150 ℃ of reducing atmospheres, namely obtain Sr
2MgSi
2O
7: Eu
2+, Dy
3+Blue long afterflow luminescent material.
Claims (2)
1. superfine rare-earth Magnesium Silicate q-agent strontium luminescent powder, it is characterized in that: this luminescent powder is with Sr
2MgSi
2O
7Be matrix, Eu
2+, Dy
3+Rare earth ion is activator, and crystalline structure is the akermanite structure of tetragonal system, and diameter of particle is less than 5 μ m, through ultraviolet or radiation of visible light 1～10 minute, can send wavelength and be near the blue visible light the 470nm, and the twilight sunset life-span reached more than 5 hours.This luminescent powder is nontoxic, without radiocontamination, to human body and environment without any detrimentally affect.
2. the preparation method of superfine rare-earth Magnesium Silicate q-agent strontium luminescent powder according to claim 1 is characterized in that:
(1) main raw material and consumption: strontium nitrate, magnesium nitrate hexahydrate, boric acid, tetraethoxy, europium sesquioxide, dysprosium oxide, press composition formula Sr
2-x-yMgSi
2O
7: Eu
2+ x, Dy
3+ y, B
3+ zCalculate the consumption of each component of configuration, wherein Eu
2+Add-on be equivalent to Sr
2+1～4mol%, Dy
3+Add-on be equivalent to Sr
2+1～4mol%, B
3+Add-on be equivalent to Sr
2+5～20mol%;
(2) accurately take by weighing each component according to above-mentioned chemical constitution, then strontium nitrate, magnesium nitrate hexahydrate and boric acid are dissolved in the appropriate amount of deionized water, europium sesquioxide, dysprosium oxide are dissolved in the certain density salpeter solution, more above-mentioned two kinds of solution are mixed, obtain nitrate solution.Tetraethoxy is dissolved in an amount of dehydrated alcohol, gained solution mixes with nitrate solution, using concentrated nitric acid regulator solution pH value is 1, placing temperature is to stir on 50～80 ℃ of constant temperature blender with magnetic force, until being evaporated to solution, moisture becomes viscosity colloidal sol, and be finally converted into thick gel, and place 80～120 ℃ of thermostatic drying chambers to carry out drying the gel that obtains, obtain the white powder xerogel;
(3) xerogel is carried out sintering 3～6 hours under the weakly reducing atmosphere in 1000～1150 ℃ of High Temperature Furnaces Heating Apparatuss, grinding after the cooling and sieve, namely obtaining particle diameter less than the superfine rare-earth Magnesium Silicate q-agent strontium long afterglow luminescent powder body of 5 μ m.
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| CN103938297A (en) * | 2014-04-29 | 2014-07-23 | 江南大学 | Europium and dysprosium co-doped strontium magnesium silicate luminescent nanofiber and preparation method thereof |
| CN106277791B (en) * | 2016-08-13 | 2019-04-09 | 华南理工大学 | A kind of high temperature resistant silicon hydrochlorate luminous ceramic glaze and preparation method thereof |
| CN106277791A (en) * | 2016-08-13 | 2017-01-04 | 华南理工大学 | A kind of high temperature resistant silicon hydrochlorate luminous ceramic glaze and preparation method thereof |
| CN107025858A (en) * | 2017-05-05 | 2017-08-08 | 邢玉凯 | A kind of manufacture method of electronic paper-type safety sign |
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| CN108716042A (en) * | 2018-05-17 | 2018-10-30 | 江苏工程职业技术学院 | A kind of preparation method of functionality heavy twist color spot silk |
| CN108587602A (en) * | 2018-05-31 | 2018-09-28 | 陕西科技大学 | A method of it is modified by long after glow luminous material surface and improves luminescent properties |
| CN109734940A (en) * | 2019-01-29 | 2019-05-10 | 江南大学 | A kind of preparation method of the luminous canopy film of rare earth silicate base composite red color |
| CN109734940B (en) * | 2019-01-29 | 2021-07-16 | 江南大学 | Preparation method of rare earth silicate-based composite red light-emitting greenhouse film |
| CN114032090A (en) * | 2021-12-03 | 2022-02-11 | 广东电网有限责任公司 | Yellow-green afterglow material and preparation method thereof |
| CN114682275A (en) * | 2022-04-07 | 2022-07-01 | 辽宁大学 | Z-type Sr2MgSi2O7:Eu2+,Dy3+/Ag3PO4Photocatalyst and preparation method thereof |
| CN114836212A (en) * | 2022-04-22 | 2022-08-02 | 重庆交通大学 | Based on SiO 2 Silicate long-afterglow luminescent material with porous morphology of aerogel and preparation method thereof |
| CN114836212B (en) * | 2022-04-22 | 2023-11-03 | 重庆交通大学 | SiO-based 2 Aerogel porous silicate long afterglow luminescent material and preparation method thereof |
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Application publication date: 20130313 |