CN102827609B - Nanometer red long-afterglow luminescent material with high afterglow performance and preparation method thereof - Google Patents
Nanometer red long-afterglow luminescent material with high afterglow performance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nanometer red long-afterglow luminescent material with high afterglow performance and a preparation method of the nanometer red long-afterglow luminescent material. The chemical formula of the material is Y202S: xEu<3+>, yMg<2+> and zTi<4+>, wherein x is from 0.01 to 0.08, y is from 0.01 to 0.06, and z is from 0.01 to 0.06; Y is yttrium, O is oxygen, S is sulfur, Eu<3+> is europium ions, Mg<2+> is magnesium ion, and Ti<4+> is titanium ion; and the material is prepared in two steps, namely alcohol thermal synthesis and calcination. The nanometer red long-afterglow luminescent material with high afterglow performance disclosed by the invention uses soluble acetate as a raw material; the preparation process is safe, non-toxic, simple and easy to operate, high in efficiency, low in cost, and easy for industrialized application; the obtained material is a nanoscale product; the afterglow time of the material is as long as 1.5 hours; and the material has high afterglow performance and good weather fastness, and can be widely used in the fields of various devices and nanometer markers and the like.
Description
Technical field
The present invention relates to nano red long after glow luminous material of a kind of high afterglow property and preparation method thereof.
Background technology
Long after glow luminous material is a kind of photo-induced energy storage functional materials, is widely used in low light level illumination, the fields such as emergent indication, building decoration and the method fine arts.Be extended to gradually again in recent years the fields such as information storage, energetic ray detection, its correlative study causes people's attention gradually.At present, blue-greenish colour and yellow-green colour long after glow luminous material are mainly rare earth doped aluminate and silicate, the luminescent properties such as its luminosity and time of persistence have all reached practical application to be needed and realizes suitability for industrialized production (" light-storing and emitting material and goods thereof ", Xiao Zhiguo, Chemical Industry Press, 2005).According to the principle of three primary colours, can be made into the long after glow luminous material of any required color with green powder, blue powder, the rouge and powder of luminosity and time of persistence and chemically stable similar temperament.The performance index and the blue and larger gap of yellow-green colour material existence such as red long afterglow luminous material its time of persistence as one of three primary colours material, can't reach the requirement of practical application.
The characteristics such as nano material has good dispersity, and sintering temperature is low, be easy to be applied to the aspects such as printing ink, pottery, coating.Find by literature search report " a kind of red long afterglow luminous material and preparation method thereof " in Chinese patent (publication number CN 101486908A).It adopts high temperature solid-state method, with Gd
2o
2s is matrix, Eu
3+for activator, appropriate doped Ti O
2, or MgO and TiO
2codoped, or SiO
2with TiO
2codoped prepares red long afterglow luminous material Gd
2o
2s:Eu, A, Ti (A=Mg, Si).This method exists weak point, at first, calcining temperature up to 1240 ℃ ~ 1280 ℃, the harsh energy consumption of condition is excessive.Secondly, raw material is to mix with the form mechanical disruption of oxide compound, be difficult in the calcination reaction process guarantee that activator and dopant ion effectively enter into matrix and form suitable luminous trap, and contain sulphur in raw material, can be to environment in the process of calcining.Again, the product of preparation need to be milled again, and size is larger, is micron level, can't be applied to the fields such as Nanoparticle labeling.
Summary of the invention
The purpose of this invention is to provide a kind of new pure phase and can send high-performance ruddiness twilight sunset, size is little, proterties is regular nanometer long after glow luminous material.
Another object of the present invention be to provide a kind of simple, efficiency is high, cost is low and be conducive to the preparation method of the above-mentioned long after glow luminous material of suitability for industrialized production.
The present invention is achieved through the following technical solutions above-mentioned purpose:
The nano red long after glow luminous material of a kind of high afterglow property, chemical formula is: Y
2o
2s:xEu
3+, yMg
2+, zTi
4+, wherein, x=0.01 ~ 0.08, y=0.01 ~ 0.06, z=0.01 ~ 0.06; Y is yttrium, and O is oxygen, and S is sulphur, Eu
3+for europium ion, Mg
2+for magnesium ion, Ti
4+for titanium ion.
The preferred nanometer monocrystalline grain of the nano red long after glow luminous material of described high afterglow property, and the particle diameter of nanometer monocrystalline grain is 300 ~ 400nm.
The preparation method of the nano red long after glow luminous material of above-mentioned high afterglow property, be to adopt pure thermal synthesis-calcining two-step approach, and concrete steps are as follows:
(1) measure 0.005 ~ 0.02 molar acetate yttrium, 0.0001 ~ 0.0006 molar acetate europium, 0.00005 ~ 0.00045 molar acetate magnesium, 0.00005 ~ 0.00045 mol sulfuric acid titanium, 0.02 ~ 0.08 mole of thiocarbamide is put in reaction vessel, add wherein again 60 ~ 120 milliliters of dehydrated alcohols, stirring and dissolving after ultrasonic dispersion, above-mentioned solution is placed in to airtight reactor, in 120 ℃ ~ 200 ℃ insulations, within 6 ~ 18 hours, obtains white product;
(2) cooled white product is carried out to filtration washing with deionized water and ethanol respectively, in 50 ~ 80 ℃ of dryings, within 6 ~ 8 hours, obtain precursor;
(3) precursor is annealed in the reducing atmosphere under 800 ~ 1100 ℃ 3 ~ 5 hours, make red long afterglow luminous material.
In the preparation method of the nano red long after glow luminous material of above-mentioned high afterglow property, described acetic acid yttrium is preferably Y (CH
3cOO)
3nH
2o, n=3 wherein, 4,5, or 6; Described acetic acid europium is preferably Eu (CH
3cOO)
3nH
2o, n=3 wherein, 4,5, or 6.Other magnesium acetates are Mg (CH
3cOO)
2, titanium sulfate is Ti (SO
4)
2, thiocarbamide is CS (NH
2)
2, ethanol is CH
3cH
2oH.
In the preparation method of the nano red long after glow luminous material of above-mentioned high afterglow property, the described reducing atmosphere of step (3) is preferably the airtight corundum crucible that is covered with the reduction carbon dust, and the plumbago crucible that presoma namely will be housed is built in the formed reducing atmosphere of airtight corundum crucible that is covered with reduction C powder.
The present invention has following beneficial effect:
(1) adopting first solubility acetate is raw material, prepares red long afterglow luminous material, is of a size of Nano grade, is far smaller than commercial red fluorescence powder size, but reaches 1.5h time of persistence, suitable with commercial red fluorescence powder.
(2) preparation-obtained nano red long after glow luminous material is carried out to material phase analysis with x-ray diffractometer, from the X-x ray diffration pattern x obtained, product is at 900 ℃ of Y that can obtain pure phase
2o
2s:Eu
3+, Mg
2+, Ti
4+, the high temperature solid-state method with respect to traditional, greatly reduce calcining temperature, saved the energy.
(3) prepared precursor and product are carried out to morphology analysis by scanning electron microscope, from the electromicroscopic photograph obtained: the nano red long after glow luminous material precursor of this high afterglow property is the nanometer disc-shaped, diameter is 2.5 ~ 5 μ m, and thickness is 80 ~ 100nm; 1100 ℃ of nano red long after glow luminous material Y of the high afterglow property prepared
2o
2s:x Eu
3+, y Mg
2+, z Ti
4+for the nanometer monocrystalline grain, and the nanometer monocrystalline particle diameter is 300 ~ 400nm.
(4) red illuminating material prepared has higher afterglow property, weathering resistance preferably, can be widely used in the fields such as various devices and Nanoparticle labeling.
(5) method safety of the synthetic preparation of pure hot method is nontoxic, simple and easy to operate, efficiency is high, cost is low, is easy to industrial applications.
The accompanying drawing explanation
Under Fig. 1 reducing atmosphere, the luminescent material X-ray diffraction pattern of 800 ~ 1100 ℃ of calcinings, wherein # represents Y
2o
2s, * represents Y
2o
3.
The nanometer disc-shaped precursor electron scanning micrograph that Fig. 2 is synthetic.
Under Fig. 3 reducing atmosphere, the luminescent material electron scanning micrograph of 800 ~ 1100 ℃ of calcinings.
Under Fig. 4 reducing atmosphere, the exciting light spectrogram of the luminescent material of 800 ~ 1100 ℃ of calcinings.
Under Fig. 5 reducing atmosphere, the utilizing emitted light spectrogram of the luminescent material of 800 ~ 1100 ℃ of calcinings.
Under Fig. 6 reducing atmosphere, the uv light irradiation that the luminescent material of 1100 ℃ of calcinings is 360nm with wavelength is after 3 minutes, the decay of afterglow curve obtained.
Embodiment
Further explain the present invention below in conjunction with embodiment, but embodiment does not limit in any form to the present invention.
embodiment 1
(1) measure 0.02 molar acetate yttrium, 0.0001 molar acetate europium, 0.0001 molar acetate magnesium, 0.0001 mol sulfuric acid titanium, taking 0.075 mole of thiocarbamide is put in reaction vessel, add wherein again 80 milliliters of dehydrated alcohols, stirring and dissolving after ultrasonic dispersion, above-mentioned solution is placed in to airtight reactor, in 200 ℃ of insulations, within 6 hours, obtains white product.
(2) cooled white product is carried out to filtration washing with deionized water and ethanol respectively, in 80 ℃ of dryings, within 6 hours, obtain precursor.
(3) precursor is annealed 5 hours in the reducing atmosphere under 800 ℃, wherein reducing atmosphere is built in by the plumbago crucible that presoma will be housed the airtight corundum crucible that is covered with reduction C powder and is formed, make the red long afterglow luminous material as shown in curve a, Fig. 3 (a) in Fig. 1, the product chemical formula finally obtained is Y
2o
2s:xEu
3+, yMg
2+, zTi
4+, wherein, x=0.01, y=0.01, z=0.01.
embodiment 2
(1) measure 0.005 molar acetate yttrium, 0.0001 molar acetate europium, 0.00005 molar acetate magnesium, 0.00005 mol sulfuric acid titanium, taking 0.02 mole of thiocarbamide is put in reaction vessel, add wherein again 60 milliliters of dehydrated alcohols, stirring and dissolving after ultrasonic dispersion, above-mentioned solution is placed in to airtight reactor, in 120 ℃ of insulations, within 10 hours, obtains white product.
(2) cooled white product is carried out to filtration washing with deionized water and ethanol respectively, in 50 ℃ of dryings, within 8 hours, obtain precursor.
(3) precursor is annealed 4 hours in the reducing atmosphere under 900 ℃, wherein reducing atmosphere is built in by the plumbago crucible that presoma will be housed the airtight corundum crucible that is covered with reduction C powder and is formed, make the red long afterglow luminous material as shown in curve b, Fig. 3 (b) in Fig. 1, the product chemical formula finally obtained is Y
2o
2s:xEu
3+, yMg
2+, zTi
4+, wherein, x=0.04, y=0.02, z=0.02.
embodiment 3
(1) measure 0.01 molar acetate yttrium, 0.0003 molar acetate europium, 0.00015 molar acetate magnesium, 0.00015 mol sulfuric acid titanium, taking 0.05 mole of thiocarbamide is put in reaction vessel, add wherein again 100 milliliters of dehydrated alcohols, stirring and dissolving after ultrasonic dispersion, above-mentioned solution is placed in to airtight reactor, in 150 ℃ of insulations, within 18 hours, obtains white product.
(2) cooled white product is carried out to filtration washing with deionized water and ethanol respectively, in 60 ℃ of dryings, within 7 hours, obtain precursor.
(3) precursor is annealed 3 hours in the reducing atmosphere under 1000 ℃, wherein reducing atmosphere is built in by the plumbago crucible that presoma will be housed the airtight corundum crucible that is covered with reduction C powder and is formed, make the red long afterglow luminous material as shown in curve c, Fig. 3 (c) in Fig. 1, the product chemical formula finally obtained is Y
2o
2s:xEu
3+, yMg
2+, zTi
4+, wherein, x=0.06, y=0.03, z=0.03.
embodiment 4
(1) measure 0.015 molar acetate yttrium, 0.0006 molar acetate europium, 0.00045 molar acetate magnesium, 0.00045 mol sulfuric acid titanium, taking 0.08 mole of thiocarbamide is put in reaction vessel, add wherein again 120 milliliters of dehydrated alcohols, stirring and dissolving after ultrasonic dispersion, above-mentioned solution is placed in to airtight reactor, in 180 ℃ of insulations, within 10 hours, obtains white product.
(2) cooled white product is carried out to filtration washing with deionized water and ethanol respectively, in 80 ℃ of dryings, within 6 hours, obtain precursor.
(3) precursor is annealed 3 hours in the reducing atmosphere under 1100 ℃, wherein reducing atmosphere is built in by the plumbago crucible that presoma will be housed the airtight corundum crucible that is covered with reduction C powder and is formed, make the red long afterglow luminous material as shown in curve d, Fig. 3 (d) in Fig. 1, the product chemical formula finally obtained is Y
2o
2s:xEu
3+, yMg
2+, zTi
4+, wherein, x=0.08, y=0.06, z=0.06.
Claims (3)
1. the preparation method of the nano red long after glow luminous material of high afterglow property, is characterized in that, adopts pure thermal synthesis-calcining two-step approach, and concrete steps are as follows:
(1) measure 0.005～0.02 molar acetate yttrium, 0.0001～0.0006 molar acetate europium, 0.00005～0.00045 molar acetate magnesium, 0.00005～0.00045 mol sulfuric acid titanium, 0.02～0.08 mole of thiocarbamide is put in reaction vessel, add wherein again 60～120 milliliters of dehydrated alcohols, stirring and dissolving after ultrasonic dispersion, above-mentioned solution is placed in to airtight reactor, in 120 ℃～200 ℃ insulations, within 6～18 hours, obtains white product;
(2) cooled white product is carried out to filtration washing with deionized water and ethanol respectively, in 50～80 ℃ of dryings, within 6～8 hours, obtain presoma;
(3) presoma is annealed in the reducing atmosphere under 800～1100 ℃ 3～5 hours, make red long afterglow luminous material;
The chemical formula of the nano red long after glow luminous material of described high afterglow property is: Y
2o
2s:xEu
3+, yMg
2+, zTi
4+, wherein, x=0.01～0.08, y=0.01～0.06, z=0.01～0.06; Y is yttrium, and O is oxygen, and S is sulphur, Eu
3+for europium ion, Mg
2+for magnesium ion, Ti
4+for titanium ion;
The nano red long after glow luminous material of described high afterglow property is the nanometer monocrystalline grain that particle diameter is 300～400nm.
2. the preparation method of the nano red long after glow luminous material of high afterglow property according to claim 1, is characterized in that, described acetic acid yttrium is Y (CH
3cOO)
3nH
2o, n=3 wherein, 4,5, or 6; Described acetic acid europium is Eu (CH
3cOO)
3nH
2o, n=3 wherein, 4,5 or 6.
3. the preparation method of the nano red long after glow luminous material of high afterglow property according to claim 1, is characterized in that, the described reducing atmosphere of step (3) is the airtight corundum crucible that is covered with the reduction carbon dust.
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| CN103194219A (en) * | 2013-04-12 | 2013-07-10 | 天津理工大学 | Microwave energy alcohol thermal growth method for red light luminous crystal |
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