CN102585815A - Orange-red long path persistence luminescent material and preparation method thereof - Google Patents
Orange-red long path persistence luminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an orange-red long path persistence luminescent material and a preparation method thereof. The luminescent material has a chemical characteristic of BaZrO3:Eux, Tiy, wherein x and y are the molar ratio coefficients of the corresponding dopantions relative to BaZrO3, wherein 0.005<=x<=0.045, and 0<y<=0.05. The preparation method comprises high-temperature solid phase method in the air. The orange-red long path persistence luminescent material is prepared by weighing raw materials according to a stoichiometric proportion, ball milling, mixing, drying, preburning in the air, grinding, carrying out high-temperature calcination in the air, grinding into powder, and other steps. A sample emits orange-red persistence light after ultraviolet light excitation, and through emission spectroscopic measurement, the main emission peak is near 594nm; and after the ultraviolet exciting light is removed, the sample has distinct orange-red long path persistence characteristic, and the persistence light is visible. The orange-red long path persistence luminescent material provided by the invention has the advantages of good chemical stability, no radioactivity, high brightness, good monochromaticity, long time of persistence, simple preparation method and no need of atmosphere protection, and is suitable for large-scale production.
Description
Technical field
The present invention relates to the orange red long after glow luminous material of a kind of high brightness high monochromaticity, the invention still further relates to the preparation method of above-mentioned luminescent material.
Technical background
Long after glow luminous material is a kind of photo-induced energy storage material; Have energy-conservation, characteristics such as can be recycled, be widely used in emergent indication, low light level illumination, industrial art and building decoration, energetic ray detection, information storage and fields such as display equipment, laser equipment.The long-afterglow material of existing visible region mainly is divided into red colour system, yellowish green colour system and blue system; Wherein the luminescent properties of yellow-green colour and blue long afterflow material has reached the needs of practical application and has realized industriallization, and these materials mainly are rare earth doped aluminate and silicate.And that the research and development of red long afterglow material make progress is slow relatively; Mostly commercial at present red colour system long-afterglow material is the sulfide system; Though the luminescent material luminosity of this system and persistence length can reach request for utilization reluctantly, its poor chemical stability is prone to deliquescence in air; And production process is complicated, and the waste environmental pollution that produces in the building-up process is serious.
Chinese invention patent 200410017538.X discloses " La
2O
2S red long afterglow luminous material and preparation method thereof " this patented claim.The luminescent material that this patented technology is set forth is with La
2O
3Be matrix, La
2O
3With S be base starting material, Eu
3+Be activator, Mg
2+, Zr
4+, Ti
4+, Nb
5+Be coactivator, yellow soda ash and Quilonum Retard are fusing assistant.Its preparation method must be accomplished under reducing environment, and the preparation process complicated and time consumption.After being excited according to the material of patent preparation, naked eyes can observe red or orange red.Although the long afterglow property of this material is better; But there are conspicuous deficiency in product and preparation method; Such as providing the reductibility environment certainly will make the cost of this kind of preparation material higher, the sulphur raw material certainly will cause environmental pollution, mixes the price that multiple expensive material certainly will be raised product altogether.Therefore, seek with synthesising property stablize, afterglow property is good, cost is low, the research of eco-friendly red colour system long after glow luminous material, especially orange red long after glow luminous material is a focus always.
Summary of the invention
The present invention proposes in view of the above problems, has solved above-mentioned various problems in the past, the purpose below realizing.That is, the orange red long after glow luminous material that the object of the present invention is to provide a kind of high brightness, high monochromaticity, chemicalstability is good and after time is long, and preparation method environmentally friendly, the simple orange red long after glow luminous material of preparation process is provided.
As the means that are used to solve above-mentioned problem, as follows.That is,
The present invention provides a kind of orange red long after glow luminous material, and its characteristic chemical formula is: BaZrO
3: Eu
x, TI
y, in the formula, 0.005≤x≤0.045,0<y≤0.05, wherein, x, y are that corresponding dopant ion is with respect to BaZrO
3The mol ratio coefficient.
In the following formula, preferred x is 0.025 ± 0.005; Y is preferred more than 0.005, and more preferably 0.015 ± 0.002, the upper limit of y preferred 0.045.
Orange red long after glow luminous material of the present invention is with BaZrO
3Be matrix, Eu
3+Be activator, an amount of doped Ti O
2Thereby than the TiO that undopes
2Situation compare, its luminosity is high, monochromaticity is good, after time is long.
The luminosity of above-mentioned orange red luminescent material is BaZrO
3: 5~9 times of Eu, radiative monochromaticity compares BaZrO
3: Eu is good, is generally 250~460 seconds after time, preferred 400~460 seconds.The present invention also provides a kind of preparation method of orange red luminescent material, may further comprise the steps:
(1) measure than the oxide/carbonate raw material that takes by weighing respective element by element chemistry,
(2) in the raw material that weighs up, add dispersion agent, the preferred absolute ethyl alcohol of dispersion agent then grinds,
(3) raw material drying that mixes after will grinding,
(4) the exsiccant raw material is carried out pre-burning,
(5) sample after the taking-up pre-burning grinds the back calcining, to obtain said orange red long after glow luminous material.
In addition, what raw materials used Ba adopted in the preferred steps (1) is its carbonate, and what Zr, Eu and Ti adopted respectively is their oxide compound.
The preferred time of grinding in the step (2) is 20~40h, more preferably 24h.Said grinding is preferably ball milling.
In the step (4), preferred dried raw material is placed in the crucible, and pre-burning 3~8h naturally cools to room temperature with stove under 700~900 ℃ atmospheric environment.Pre-burning 4h. under 850 ℃ atmospheric environment more preferably
In the step (5), preferably with pre-burning and the crucible of packing into of the sample after grinding, in air atmosphere, be warming up to 1250~1550 ℃, calcining 4~8h naturally cools to room temperature with stove.More preferably in air atmosphere, be warming up to 1400 ℃, calcining 5h naturally cools to room temperature with stove.
Adopt pre-burning and two stages of calcining in the preferred manufacturing procedure of the present invention, dried raw material is placed in the crucible, pre-burning 3~8h under 700~900 ℃ air ambient.Sample after pre-burning the is ground crucible of packing into is warming up to 1250~1550 ℃ in air atmosphere, calcining 4~8h naturally cools to room temperature with stove.Adopt this method to help to improve the percent crystallinity and the purity of material.
In addition, in raw material, add in the time of can also before pre-burning, grinding among the preparation method of the present invention with respect to substrate material BaZrO
3The mol ratio coefficient is 0.05~0.15 boron oxide compound (B
2O
3) or its acid (H
3BO
3) as fusing assistant.
Preferred boron oxide compound or its acid are with respect to substrate material BaZrO
3The mol ratio coefficient is 0.10 ± 0.02.
Fusing assistant boron oxide compound (B
2O
3) or its acid (H
3BO
3) adding reduced crystalline phase nucleation temperature of reaction and grain growing reaction energy barrier, thereby accelerate surface reaction speed, and fusing assistant boron oxide compound (B
2O
3) or its acid (H
3BO
3) add the degree of depth and the density very likely increased the electronic defects trap level, so the adding of fusing assistant not only helps sintering but also can improve the luminescent properties of material.
The present invention also provides a kind of BaZrO that is mixed with fusing assistant (oxide compound of boric acid or boron)
3: Eu
x, Ti
y, 0.015≤x in the formula≤0.045,0<y≤0.05, wherein, x, y are that corresponding dopant ion is with respect to BaZrO
3The mol ratio coefficient.
The above-mentioned BaZrO that is mixed with fusing assistant (oxide compound of boric acid or boron)
3: Eu
x, Ti
yThe initial luminosity of luminescent material is BaZrO
3: 9~11 times of Eu, be 300~630 seconds after time, preferred 500~630 seconds, more preferably about 600 seconds.
In addition, with the said BaZrO of the fusing assistant that undopes
3: Eu
x, Ti
yAnd BaZrO
3: Eu compares, and is mixed with the BaZrO of fusing assistant
3: Eu
x, Ti
yThe radiative monochromaticity of luminescent material is good, and initial luminosity is high.
The orange red long after glow luminous material of the present invention adopts high temperature solid-state method synthetic, and the emission main peak is positioned near the 594nm, and brightness is high, and after time is longer, and has better monochromaticity, fusing assistant H
3BO
3(perhaps B
2O
3) adding let material of the present invention have higher initial brightness.
What the substrate material of the orange red long after glow luminous material of the present invention was selected for use is that chemical property is stable, high temperature resistant, the BaZrO of high-purity phase
3, between this matrix and Eu and the Ti ion very high energy transfer efficiency is arranged.Mixing altogether of being adopted also has very high energy transfer efficiency between ion Eu and the Ti.Above factor all helps stimulated luminescence, makes the luminescent material after mixing altogether can send the brightness height, and monochromaticity is good, the orange-red light that obviously prolong after time.The orange red long after glow luminous material of the present invention does not contain radioelement, and environment is not almost polluted.And preparation method of the present invention is simple, and the atmosphere that do not need protection is fit to large-scale commercial prodn.
The orange red long after glow luminous material of the present invention has very big potential using value in fields such as some display equipments and laser equipments.Suitable codoped boron oxide compound (B also
2O
3) or its acid (H
3BO
3) come the further initial luminosity of this material of raising as fusing assistant.
Description of drawings
Fig. 1 is the XRD figure spectrum of long-afterglow luminescent powder of the present invention.
(a): BaZrO
3: Eu
0.025(b): BaZrO
3: Eu
0.025, Ti
0.005(c): BaZrO
3: Eu
0.025, Ti
0.015(d): BaZrO
3: Eu
0.025, Ti
0.045(f): BaZrO
3: Eu
0.025, Ti
0.015Wherein (a) and (b), (c) and (d) calcining temperature of four appearance all be 1400 ℃, (f) calcining temperature of sample is 1550 ℃.
Fig. 2 is the emmission spectrum of long-afterglow luminescent powder of the present invention (calcining temperature is 1400 ℃).
(a):BaZrO
3:Eu
0.025;(b):BaZrO
3:Eu
0.025,Ti
0.005;(c):BaZrO
3:Eu
0.025,Ti
0.015;(d):BaZrO
3:Eu
0.025,Ti
0.045.
Fig. 3 is the long-afterglow luminescent powder (BaZrO that makes under the different calcining temperatures of the present invention
3: Eu
0.025, Ti
0.005) emmission spectrum.(a): calcining temperature is 1400 ℃; (f): calcining temperature is 1550 ℃.
Fig. 4 is the typical decay of afterglow curve of long-afterglow luminescent powder of the present invention.Wherein
(a):BaZrO
3:Eu
0.025;(b):BaZrO
3:Eu
0.025,Ti
0.015;
Fig. 5 is the XRD figure spectrum of long-afterglow luminescent powder of the present invention.(a): BaZrO wherein
3: Eu
0.025(b): BaZrO
3: Eu
0.025, Ti
0.015(c): add H in the preparation
3BO
3BaZrO for fusing assistant
3: Eu
0.025, Ti
0.015
Fig. 6 is the emmission spectrum of long-afterglow luminescent powder of the present invention.(a): BaZrO wherein
3: Eu
0.025(b): BaZrO
3: Eu
0.025, Ti
0.015(c): added H in the preparation
3BO
3BaZrO for fusing assistant
3: Eu
0.025, Ti
0.015
Fig. 7 is the decay of afterglow curve of long-afterglow luminescent powder of the present invention.Wherein
(a): BaZrO
3: Eu
0.025(b): BaZrO
3: Eu
0.025, Ti
0.015(c): added H in the preparation
3BO
3BaZrO for fusing assistant
3: Eu
0.025, Ti
0.015
Embodiment
Embodiment
Comparative example 1. raw materials are BaCO
3(commercially available, analytical pure), ZrO
2(commercially available, analytical pure) and Eu
2O
3(commercially available, 99.99wt%) mol ratio between them should be mutually: 0.04: 0.04: 0.0125.To place the ball milling bottle by the load weighted raw material of stoichiometric ratio, add an amount of absolute ethyl alcohol, fully grind more than 24 hours on the ball mill; The raw material that ball milling is good is placed in the baking oven after the drying, in agate mortar, grinds, and then raw material is placed the resistance furnace pre-burning, and 850 ℃ of insulation 4h cool to room temperature with the furnace in the air atmosphere; Sample after the pre-burning grinds in agate mortar again, then packs sample in the crucible into, places High Temperature Furnaces Heating Apparatus to calcine, and 1400 ℃ of insulation 5h cool to room temperature with the furnace in the air atmosphere; Can obtain white powder product B aZrO after the grinding
3: Eu
0.025Identify through X ray, shown in (a) among Fig. 1 and Fig. 5, the diffraction peak data and the BaZrO of gained sample
3The diffraction data of JCPDS standard card (06-399) consistent.Explain that the gained sample is BaZrO
3Pure phase, crystalline structure and BaZrO
3Identical, belong to a cube phase.The gained sample sends orange red long-persistence luminous after the 260nm optical excitation, and emmission spectrum shows like (a) among Fig. 2: emmission spectrum has two peak values that intensity is suitable, respectively near the 574n and near the 5594nm.A little less than this sample luminosity, and the difference of main peak value and other peak value size is little, and promptly the monochromaticity of sample is bad.The decay of afterglow curve of this luminescent material such as (a) among Fig. 4 can find out that the after time of this sample is shorter
Embodiment 2. raw materials are BaCO
3(commercially available, analytical pure), ZrO
2(commercially available, analytical pure), Eu
2O
3(commercially available, 99.99wt%) and TiO
2(commercially available, 99.99wt%) mol ratio between them should be mutually: 0.04: 0.04: 0.0125: 0.015.Adopt comparative example 1 identical preparation method and preparation flow, finally can obtain white powder product B aZrO
3: Eu
0.025, Ti
0.015Shown in (b) among (c) and Fig. 4 among Fig. 1, the diffraction peak data and the BaZrO of gained sample
3The diffraction data of JCPDS standard card (06-399) consistent.Explain that the gained sample is BaZrO
3Pure phase, crystalline structure and BaZrO
3Identical, belong to a cube phase.The gained sample sends macroscopic orange red steady persistence after the 260nm optical excitation, emmission spectrum, and like (c) among Fig. 2, the main peak value of emmission spectrum that can find out this material is near 594nm.This luminescent material brightness height and monochromaticity are good.The decay of afterglow curve of this luminescent material such as (b) among Fig. 3 can find out that through this figure obviously prolong after time and decay of afterglow is index law.
Embodiment 3. raw materials are BaCO
3(commercially available, analytical pure), ZrO
2(commercially available, analytical pure), Eu
2O
3(commercially available, 99.99wt%) and TiO
2(commercially available, 99.99wt%) mol ratio between them should be mutually: 0.04: 0.04: 0.0125: 0.045.Adopt comparative example 1 identical preparation method and preparation flow, finally can obtain white powder product B aZrO
3: Eu
0.025, Ti
0.045Shown in (d) among Fig. 1, the diffraction peak data and the BaZrO of gained sample
3The diffraction data of JCPDS standard card (06-399) consistent.Explain that the gained sample is BaZrO
3Pure phase, crystalline structure and BaZrO
3Identical, belong to a cube phase.The gained sample sends macroscopic orange red steady persistence after the 260nm optical excitation, emmission spectrum, and like (d) among Fig. 2, the main peak value of emmission spectrum that can find out this material is near 594nm.This luminescent material brightness height and monochromaticity are good.Be index law than long and decay of afterglow the after time of this luminescent material.
Embodiment 4. raw materials are BaCO
3(commercially available, analytical pure), ZrO
2(commercially available, analytical pure), Eu
2O
3(commercially available, 99.99wt%) and TiO
2(commercially available, 99.99wt%) mol ratio between them should be mutually: 0.04: 0.04: 0.0125: 0.015.Adopt embodiment 1 identical preparation method and preparation flow, but calcining temperature changes to 1550 ℃, other parameter constants finally can obtain white powder product B aZrO
3: Eu
0.025, Ti
0.015Shown in (f) among Fig. 1, the diffraction peak data and the BaZrO of gained sample
3The diffraction data of JCPDS standard card (06-399) consistent.Explain that the gained sample is BaZrO
3Pure phase, crystalline structure and BaZrO
3Identical, belong to a cube phase.The gained sample sends macroscopic orange red steady persistence after the 260nm optical excitation, emmission spectrum, and like (f) among Fig. 3, the main peak value of emmission spectrum that can find out this material is near 594nm.This luminescent material brightness height and monochromaticity are good.Be index law than long and decay of afterglow the after time of this luminescent material.
Embodiment 5. raw materials are BaCO
3(commercially available, analytical pure), ZrO
2(commercially available, analytical pure), Eu
2O
3(commercially available, 99.99wt%), TiO
2(commercially available, 99.99wt%) and H
3BO
3(commercially available, analytical pure) mol ratio between them should be mutually: 0.04: 0.04: 0.0125: 0.015: 0.05.Adopt comparative example 1 identical preparation method and preparation flow, finally can obtain being mixed with the white powder product B aZrO of fusing assistant
3: Eu
0.025, Ti
0.015The diffraction peak data and the BaZrO of gained sample
3The diffraction data of JCPDS standard card (06-399) consistent.The gained sample sends macroscopic orange red steady persistence after the 260nm optical excitation, the main peak value of the emmission spectrum of this material and does not add H near 594nm
3BO
3Make fusing assistant and get that sample compares that initial brightness is greatly improved and monochromaticity is good, after time is long, decay of afterglow is index law.
Embodiment 6. raw materials are BaCO
3(commercially available, analytical pure), ZrO
2(commercially available, analytical pure), Eu
2O
3(commercially available, 99.99wt%), TiO
2(commercially available, 99.99wt%) and H
3BO
3(commercially available, analytical pure) mol ratio between them should be mutually: 0.04: 0.04: 0.0125: 0.015: 0.10.Adopt comparative example 1 identical preparation method and preparation flow, finally can obtain being mixed with the white powder product B aZrO of fusing assistant
3: Eu
0.025, Ti
0.015Shown in (c) among Fig. 5, the diffraction peak data and the BaZrO of gained sample
3The diffraction data of JCPDS standard card (06-399) consistent.Explain that the gained sample is BaZrO
3Pure phase, crystalline structure and BaZrO
3Identical, belong to a cube phase.The gained sample sends macroscopic orange red steady persistence after the 260nm optical excitation, emmission spectrum, and show like (c) among Fig. 6: emission spectra peak is near 594nm.The initial brightness of this luminescent material is high, monochromaticity is good, after time is long and decay of afterglow is index law.It is preferred mix proportion scheme.The decay of afterglow curve of this luminescent material such as (c) among Fig. 7.
Embodiment 7, and raw material is BaCO
3(commercially available, analytical pure), ZrO
2(commercially available, analytical pure), Eu
2O
3(commercially available, 99.99wt%), TiO
2(commercially available, 99.99wt%) and H
3BO
3(commercially available, analytical pure) mol ratio between them should be mutually: 0.04: 0.04: 0.0125: 0.015: 0.15.Adopt comparative example 1 identical preparation method and preparation flow, finally can obtain being mixed with the white powder product B aZrO of fusing assistant
3: Eu
0.025, Ti
0.015The diffraction peak data and the BaZrO of gained sample
3The diffraction data of JCPDS standard card (06-399) consistent.The gained sample sends macroscopic orange red steady persistence after the 260nm optical excitation, the main peak value of the emmission spectrum of this material is near 594nm, and initial brightness is high, monochromaticity is good, after time is long and decay of afterglow is index law.
Embodiment 8, and raw material is BaCO
3(commercially available, analytical pure), ZrO
2(commercially available, analytical pure), Eu
2O
3(commercially available, 99.99wt%), TiO
2(commercially available, 99.99wt%) and H
3BO
3(commercially available, analytical pure) mol ratio between them should be mutually: 0.04: 0.04: 0.0125: 0.015: 0.10.Adopt comparative example 1 identical preparation method and preparation flow, but calcining temperature is adjusted into 1250 ℃. finally can obtain being mixed with the white powder product B aZrO of fusing assistant
3: Eu
0.025, Ti
0.015The diffraction peak data and the BaZrO of gained sample
3The diffraction data of JCPDS standard card (06-399) consistent.Explain that the gained sample is BaZrO
3Pure phase, crystalline structure and BaZrO
3Identical, belong to a cube phase.The gained sample sends macroscopic orange red steady persistence after the 260nm optical excitation, emmission spectrum, and emission spectra peak is near 594nm.The initial brightness of this luminescent material is high, monochromaticity is good, after time is long and decay of afterglow is index law.
Embodiment 9, and raw material is BaCO
3(commercially available, analytical pure), ZrO
2(commercially available, analytical pure), Eu
2O
3(commercially available, 99.99wt%), TiO
2(commercially available, 99.99wt%) and H
3BO
3(commercially available, analytical pure) mol ratio between them should be mutually: 0.04: 0.04: 0.0125: 0.015: 0.10.Adopt comparative example 1 identical preparation method and preparation flow, but calcining temperature is adjusted into 1550 ℃.Finally can obtain being mixed with the white powder product B aZrO of fusing assistant
3: Eu
0.025, Ti
0.015The diffraction peak data and the BaZrO of gained sample
3The diffraction data basically identical of JCPDS standard card (06-399).The gained sample sends macroscopic orange red steady persistence after the 260nm optical excitation, emmission spectrum, and emission spectra peak is near 594nm.The initial brightness of this luminescent material is high, monochromaticity is good, after time is long and decay of afterglow is index law.
Utilizability in the industry
What the substrate material of the orange red long after glow luminous material of the present invention was selected for use is that chemical property is stable, high temperature resistant, the BaZrO of high-purity phase
3, between this matrix and Eu and the Ti ion very high energy transfer efficiency is arranged.Mixing altogether of being adopted also has very high energy transfer efficiency between ion Eu and the Ti.Above factor all helps stimulated luminescence, makes the luminescent material after mixing altogether can send the brightness height, and monochromaticity is good, the orange-red light that obviously prolong after time.The orange red long after glow luminous material of the present invention does not contain radioelement, and environment is not almost polluted.And preparation method of the present invention is simple, and the atmosphere that do not need protection is fit to large-scale commercial prodn.
The orange red long after glow luminous material of the present invention has very big potential using value in fields such as some display equipments and laser equipments.Also can in the preparation process, suitably mix boron oxide compound (B
2O
3) or its acid (H
3BO
3) come the further initial luminosity of this material of raising as fusing assistant.
Claims (10)
1. orange red long after glow luminous material, its chemical feature formula is: BaZrO
3: Eu
x, Ti
y, 0.015≤x in the formula≤0.045,0<y≤0.05, wherein, x, y are that corresponding dopant ion is with respect to BaZrO
3The mol ratio coefficient.
2. orange red long after glow luminous material according to claim 1 is characterized in that the luminosity of said luminescent material is BaZrO
3: 5~9 times of Eu, be 250~460 seconds after time, preferred 400~460 seconds; Radiative monochromaticity compares BaZrO
3: Eu is high.
3. the preparation method of claim 1 or 2 described orange red long after glow luminous material is characterized in that, may further comprise the steps:
(1) measure than oxide compound that takes by weighing respective element or carbonate raw material by element chemistry,
(2) in the raw material that weighs up, add dispersion agent, the preferred absolute ethyl alcohol of dispersion agent then grinds,
(3) raw material drying that mixes after will grinding,
(4) the exsiccant raw material is carried out pre-burning,
(5) sample after the taking-up pre-burning grinds the back calcining, to obtain said orange red long after glow luminous material.
4. preparation method according to claim 3 is characterized in that, in step (2), milling time is 20~40h.
5. according to claim 3 or 4 described preparing methods, it is characterized in that in step (2), said grinding is a ball milling.
6. according to claim 3 or 4 described preparing methods, it is characterized in that, in step (4), dried raw material is placed in the crucible, pre-burning 3~8h under 700~900 ℃ atmospheric environment.
7. according to claim 3 or 4 described preparing methods, it is characterized in that, in step (5), with pre-burning and the crucible of packing into of the sample after grinding, in air atmosphere, be warming up to 1250~1550 ℃, calcining 4~8h.
8. according to each described preparation method in the claim 3~7, it is characterized in that, in step (2), in raw material, add during grinding with respect to substrate material BaZrO
3The mol ratio coefficient is 0.05~0.15 boron oxide compound (B
2O
3) or its acid (H
3BO
3) as fusing assistant, to improve the initial luminosity of said material.
9. the orange red long after glow luminous material of a preparation method according to claim 7 preparation.
10. orange red long after glow luminous material according to claim 8 is characterized in that, the initial luminosity of said luminescent material is BaZrO
3: 9~11 times of Eu, be 300~630 seconds after time, preferred 500~630 seconds, more preferably about 600 seconds; Radiative monochromaticity compares BaZrO
3: Eu is high, and initial luminosity is than the said BaZrO of the fusing assistant that undopes in the preparation
3: Eu
x, Ti
yAnd BaZrO
3: Eu is high.
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CN111892924A (en) * | 2020-08-14 | 2020-11-06 | 合肥工业大学 | Cu ion doped gallate base orange red luminescent material and preparation method thereof |
CN112662396A (en) * | 2020-12-29 | 2021-04-16 | 威海市泓淋电力技术股份有限公司 | Solid solution type red long-afterglow luminescent material and preparation method thereof |
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Cited By (3)
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CN111892924A (en) * | 2020-08-14 | 2020-11-06 | 合肥工业大学 | Cu ion doped gallate base orange red luminescent material and preparation method thereof |
CN111892924B (en) * | 2020-08-14 | 2022-06-14 | 合肥工业大学 | Cu ion doped gallate base orange red luminescent material and preparation method thereof |
CN112662396A (en) * | 2020-12-29 | 2021-04-16 | 威海市泓淋电力技术股份有限公司 | Solid solution type red long-afterglow luminescent material and preparation method thereof |
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