CN101565614B - Orange-red long afterglow Luminescent Material - Google Patents

Orange-red long afterglow Luminescent Material Download PDF

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CN101565614B
CN101565614B CN200910140531A CN200910140531A CN101565614B CN 101565614 B CN101565614 B CN 101565614B CN 200910140531 A CN200910140531 A CN 200910140531A CN 200910140531 A CN200910140531 A CN 200910140531A CN 101565614 B CN101565614 B CN 101565614B
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raw material
sno
sintering
red long
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CN101565614A (en
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刘伟生
巨正花
魏瑞平
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Lanzhou University
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Lanzhou University
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Abstract

The present invention relates to a luminescent Material which can send out orange-red light through the inspiration of ultraviolet light or sunlight and has long afterglow, and a method for preparing the material. The luminescent material of the invention is an orange-red long afterglow luminescent material with a general formula of Ca(2-x-y)SnO4:Smx, My, wherein M is zinc or cadmium or the combination of zinc and cadmium; x and y are the molar ratio coefficients of corresponding doped ions relatively to the Ca2SnO4, wherein, x=0.001-0.150, and y=0-0.150. The preparing method of the luminescent material according to the invention adopts a high-temperature solid phase method.

Description

A kind of orange red long after glow luminous material
Technical field
The present invention relates to a kind ofly can send orange-red light, have luminescent material than steady persistence through a UV-light or a day optical excitation, and this preparation methods.
Background technology
Long after glow luminous material is one type of embedded photoluminescent material, can absorb ambient light according to energy and with store energy, close excitation light source after, at room temperature slowly release the form of energy stored with visible light.Has pollution-free, safe, energy-conservation, economic dispatch advantage.Since nineteen nineties; People have invented the rare earth ion doped aluminates system and the long after glow luminous material of silicate systems successively; These two types of materials are all increasing than the long-afterglow material of traditional sulfide system aspect luminosity, after time, the chemicalstability; But the glow color of these two big types of luminescent materials is generally green, blueness, blue-greenish colour etc., is difficult to satisfy the demand.Therefore, people invest sight the R and D of ruddiness long-afterglow material.Because the special optical property of red long afterglow material makes its range of application than green or blue long afterflow material wider.
Red long afterglow material mainly comprises rare-earth activated alkaline earth sulfide, oxysulfide, titanates of alkali-earth metals system and phosphate system.The twilight sunset and the brightness of the red long afterglow material of sulfur-bearing are better, but chemicalstability is relatively poor, and application is restricted.Alkaline earth titanate system red long afterglow material luminosity is low, and after time is short.Phosphate system red long afterglow material with low cost, but preparation needs reducing atmosphere protection, complex process mostly.
Chinese invention patent application 200410017538.X discloses name and has been called " La 2O 2S red long afterglow luminous material and preparation method " patented claim technology.The disclosed red long afterglow luminous material of this patent is with La 2O 2S is a matrix, La 2O 3With S be base starting material, Eu 3+Be exciting agent, Mg 2+, Zr 4+, Ti 4+, Nb 5+For being total to exciting agent, Na 2CO 3And Li 2CO 3Be fusing assistant.Its preparation method must be under the gac reducing atmosphere, and 1200 ℃ of calcinations 4 hours after cooling is come out of the stove, through pulverizing, wash and sieving, obtain product.After material excited, naked-eye observation was orange red or red to twilight sunset.Although the afterglow property of this kind long-afterglow material is better, but there are following shortcoming and defect in this product and preparation method: adopt sulphur to make raw material, the waste gas of generation has very big harm to human body and environment; Production process adopts the reducing atmosphere protection, and complex manufacturing and production cost are higher; The fusing assistant Na that uses 2CO 3And Li 2CO 3Cost is higher.Except that these deficiencies, the cost of material of prior art is high, especially contains expensive rare-earth europium, makes the cost of product high.Therefore, still need stable in properties now, afterglow property is good, red and orange red long-afterglow material with low cost.
Summary of the invention
The present invention provides a kind of and overcomes that prior art is insufficient can be sent orange-red light, have the luminescent material than steady persistence through a UV-light or a day optical excitation.
Luminescent material general formula of the present invention is Ca (2-x-y)SnO 4: Sm x, M yOrange red long after glow luminous material, wherein: M is zinc or cadmium, or the combination of zinc and cadmium; X, y are that corresponding dopant ion is with respect to Ca 2SnO 4The mol ratio coefficient, wherein: x=0.001～0.150, y=0～0.150.
The chemical formula of a kind of concrete orange red long after glow luminous material of the present invention is Ca 2SnO 4: Sm 0.01, can reach 45～380 minutes persistence.
The chemical formula of the concrete orange red long after glow luminous material of another kind of the present invention is Ca 2SnO 4: Sm 0.01, Zn 0.01, sustainable 180 minutes of twilight sunset.
The chemical formula of the concrete orange red long after glow luminous material of another kind of the present invention is Ca 2SnO 4: Sm 0.01, Cd 0.01, sustainable 235 minutes of twilight sunset.
The preparation method of arbitrary orange red long after glow luminous material of the present invention adopts high temperature solid-state method; Promptly by the composition of materials chemistry formula take by weighing respective element oxide compound or/and carbonate or/and nitrate salt or/and acetate or/and oxalate; Use absolute ethyl alcohol or acetone to be dispersion agent, each raw material is ground to micron order, carry out sintering at 1100～1300 ℃; The cooling back is taken out and is ground, and obtains material requested.
When being the grinding before sintering, preferred manufacturing procedure of the present invention in raw material, adds absolute ethyl alcohol or acetone as dispersion agent by 3～6ml/ (gram raw material).
Preferred manufacturing procedure of the present invention can also be before sintering grinding the time add the H of raw material weight 0.5～6% at raw material 3BO 3Or/and NH 4Cl is as fusing assistant.The results showed, during grinding before sintering, in raw material, add the H that presses raw material weight 0.5～3% simultaneously 3BO 3NH with raw material weight 0.5～3% 4Cl has best effect.
Adopt twice sintering in the preferred manufacturing procedure of the present invention, promptly raw material through abundant ground and mixed after evenly first with it 1100～1300 ℃ of sintering 3～6 hours, be cooled to regrinding mixing after the room temperature, carry out sintering 1～4 hour second time at 800～1200 ℃ again.
Material of the present invention is to be matrix with positive stannate, and adding rare earth ion is activator with other ion, in positive stannate, is realizing orange red photoemissive steady persistence performance, and the ideal effect is arranged.
When grinding, add a certain amount of absolute ethyl alcohol among the preparation method of the present invention or acetone can make the more even of raw materials mix as dispersion agent, can significantly reduce the grinding required time simultaneously.Test shows, directly grinds as not adding dispersion agent, need the longer time to grind just and can reach desired granularity, and raw materials mix is inhomogeneous.
The present invention adds a certain amount of boric acid as fusing assistant or/and ammonium chloride in raw material, not only can reduce the dephasign of product in mutually, but also can in the luminescent properties that improves material, prolong after time.
Research also shows, adopts double sintering can reduce the dephasign of product in mutually in the preparation process of the present invention.
Its preparation method of the present invention is simple, helps scale operation, and low production cost, product are easy to grind, and stable in properties is "dead", can not work the mischief to environment, is a kind of long after glow luminous material with wide application prospect.
Description of drawings
Fig. 1 is Ca 2SnO 4: Sm 0.01The exciting light spectrogram.
Fig. 2 is Ca 2SnO 4: Sm 0.01Emmission spectrum figure.
Fig. 3 is Ca 2SnO 4: Sm 0.01Double-log decay of afterglow graphic representation.
Fig. 4 is the X-ray powder diffraction figure (4-2～4) of preparing product under powdery diffractometry standard card 74-1493 (4-1) and the different condition.Wherein 4-4 is Ca 2SnO 4: Sm 0.01XRD figure.Among the figure:
1-does not have fusing assistant; 1100～1300 degrees centigrade 3～6 hours
2-adds boric acid; 1100～1300 degrees centigrade 3～6 hours
3-adds boric acid and ammonium chloride; 1100～1300 degrees centigrade 3～6 hours
4-adds boric acid and ammonium chloride; 1100～1300 degrees centigrade 3～6 hours; 800～1200 degrees centigrade 1～4 hour
Fig. 5 is Ca 2SnO 4: Sm 0.01The exciting light spectrogram.
Fig. 6 is Ca 2SnO 4: Sm 0.01Emmission spectrum figure.
Fig. 7 is Ca 2SnO 4: Sm 0.01Double-log decay of afterglow graphic representation.
Fig. 8 is Ca 2SnO 4: Sm 0.01The exciting light spectrogram.
Fig. 9 is Ca 2SnO 4: Sm 0.01Emmission spectrum figure.
Figure 10 is Ca 2SnO 4: Sm 0.01The decay of afterglow graphic representation.
Figure 11 is Ca 2SnO 4: Sm 0.01, Zn 0.01The exciting light spectrogram.
Figure 12 is Ca 2SnO 4: Sm 0.01, Zn 0.01Emmission spectrum figure.
Figure 13 is Ca 2SnO 4: Sm 0.01, Zn 0.01Double-log decay of afterglow graphic representation.
Figure 14 is Ca 2SnO 4: Sm 0.01, Cd 0.01The exciting light spectrogram.
Figure 15 is Ca 2SnO 4: Sm 0.01, Cd 0.01Emmission spectrum figure.
Figure 16 is Ca 2SnO 4: Sm 0.01, Cd 0.01Double-log decay of afterglow graphic representation.
It below is most preferred embodiment of the present invention.
Embodiment
Embodiment 1
According to chemical formula Ca 2SnO 4: Sm 0.01, accurately take by weighing the oxide compound of respective element or the H of carbonate and 2-3% 3BO 3, above-mentioned raw materials is poured in the agate mortar, press 3～6ml/ (gram raw material) adding absolute ethyl alcohol or acetone again as dispersion agent; After fully grinding mixing, change corundum crucible over to, under air atmosphere, in 1100～1300 ℃ of sintering 3～6h; Be cooled to room temperature, take out the sample regrinding, in 800～1200 ℃ of insulation 1～4h; Be cooled to room temperature, take out the sample grinding and obtain example materials.This material appearance is white in color, and the main thing of XRD test shows is Ca mutually 2SnO 4The excitation spectrum of this material is made up of a series of peaks in 320～575nm scope, and highest peak is positioned at 408nm, and other peak position is in 348,364,378,478 and the 560nm place, referring to accompanying drawing 1.The emmission spectrum of this material has 3 strong peaks, and highest peak is positioned at the 608nm place, other two peak positions in 565 with the 652nm place, referring to accompanying drawing 2.It is x=0.53 that XYZ chromaticity diagram calculates its radiative chromaticity coordinates value, and y=0.47 is positioned at the orange-red light emitting area.Behind this material process uv lamp or the sun exposure, in the dark demonstrate orange red afterglow.Example materials is after the solar simulated light source shines 10 minutes down, at the discernmible luminosity (0.32mcd/m of human eye 2) above can be luminous more than 45 minutes, referring to accompanying drawing 3.Decay of afterglow curve index of coincidence attenuation law.
Embodiment 2
According to chemical formula Ca 2SnO 4: Sm 0.01, accurately take by weighing oxide compound or the carbonate and the raw material weight 0.5～3%H of respective element 3BO 3With 0.5～3% NH 4Cl pours above-mentioned material in the agate mortar into, presses 3～6ml/ (gram raw material) adding absolute ethyl alcohol or acetone again as dispersion agent; Change corundum crucible over to after fully grinding mixing, under air atmosphere, in 1100～1300 ℃ of sintering 3～6h; Be cooled to room temperature, take out the sample regrinding, in 800～1200 ℃ of insulation 1～4h; Be cooled to room temperature, take out the sample grinding and obtain example materials.Accompanying drawing 4 has provided the XRD figure of preparing product under the different condition.This material appearance is white in color, and the main thing of XRD test shows is Ca mutually 2SnO 4, referring to accompanying drawing 4-4.The excitation spectrum of this material is made up of a series of peaks in 320～575nm scope, and highest peak is positioned at 408nm, and other peak position is in 348,364,378,478 and the 560nm place, referring to accompanying drawing 5.The emmission spectrum of this material has 3 strong peaks, and highest peak is positioned at the 608nm place, other two peak positions in 565 with the 652nm place, referring to accompanying drawing 6.Behind this material process uv lamp or the sun exposure, in the dark demonstrate orange red afterglow.Example materials is after the solar simulated light source shines 10 minutes down, at the discernmible luminosity (0.32mcd/m of human eye 2) above can be luminous more than 380 minutes, referring to accompanying drawing 7.Decay of afterglow curve index of coincidence attenuation law.
Embodiment 3
According to chemical formula Ca 2SnO 4: Sm 0.01, accurately take by weighing oxide compound or the carbonate and the raw material weight 1～3%H of respective element 3BO 3With 0.5～3% NH 4Cl pours above-mentioned material in the agate mortar into, presses 3～6ml/ (gram raw material) adding absolute ethyl alcohol or acetone again as dispersion agent; Change corundum crucible over to after fully grinding mixing, under air atmosphere, in 1100～1300 ℃ of sintering 3～6h; Be cooled to room temperature, take out the sample regrinding, in 800～1200 ℃ of insulation 1～4h; Be cooled to room temperature, take out the sample grinding and obtain example materials.This material appearance is white in color, and the main thing of XRD test shows is Ca mutually 2SnO 4The excitation spectrum of this material is made up of a series of peaks in the 320-575nm scope, and highest peak is positioned at 408nm, and other peak position is in 348,364,378,478 and the 560nm place, referring to accompanying drawing 8.The emmission spectrum of this material has 3 strong peaks, and highest peak is positioned at the 608nm place, other two peak positions in 565 with the 652nm place, referring to accompanying drawing 9.It is x=0.54 that XYZ chromaticity diagram calculates its radiative chromaticity coordinates value, and y=0.46 is positioned at the orange-red light emitting area.Behind this material process uv lamp or the sun exposure, in the dark demonstrate orange red afterglow.Example materials is after shining 10 minutes under the solar simulated light source, at the discernmible luminosity (0.32mcd/m of human eye 2) above can be luminous more than 210 minutes, referring to accompanying drawing 10.Decay of afterglow curve index of coincidence attenuation law.
Embodiment 4
According to chemical formula Ca 2SnO 4: Sm 0.01, Zn 0.01, accurately take by weighing oxide compound or the carbonate and the raw material weight 0.5～3%H of respective element 3BO 3With 0.5～3% NH 4Cl pours above-mentioned material in the agate mortar into, presses 3～6ml/ (gram raw material) adding absolute ethyl alcohol or acetone again as dispersion agent; Change corundum crucible over to after fully grinding mixing, under air atmosphere, in 1100～1300 ℃ of sintering 3～6h; Be cooled to room temperature, take out the sample regrinding, in 800～1200 ℃ of insulation 1～4h; Be cooled to room temperature, take out the sample grinding and obtain example materials.This material appearance is white in color, and the main thing of XRD test shows is Ca mutually 2SnO 4The excitation spectrum of this material is made up of a series of peaks in 320～575nm scope, and highest peak is positioned at 408nm, and other peak position is in 348,364,378,478 and the 560nm place, referring to accompanying drawing 11.The emmission spectrum of this material has 3 strong peaks, and highest peak is positioned at the 608nm place, at the 600nm place acromion is arranged, other two peak positions in 565 with the 652nm place, referring to accompanying drawing 12.Behind this material process uv lamp or the sun exposure, in the dark demonstrate orange red afterglow.Example materials is after the solar simulated light source shines 10 minutes down, at the discernmible luminosity (0.32mcd/m of human eye 2) above can be luminous more than 180 minutes, referring to accompanying drawing 13.Decay of afterglow curve index of coincidence attenuation law.
Embodiment 5
According to chemical formula Ca 2SnO 4: Sm 0.01, Cd 0.01, accurately take by weighing oxide compound or the carbonate or the nitrate salt of respective element and the H of raw material weight 1～3% 3BO 3With 0.5～3% NH 4Cl pours above-mentioned material in the agate mortar into, adds absolute ethyl alcohol as dispersion agent by 3～6ml/ (gram raw material) again; Change corundum crucible over to after fully grinding mixing, under air atmosphere, in 1100～1300 ℃ of sintering 3～6h; Be cooled to room temperature, take out the sample regrinding, in 800～1200 ℃ of insulation 1～4h; Be cooled to room temperature, take out the sample grinding and obtain example materials.This material appearance is white in color, and the main thing of XRD test shows is Ca mutually 2SnO 4The excitation spectrum of this material is made up of a series of peaks in the 320-575nm scope, and highest peak is positioned at 408nm, and other peak position is in 348,364,378,478 and the 560nm place, referring to accompanying drawing 14.The emmission spectrum of this material has 3 strong peaks, and highest peak is positioned at the 608nm place, other two peak positions in 565 with the 652nm place, referring to accompanying drawing 15.Behind this material process uv lamp or the sun exposure, in the dark demonstrate orange red afterglow.Example materials is after the solar simulated light source shines 10 minutes down, at the discernmible luminosity (0.32mcd/m of human eye 2) above can be luminous more than 235 minutes, referring to accompanying drawing 16.Decay of afterglow curve index of coincidence attenuation law.

Claims (9)

1. a general formula is Ca (2-x-y)SnO 4: Sm x, M yOrange red long after glow luminous material, wherein: M is zinc or cadmium, or the combination of zinc and cadmium; X, y are that corresponding dopant ion is with respect to Ca 2SnO 4The mol ratio coefficient, wherein: x=0.001～0.150, y=0～0.150.
2. orange red long after glow luminous material, its chemical formula is Ca 2SnO 4: Sm 0.01
3. orange red long after glow luminous material, its chemical formula is Ca 2SnO 4: Sm 0.01, Zn 0.01
4. orange red long after glow luminous material, its chemical formula is Ca 2SnO 4: Sm 0.01, Cd 0.01
5. the preparation method of the described arbitrary orange red long after glow luminous material of claim 1 to 4; It is characterized in that composition by the materials chemistry formula take by weighing respective element oxide compound or/and carbonate or/and nitrate salt or/and acetate or/and oxalate; After abundant ground and mixed is even, carry out sintering at 1100～1300 ℃; The cooling back is taken out and is ground, and obtains needed material.
6. preparation method according to claim 5 adds absolute ethyl alcohol or acetone as dispersion agent by 3～6ml/ (gram raw material) when it is characterized in that the grinding before the sintering in raw material.
7. preparation method according to claim 6, the H that in raw material, adds as fusing assistant when it is characterized in that the grinding before the sintering by 0.5～6% of raw material weight 3BO 3Or/and NH 4Cl.
8. preparation method according to claim 7 adds the H of raw material weight 0.5～3% simultaneously in raw material when it is characterized in that the grinding before the sintering 3BO 3NH with raw material weight 0.5～3% 4Cl.
9. according to the described arbitrary preparation method of claim 5 to 8; It is characterized in that raw material through abundant ground and mixed evenly the back first with raw material 1100～1300 ℃ of sintering 3～6 hours; Be cooled to regrinding mixing after the room temperature, carry out sintering 1～4 hour second time at 800～1200 ℃ again.
CN200910140531A 2009-04-30 2009-04-30 Orange-red long afterglow Luminescent Material Expired - Fee Related CN101565614B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2881449B1 (en) * 2012-07-31 2017-03-01 Ocean's King Lighting Science & Technology Co., Ltd. Stannate fluorescent material and method for preparing same
CN104877678A (en) * 2015-05-11 2015-09-02 上海应用技术学院 Yellow long-afterglow luminescent material and preparation method thereof
CN109370579B (en) * 2018-12-04 2020-05-15 华北电力大学 Green light long afterglow 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
CN115873594A (en) * 2022-12-06 2023-03-31 济南大学 Low-temperature solution method synthesis process of transparent cadmium-based long-afterglow crystal

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Hisanori Yamane,et al.Preparation, crystal structure, and photoluminescence of Ca2SnO4:Eu3+,Y3+.《Journal of Solid State Chemistry》.2008,第181卷2559-2564. *

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