CN101486908A - Red long afterglow luminous material and preparing process thereof - Google Patents

Red long afterglow luminous material and preparing process thereof Download PDF

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Publication number
CN101486908A
CN101486908A CNA2009100940798A CN200910094079A CN101486908A CN 101486908 A CN101486908 A CN 101486908A CN A2009100940798 A CNA2009100940798 A CN A2009100940798A CN 200910094079 A CN200910094079 A CN 200910094079A CN 101486908 A CN101486908 A CN 101486908A
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long afterglow
red long
luminescent material
red
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王飞
刘利军
杨斌
马文会
刘大春
戴永年
王其洪
于凯立
谢克强
伍继君
刘永成
周晓奎
汪竞福
徐宝强
秦博
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The invention relates to a red long afterglow luminescent material and preparation thereof; the red long afterglow luminescent material takes Gd2O2S as a matrix and Eu<3+> as an activator and appropriately intermingles TiO2; MgO is codoped with TiO2; and SiO2 is codoped with TiO2. The composition thereof is Gd2O2S:Eu<3+>, Ti<4+>; Gd2O2S:Eu<3+>, Mg<2+>, Ti<4+> or Gd2O2S:Eu<3+>, Si<4+>, and Ti <4+>. The mass percentage content of each raw material to prepare the luminescent material is as follows: 32.27 percent to 33.98 percent of gadolinium oxide; 1.02 percent to 2.73 percent of europia, 32.0 percent to 38.0 percent of sulfur, 23.1 percent to 28.2 percent of anhydrous sodium carbonate, 3.9 percent to 4.8 percent of lithium carbonate, 0 to 0.58 percent of magnesia, 0 to 0.87 percent of silicon dioxide and 0.19 percent to 1.15 percent of titanic oxide; in addition, the mole ratio of gadolinium oxide and europia is that: n(Gd#-(2O3)):n(Eu#-(2O3)) equals to 11.50 to 32.33. The roasting temperature is 1240 DEG C to 1280 DEG C, and the heat preserving time is 2.0 to 3.0h. The emission peak value of the luminescent material is about 627nm. Through the irradiation of an ultraviolet lamp or visible light (such as the ray of the sun and a fluorescent lamp), the red long afterglow luminescent material is characterized by obvious, bright and pure red long afterglow luminescence, and can be used for emergency indicating lights, such as emergency exit direction for crowd evacuation when service interruption occurs in the public places, fire exit signs, red alert of other specific occasions, etc.

Description

A kind of red long afterglow luminous material and preparation method thereof
Technical field
The present invention relates to a kind of novel red long after glow luminous material and preparation method thereof, be specifically related to Gd 2O 2S is a matrix, Eu 3+Be activator, an amount of doped Ti O 2, MgO and TiO 2Codoped, or SiO 2With TiO 2Red long afterglow luminous material of codoped and preparation method thereof belongs to the luminescent material technical field.
Background technology
Nontoxic, harmless, "dead" and fluorescent lifetime is long, luminosity is high, stability of material is good advantage that rare earth long-afterglow luminescent material has, have characteristics energy-conservation, that can be recycled, be a class photo-induced energy storage functional materials, be widely used in fields such as low light level illumination, emergent pilot lamp, building decoration, industrial art, information storage and energetic ray detection.At present, blue-greenish colour and yellow-green colour long-afterglow material mainly are rare earth doped aluminate and silicate, and luminescent properties such as its luminosity and time of persistence have reached practical application and need and realize suitability for industrialized production; For example, Patent Office of the People's Republic of China's invention disclosed name is called " a kind of aluminate luminescent material and preparation thereof " (number of patent application: be exactly a kind of rear-earth-doped aluminate long after glow luminous material 200710044112.7), this material is with Eu 2+Activate, have long, good luminescent properties such as luminosity is high, stability of material is good of afterglow time.This class long after glow luminous material has been subjected to the single restriction of the color development of material own, the color of the after-glow light that it sent is blue-greenish colour and yellow-green colour, although handle the change that can cause glow color by various dyeing, but, because the characteristic of the dyestuff that coats itself, the dyestuff of these coatings can not use under the pyritous condition.
The red long afterglow luminous material of efficient stable is the emphasis that the researchist pays close attention to and develops always, the denomination of invention of authorizing as Patent Office of the People's Republic of China is " long persistence luminous sulfide material and manufacture method " (patent No.: patent 97111381.5), introduced a kind of red long afterglow luminous material MS:Eu, A, B, activator are Eu 3+, but feature limits such as its instability, weathering resistance difference its application.Another denomination of invention that Patent Office of the People's Republic of China is authorized be " red rare-earth phosphorescent body with long afterglow " (patent No.: patented technology 02125512.1), a kind of rare-earth red long persistence phosphor is disclosed, chemical constitution is Y 2O 2S:Sm, Mg, Ti.Adopt Y 2O 3With S as base starting material, Na 2CO 3As fusing assistant, Sm 3+Be exciting agent, Mg 2+And Ti 4+As being total to exciting agent, gac is as reductive agent, and product high temperature is come out of the stove, hot salt acid soak 1.5~2.0h, hot wash.The emission peak of this material is positioned at 607.9nm~608nm, and color is orange red partially.In this patent and not mentioned all the other brightness times, and colourity is impure, and is still far away apart from practical application, remains further research.In addition, use hydrochloric acid soln in its preparation process, environment is produced pollute.And with Gd 2O 2S is the long after glow luminous material of matrix, rarely has report at present.
Summary of the invention
An object of the present invention is synthetic a kind of novel red long afterglow luminous material, this material is with Gd 2O 2S is a matrix, Eu 3+Be activator, an amount of doped Ti O 2, or MgO and TiO 2Codoped, or SiO 2With TiO 2The long after glow luminous material of codoped; The surplus light that sends shows that pure red is luminous, and the brightness height of surplus light, and time of persistence is long.Another object of the present invention is to provide a kind of preparation method of above-mentioned luminescent material,, and environment do not produced harmful effect with the red long afterglow luminous material of present method preparation, not only stable performance.
The object of the present invention is achieved like this:
Synthetic luminescent material of the present invention consists of Gd 2O 2S:Eu 3+, Ti 4+, being hexagonal system structure, emission wavelength is about 627nm, through sunlight or fluorescent light irradiation, sends pure ruddiness, has significant long-persistence luminous characteristic.
It is gadolinium sesquioxide (Gd that the present invention prepares the used substrate material of above-mentioned luminescent material 2O 3), sulphur (S), activator is europium sesquioxide (Eu 2O 3), fusing assistant is anhydrous sodium carbonate (Na 2CO 3), Quilonum Retard (Li 2CO 3), doping agent is titanium dioxide (TiO 2), above-mentioned materials is by behind its quantitative mixing, and the preparation of phosphorescent substance is carried out under heating calcination state.
In order to increase trap depth, prolong time of persistence, luminescent material of the present invention is formed more preferably Gd 2O 2S:Eu 3+, Mg 2+, Ti 4+Or Gd 2O 2S:Eu 3+, Si 4+, Ti 4+Prepare the used matrix of its luminescent material except that same with above-mentioned matrix phase, its doping agent has also increased magnesium oxide (MgO) and silicon-dioxide (SiO respectively 2).
Preparation method of the present invention is: it is gadolinium sesquioxide (Gd that the present invention prepares the used raw material of above-mentioned long after glow luminous material 2O 3), europium sesquioxide (Eu 2O 3), sulphur (S), anhydrous sodium carbonate (Na 2CO 3), Quilonum Retard (Li 2CO 3), magnesium oxide (MgO), silicon-dioxide (SiO 2), titanium dioxide (TiO 2); The quality percentage composition of each raw material is respectively: gadolinium sesquioxide (Gd 2O 3): 32.27%~33.98%, europium sesquioxide (Eu 2O 3): 1.02%~2.73%, sulphur (S): 32.0%~38.0%, anhydrous sodium carbonate (Na 2CO 3): 23.1%~28.2%, Quilonum Retard (Li 2CO 3): 3.9%~4.8%, magnesium oxide (MgO): 0~0.58%, silicon-dioxide (SiO 2): 0~0.87%, titanium dioxide (TiO 2): 0.19%~1.15%, and gadolinium sesquioxide (Gd 2O 3) and europium sesquioxide (Eu 2O 3) the ratio (mol ratio) of amount of substance be n (Gd2O3): n (Eu2O3=11.50~32.33.Its preparation process is: after selected raw material is accurately taken by weighing according to aforementioned proportion, fully grind mixing in agate mortar, be pressed into the suitable sheet of size with tabletting machine, put into corundum crucible, build lid, place the High Temperature Furnaces Heating Apparatus internal heating, 350 ℃ of insulation 20~30min, 1240 ℃~1280 ℃ insulation 2.0~3.0h are cooled to room temperature, product is come out of the stove, with deionized water washing, filtration, 90 ℃~110 ℃ freeze-day with constant temperature 3.0h~5.0h can obtain the white powder product in thermostatic drying chamber.
Reaction mechanism of the present invention is:
(1)Na 2CO 3+S→Na 2S+Na 2S x+CO 2
Na 2S+Na 2S x+Gd 2O 3+Eu 2O 3+TiO 2→Gd 2O 2S:Eu 3+,Ti 4+
(2)Na 2CO 3+S→Na 2S+Na 2S x+CO 2
Na 2S+Na 2S x+Gd 2O 3+Eu 2O 3+MgO+TiO 2→Gd 2O 2S:Eu 3+,Mg 2+,Ti 4+
(3)Na 2CO 3+S→Na 2S+Na 2S x+CO 2
Na 2S+Na 2S x+Gd 2O 3+Eu 2O 3+TiO 2+SiO 2→Gd 2O 2S:Eu 3+,Si 4+,Ti 4+
The invention has the beneficial effects as follows: because long after glow luminous material of the present invention adopts Eu 3+As activator, emission peak is positioned at the 627nm place, and colourity is purer, shows that pure red is luminous.The substrate material of long after glow luminous material of the present invention is selected highly stable, the resistant to elevated temperatures Gd of chemical property for use 2O 2S, Gd simultaneously 2O 2S and Eu 3+Have very high energy transfer efficiency, help stimulated luminescence, after the doped metal ion, the brightness height that is sent, colourity is pure, and obviously prolong time of persistence, and improved crystalline structure simultaneously.Do not use hydrochloric acid soln among the preparation method of long after glow luminous material of the present invention, environment is not almost polluted.
Description of drawings:
Fig. 1 is that embodiment 1 makes sample sample Gd 2O 2S:Eu 3+, Ti 4+XRD figure spectrum;
Fig. 2 is that embodiment 2 makes sample sample Gd 2O 2S:Eu 3+, Mg 2+, Ti 4+Emmission spectrum;
Fig. 3 is that embodiment 3 makes sample sample Gd 2O 2S:Eu 3+, Si 4+, Ti 4+The SEM photo.
Embodiment
Below in conjunction with the invention will be further described in conjunction with example:
Embodiment 1
Proportioning raw materials:
Material name: quality: shared mass percent:
Gadolinium sesquioxide (Gd 2O 3) 11.6545g 33.43%
Europium sesquioxide (Eu 2O 3) 0.5955g 1.71%
Sulphur (S) 12.2500g 35.14%
Anhydrous sodium carbonate (Na 2CO 3) 8.7475g 25.09%
Quilonum Retard (Li 2CO 3) 1.4821g 4.25%
Titanium dioxide (TiO 2) 0.1352g 0.39%
Fully grind in agate mortar, mixing is pressed into the suitable sheet of size with tabletting machine, put into corundum crucible, build lid, place the High Temperature Furnaces Heating Apparatus internal heating, 350 ℃ of insulation 20min, 1240 ℃ of insulation 3.0h, be cooled to room temperature, product is come out of the stove, with deionized water washing, filtration, 110 ℃ of freeze-day with constant temperature 3.0h in thermostatic drying chamber can obtain white powder sample Gd 2O 2S:Eu 3+, Ti 4+Identify through X-ray diffraction, as shown in Figure 1, the diffraction peak data and the Gd of obtained sample 2O 2(card number: diffraction data basically identical 26-1422) illustrates the crystalline structure and the Gd of obtained sample to the JCPDS standard card of S 2O 2S is identical, belongs to hexagonal system.Luminescent spectrum is measured and to be shown: emission peak wavelength is about 627nm, and through ultraviolet lamp or visible light (as sunlight and fluorescent lamp) irradiation, this luminescent material presents strong red long-afterglow emission, and brightness height, colourity are pure.
Embodiment 2
Proportioning raw materials:
Material name: quality: shared mass percent:
Gadolinium sesquioxide (Gd 2O 3) 11.6545g 33.30%
Europium sesquioxide (Eu 2O 3) 0.5955g 1.70%
Sulphur (S) 12.2500g 35.00%
Anhydrous sodium carbonate (Na 2CO 3) 8.6319g 24.66%
Quilonum Retard (Li 2CO 3) 1.4625g 4.18%
Magnesium oxide (MgO) 0.1352g 0.39%
Titanium dioxide (TiO 2) 0.2704g 0.77%
Fully grind in agate mortar, mixing is pressed into the suitable sheet of size with tabletting machine, put into little corundum crucible, build lid, place the High Temperature Furnaces Heating Apparatus internal heating, 300 ℃ of insulation 30min, 1280 ℃ of insulation 2.0h, be cooled to room temperature, product is come out of the stove, with deionized water washing, filtration, 90 ℃ of freeze-day with constant temperature 5.0h in thermostatic drying chamber can obtain white powder sample Gd 2O 2S:Eu 3+, Mg 2+, Ti 4+Identify the crystalline structure of this product and Gd through X-ray diffraction 2O 2S is identical, belongs to hexagonal system.The emmission spectrum of sample as shown in Figure 2, as seen: emission peak master peak value wavelength is about 627nm, and its intensity is better than other peak value far away, and through ultraviolet lamp or visible light (as sunlight and fluorescent lamp) irradiation, this luminescent material presents bright pure red steady persistence emission.
Embodiment 3
Proportioning raw materials:
Material name: quality: shared mass percent:
Gadolinium sesquioxide (Gd 2O 3) 11.6545g 33.30%
Europium sesquioxide (Eu2O 3) 0.5955g 1.70%
Sulphur (S) 12.2500g 35.00%
Anhydrous sodium carbonate (Na2CO 3) 8.5741g 24.50%
Quilonum Retard (Li 2CO 3) 1.4527g 4.15%
Silicon-dioxide (SiO 2) 0.2028g 0.58%
Titanium dioxide (TiO 2) 0.2704g 0.77%
Fully grind in agate mortar, mixing is pressed into the suitable sheet of size with tabletting machine, put into little corundum crucible, build lid, place the High Temperature Furnaces Heating Apparatus internal heating, 330 ℃ of insulation 25min, 1250 ℃ of insulation 2.5h, be cooled to room temperature, product is come out of the stove, with deionized water washing, filtration, 100 ℃ of freeze-day with constant temperature 4.0h in thermostatic drying chamber can obtain white powder sample Gd 2O 2S:Eu 3+, Si 4+, Ti 4+Identify the crystalline structure of this product and Gd through X-ray diffraction 2O 2S is identical, belongs to hexagonal system.Luminescent spectrum is measured and shown: emission peak main peak value wavelength is about 627nm.Accompanying drawing 3 is the SEM photo of preparation sample, and as seen: the pattern of this sample particle is the class sphere, and crystalline structure is intact, favorable dispersity, and size is between 5~12 μ m.Through the irradiation of ultraviolet lamp or visible light (as sunlight and fluorescent lamp), this luminescent material presents strong red long-afterglow emission, and brightness height, colourity are pure.

Claims (4)

1, a kind of red long afterglow luminous material is characterized in that: the consisting of of this material: Gd 2O 2S:Eu 3+, Ti 4+
2, a kind of red long afterglow luminous material according to claim 1 is characterized in that: the consisting of of this material: Gd 2O 2S:Eu 3+, Mg 2+, Ti 4+
3, a kind of red long afterglow luminous material according to claim 1 is characterized in that: the consisting of of this material: Gd 2O 2S:Eu 3+, Si 4+, Ti 4+
4, the preparation method of claim 1,2 or 3 described a kind of red long afterglow luminous materials is characterized in that: preparing the used raw material of above-mentioned red long afterglow luminous material is gadolinium sesquioxide (Gd 2O 3), europium sesquioxide (Eu 2O 3), sulphur (S), anhydrous sodium carbonate (Na 2CO 3), Quilonum Retard (Li 2CO 3), magnesium oxide (MgO), silicon-dioxide (SiO 2), titanium dioxide (TiO 2);
The quality percentage composition of each raw material is respectively: gadolinium sesquioxide (Gd 2O 3): 32.27%~33.98%, europium sesquioxide (Eu 2O 3): 1.02%~2.73%, sulphur (S): 32.0%~38.0%, anhydrous sodium carbonate (Na 2CO 3): 23.1%~28.2%, Quilonum Retard (Li 2CO 3): 3.9%~4.8%, magnesium oxide (MgO): 0~0.58%, silicon-dioxide (SiO 2): 0~0.87%, titanium dioxide (TiO 2): 0.19%~1.15%, and gadolinium sesquioxide (Gd 2O 3) and europium sesquioxide (Eu 2O 3) the ratio (mol ratio) of amount of substance be n (Gd2O3): n (Eu2O3)=11.50~32.33;
Its preparation process is: after selected raw material is accurately taken by weighing according to aforementioned proportion, in agate mortar, fully grind, mixing, be pressed into the suitable sheet of size with tabletting machine, put into corundum crucible, build lid, place the High Temperature Furnaces Heating Apparatus internal heating, 300 ℃~350 ℃ insulation 20~30min, 1240 ℃~1280 ℃ insulation 2.0~3.0h are cooled to room temperature, product is come out of the stove, with deionized water washing, filtration, 90 ℃~110 ℃ freeze-day with constant temperature 3.0h~5.0h can obtain the white powder product in thermostatic drying chamber.
CNA2009100940798A 2009-02-04 2009-02-04 Red long afterglow luminous material and preparing process thereof Pending CN101486908A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102352250A (en) * 2011-07-22 2012-02-15 彩虹集团电子股份有限公司 Method for preparing green gadolinium terbium oxysulfide phosphor
CN103194234A (en) * 2013-04-12 2013-07-10 天津理工大学 Blue light excited solid solution fluorescent material
CN106047346A (en) * 2016-05-30 2016-10-26 南京信息工程大学 Red fluorescent material for AC-LED and preparation method thereof
CN113621365A (en) * 2021-09-10 2021-11-09 江苏师范大学 Preparation method of europium-doped high-luminous-intensity red silicate fluorescent material
CN113684575A (en) * 2021-09-18 2021-11-23 桐乡市华家那羊绒服饰有限公司 Antibacterial cashmere knitted yarn and preparation method thereof
CN117801820A (en) * 2023-12-28 2024-04-02 广州珠江光电新材料有限公司 Red long afterglow material and preparation method thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102352250A (en) * 2011-07-22 2012-02-15 彩虹集团电子股份有限公司 Method for preparing green gadolinium terbium oxysulfide phosphor
CN103194234A (en) * 2013-04-12 2013-07-10 天津理工大学 Blue light excited solid solution fluorescent material
CN106047346A (en) * 2016-05-30 2016-10-26 南京信息工程大学 Red fluorescent material for AC-LED and preparation method thereof
CN106047346B (en) * 2016-05-30 2018-11-16 南京信息工程大学 A kind of red fluorescence material and preparation method thereof for AC-LED
CN113621365A (en) * 2021-09-10 2021-11-09 江苏师范大学 Preparation method of europium-doped high-luminous-intensity red silicate fluorescent material
CN113684575A (en) * 2021-09-18 2021-11-23 桐乡市华家那羊绒服饰有限公司 Antibacterial cashmere knitted yarn and preparation method thereof
CN113684575B (en) * 2021-09-18 2022-07-01 桐乡市华家那羊绒服饰有限公司 Antibacterial cashmere knitted yarn and preparation method thereof
CN117801820A (en) * 2023-12-28 2024-04-02 广州珠江光电新材料有限公司 Red long afterglow material and preparation method thereof
CN117801820B (en) * 2023-12-28 2024-07-05 广州珠江光电新材料有限公司 Red long afterglow material and preparation method thereof

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