CN1544577A - Method for preparing green long-time afterglow luminescent powder - Google Patents

Method for preparing green long-time afterglow luminescent powder Download PDF

Info

Publication number
CN1544577A
CN1544577A CNA2003101100526A CN200310110052A CN1544577A CN 1544577 A CN1544577 A CN 1544577A CN A2003101100526 A CNA2003101100526 A CN A2003101100526A CN 200310110052 A CN200310110052 A CN 200310110052A CN 1544577 A CN1544577 A CN 1544577A
Authority
CN
China
Prior art keywords
sintering
cooling
oxide
alkaline earth
nitrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2003101100526A
Other languages
Chinese (zh)
Inventor
锵 苏
苏锵
赫泓
吕玉华
李成宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CNA2003101100526A priority Critical patent/CN1544577A/en
Publication of CN1544577A publication Critical patent/CN1544577A/en
Pending legal-status Critical Current

Links

Landscapes

  • Luminescent Compositions (AREA)

Abstract

The invention relates to a process for preparing green long persistence luminescent material, wherein the chemical constitution of the long persistence material is disclosed in the specification, where a=0.05-1.05, x=0.004-0.1, y=0.004-0.1, M is one or more of Ca, Sr, Ba. The preparation process includes, weighing the raw materials by proportion, grinding and mixing homogeneously, subjecting the mixed materials for agglomeration 1-10h at 100 deg. C to 1200 deg. C in reducing atmosphere, cooling down, grinding to obtain the product. A pre-calcination procedure is preferably included in the invention for better effect.

Description

A kind of preparation method of green long afterglow fluorescent material
Technical field
The invention belongs to a kind of preparation method of green long afterglow luminescent material.In particular, the composition and the preparation method that belong to a kind of green long afterglow fluorescent material of boron aluminium strontium system of mixing the europium dysprosium altogether.
Background technology
Long-afterglow material is exactly the energy that can store ambient light irradiation, (refers to room temperature) then under a certain temperature, discharges the material of these stored energys lentamente with the form of visible light.This class material can be made luminescent coating, luminescent ink, Noctilucent ceramics, luminous plastics, luminous fiber, luminescent paper, noctilucence glass etc., can be used for fields such as building decoration, communications and transportation, military affairs.
People research long-afterglow material early is a sulfide material, but the sulfide long-afterglow material exists obvious defects,, time of persistence low as after-glow brightness weak point, poor chemical stability, easy deliquescence etc.
The mid-90, found new type long-persistence material SrAl 2O 4: Eu 2+, Dy 3+(1996 the 143rd volume 2670-2673 pages or leaves of J.Electrochem.Soc.), after UV-light or day optical excitation, the persistent green long afterglow of energy emitting bright, the twilight sunset emission peak is positioned at 520nm, is Eu 2+5d- 8S 7/2Transition, its after-glow brightness, time of persistence, materials chemistry stability are all considerably beyond the sulfide long-afterglow material.
Relevant aluminate green steady persistence patent is existing, as Chinese patent publication number CN1053807A, has proposed a kind of europkium-activated strontium aluminate long-afterglow material, but has not used mixing altogether of dysprosium.Chinese patent publication number CN 115779 has proposed a kind of polyion activated alkaline earth aluminate persistent material, has wherein only used small amounts boron and has made fusing assistant.To add up to the ratio with oxygen be 2: 4 for boron and aluminium in the long-afterglow material of Chinese patent notification number CN 1063211C invention, the boracic aluminates system of Chinese patent notification number CN 1086407C invention (boron compares less than 1: 4.5 with aluminium atom number) steady persistence system sintering temperature is 1250-1600 ℃, though Chinese patent Granted publication CN 1101844C name is called " rare-earth activated alkaline-earth metal aluminium borate long-afterglow fluorescent body ", wherein the content of boron seldom (sees that from embodiment boron and aluminium atom number compare also less than 1: 4.5).
In some aluminates system green long afterglow patents, be mostly to mix a certain amount of boron-containing compound, the effect of playing flux and improving afterglow property is invention and the bibliographical information of the green long afterglow material of aluminium borate but also there is not principal phase.
Summary of the invention
The purpose of this invention is to provide a kind of green long afterglow fluorescent material;
Another object of the present invention provides a kind of preparation method of green long afterglow fluorescent material.
The general sintering temperature of aluminate fluorescent powder is higher, and this fluorescent material low as the aluminium borate sintering temperature be 1100 ℃-1200 ℃, need not use the more expensive Si-Mo rod stove of price, only need a common silicon carbon rod stove to get final product, again energy savings.Traditional green long afterglow luminescent powder twilight sunset peak value multidigit is in about 520nm, and the twilight sunset peak value of this fluorescent material is positioned at about 492nm.And the present invention proposes the green long afterglow material that principal phase is an aluminium borate first.
The chemical constitution of green long afterglow material that the present invention mixes the boron strontium aluminate system of europium dysprosium altogether is:
(1-x-y) MO: 3Al 2O 3: aB 2O 3: xEu 2O 3: yDy 2O 3A=0.95-1.05 wherein, x=0.004-0.1, y=0.004-0.1, M are one or more among Ca, Sr, the Ba.
The present invention selects traditional solid-phase synthesis, raw material is strontium oxide or heats lime carbonate, nitrocalcite, the caoxalate that Strontium carbonate powder, strontium nitrate, strontium oxalate, calcium oxide or the heating that can generate strontium oxide can generate calcium oxide, barium oxide or heating can generate barytic barium carbonate, nitrate of baryta, barium oxalate, aluminum oxide, boron oxide or boric acid, europium sesquioxide or heating can generate the europium nitrate of europium sesquioxide, and dysprosium oxide or heating can generate the Dysprosium trinitrate of dysprosium oxide.Accurate raw materials weighing in proportion, behind the porphyrize mixing with mixed material in reducing atmosphere at 1100 ℃ of-1200 ℃ of sintering 1-10h, also can carry out in two steps, earlier sintering under air, cooling, after the grinding, high temperature reduction under reducing atmosphere again, cooling is ground, and namely gets product.If through the pre-burning better effects if.Reducing atmosphere is meant ammonia, hydrogen+nitrogen or carbon monoxide.
Aluminium borate long-afterglow material of the present invention also can adopt other methods such as coprecipitation method, sol-gel method, combustion method synthetic, can reach similar result.
The alkaline earth aluminium borate long-afterglow material that europium dysprosium of the present invention is mixed altogether after day optical excitation, in the dark can be seen bright green emitting.After being excited by fluorescent lamp, promptly more than 10 hours, keep in Dark Place in twilight sunset sustainable evening, the next morning, in the dark the twilight sunset naked eyes can be debated.
Description of drawings
Accompanying drawing 1 is X-ray powder diffraction figure, and as can be seen from the figure the principal phase of green long-time afterglow luminescent powder of the present invention is SrAl 3BO 7
Embodiment
Embodiment 1
Material molar ratio is SrO, Al 2O 3, HBO 3, Eu 2O 3, Dy 2O 3=0.96: 1.5: 0.95: 0.01: 0.01.Accurate raw materials weighing in proportion, behind the porphyrize mixing, at 500 ℃ of pre-burning 1h, cooling, after the grinding, again in the reducing atmosphere of (hydrogen+nitrogen) at 1100 ℃ of sintering 10h, cooling is ground, and promptly gets product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.
Embodiment 2
Material molar ratio is SrCO 3: Al 2O 3: HBO 3: Eu 2O 3: Dy 2O 3=0.96: 1.5: 1: 0.01: 0.01, accurate raw materials weighing behind the porphyrize mixing, at 500 ℃ of pre-burning 1h, is cooled off in proportion, after the grinding, at 1150 ℃ of sintering 4h, cooling is after the grinding, again in (hydrogen+nitrogen) atmosphere in 1100 ℃ of sintering 7h, cooling is ground, and namely gets product.With Philip standard incandescent lamp irradiation sample, the illumination at sample place is 101.5 * 10LX, shines after 10 minutes, stops irradiation, by being furnished with MinoltaCS-100A chromascope (Japan) the beginning image data of Minolta DP-101 data handler, the original intensity of sample is about 2.0cd/m simultaneously 2, more than the time of persistence 10h, the after-glow light spectrum peak is positioned at 492nm; Ultraviolet all can excite to visual range (as 200-450nm); X-ray diffractogram as shown in Figure 1.
Embodiment 3
Material molar ratio is Sr (NO 3) 2: Al 2O 3: B 2O 3: Eu 2O 3: Dy 2O 3=2: 3,1.05: 0.004: 0.004, accurate raw materials weighing in proportion, behind the porphyrize mixing, at 1150 ℃ of sintering 4h, again in (hydrogen+nitrogen) atmosphere in 1150 ℃ of sintering 10h, cooling is ground, and namely gets product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.
Embodiment 4
Material molar ratio is SrC 2O 4: Al 2O 3: HBO 3: Eu (NO 3) 3: Dy (NO 3) 3=0.8: 1.5: 1: 0.1: 0.1, accurate raw materials weighing in proportion, behind the porphyrize mixing, at 1200 ℃ of sintering 1h, after cooling is ground, 1150 ℃ of sintering 10h in carbon monoxide atmosphere, cooling is ground, and namely gets product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.
Embodiment 5
Material molar ratio is SrCO 3: CaCO 3: Al 2O 3: HBO 3: Eu 2O 3: Dy 2O 3=0.86: 0.1: 1.5: 1: 0.01: 0.01, accurate raw materials weighing in proportion, behind the porphyrize mixing, at 1150 ℃ of sintering 4h, after cooling is ground, 1150 ℃ of sintering 7h in (hydrogen+nitrogen) atmosphere, cooling is ground, and namely gets product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.
Embodiment 6
Material molar ratio is SrCO 3: BaCO 3: Al 2O 3: HBO 3: Eu 2O 3: Dy 2O 3=0.86: 0.1: 1.5: 1: 0.01: 0.01, accurate raw materials weighing in proportion, behind the porphyrize mixing, at 1150 ℃ of sintering 4h, after cooling is ground, 1150 ℃ of sintering 1h in (hydrogen+nitrogen) atmosphere, cooling is ground, and namely gets product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.
Embodiment 7
Material molar ratio is SrC0 3: Ca (NO 3) 2: Al 2O 3: HBO 3: Eu 2O 3: Dy 2O 3=0.86: 0.1: 1.5: 1: 0.01: 0.01, accurate raw materials weighing in proportion, behind the porphyrize mixing, at 1150 ℃ of sintering 4h, after cooling is ground, 1150 ℃ of sintering 7h in (hydrogen+nitrogen) atmosphere, cooling is ground, and namely gets product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.
Embodiment 8
Material molar ratio is SrCO 3: Ba (NO 3) 2: Al 2O 3: HBO 3: Eu 2O 3: Dy 2O 3=0.86: 0.1: 1.5: 1: 0.01: 0.01, accurate raw materials weighing in proportion, behind the porphyrize mixing, at 1100 ℃ of sintering 4h, after cooling is ground, 1150 ℃ of sintering 1h in (hydrogen+nitrogen) atmosphere, cooling is ground, and namely gets product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.
Embodiment 9
Material molar ratio is SrCO 3: CaC 2O 4: Al 2O 3: HBO 3: Eu 2O 3: Dy 2O 3=0.86: 0.1: 1.5: 1: 0.01: 0.01, accurate raw materials weighing in proportion, behind the porphyrize mixing, at 1150 ℃ of sintering 4h, after cooling is ground, 1150 ℃ of sintering 7h in (hydrogen+nitrogen) atmosphere, cooling is ground, and namely gets product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.
Embodiment 10
Material molar ratio is SrCO 3: BaC 2O 4: Al 2O 3: HBO 3: Eu 2O 3: Dy 2O 3=0.86: 0.1: 1.5: 1: 0.01: 0.01, accurate raw materials weighing in proportion, behind the porphyrize mixing, at 1150 ℃ of sintering 4h, after cooling is ground, 1150 ℃ of sintering 1h in (hydrogen+nitrogen) atmosphere, cooling is ground, and namely gets product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.
Embodiment 11
Material molar ratio is SrCO 3: Al 2O 3: HBO 3: Eu 2O 3: Dy 2O 3=0.96: 1.5: 1: 0.01: 0.01, accurate raw materials weighing behind the porphyrize mixing, at 500 ℃ of pre-burning 1h, is cooled off in proportion, after the grinding, at 1150 ℃ of sintering 4h, cooling is after the grinding, again under the condition that carbon dust exists in 1200 ℃ of sintering 7h, cooling is ground, and namely gets product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.
Embodiment 12
Material molar ratio is SrCO 3: Al 2O 3: HBO 3: Eu 2O 3: Dy 2O 3=0.96: 1.5: 1: 0.01: 0.01, accurate raw materials weighing is dissolved in raw material in certain density rare nitric acid in proportion, the solution clear heats slowly evaporate to dryness of little fire then, takes out fully and grinds, at 500 ℃ of pre-burning 1h, cooling is after the grinding, in 1150 ℃ of sintering 4h, cooling is after the grinding under the condition that carbon dust exists, again under the condition that carbon dust exists in 1150 ℃ of sintering 7h, cooling is ground, and namely gets product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.
Embodiment 13
Material molar ratio is SrCO 3: Al 2O 3: HBO 3: Eu 2O 3: Dy 2O 3=0.96: 1.5: 1: 0.01: 0.01, accurate raw materials weighing in proportion is behind the porphyrize mixing, at 500 ℃ of pre-burning 1h, cooling, after the grinding, 1150 ℃ of sintering 4h under the condition that ammonia exists, cooling, after the grinding, again under the condition that ammonia exists in 1150 ℃ of sintering 7h, cooling, grind, namely get product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.
Embodiment 14
Material molar ratio is SrCO 3: Al 2O 3: HBO 3: Eu 2O 3: Dy 2O 3=0.96: 1.5: 1: 0.01: 0.01, accurate raw materials weighing in proportion, behind the porphyrize mixing, at 500 ℃ of pre-burning 1h, cooling, after the grinding, again under the condition that carbon-point exists in 1150 ℃ of sintering 7h, cooling is ground, and namely gets product.Product can be by the day optical excitation, more than the sustainable 10h of twilight sunset.

Claims (5)

1. the chemical constitution of a green long afterglow fluorescent material is:
(1-x-y)MO:3Al 2O 3:aB 2O 3:xEu 2O 3:yDy 2O 3
A=0.95-1.05 wherein, x=0.004-0.1, y=0.004-0.1, M are one or more among Ca, Sr, the Ba.
2. the preparation method of a green long afterglow fluorescent material, raw material is alkaline earth carbonate, alkaline earth nitrate, the alkaline earth oxalate that alkaline-earth oxide or heating can generate alkaline-earth oxide, aluminum oxide, boron oxide or boric acid, europium sesquioxide or heating can generate the europium nitrate of europium sesquioxide, and dysprosium oxide or heating can generate the Dysprosium trinitrate of dysprosium oxide; Accurate raw materials weighing in proportion, behind the porphyrize mixing with mixing raw material in reducing atmosphere at 1100 ℃ of-1200 ℃ of sintering 1-10h, cooling is ground, and promptly gets product.
3. according to the preparation method of claim 1 and 2, wherein said alkaline earth carbonate is: Strontium carbonate powder, lime carbonate or barium carbonate.
4. according to the preparation method of claim 1 and 2, wherein said alkaline earth nitrate is: strontium nitrate, nitrocalcite or nitrate of baryta.
5. according to the preparation method of claim 1 and 2, wherein said alkaline earth oxalate is: strontium oxalate, caoxalate or barium oxalate.
CNA2003101100526A 2003-11-17 2003-11-17 Method for preparing green long-time afterglow luminescent powder Pending CN1544577A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNA2003101100526A CN1544577A (en) 2003-11-17 2003-11-17 Method for preparing green long-time afterglow luminescent powder

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNA2003101100526A CN1544577A (en) 2003-11-17 2003-11-17 Method for preparing green long-time afterglow luminescent powder

Publications (1)

Publication Number Publication Date
CN1544577A true CN1544577A (en) 2004-11-10

Family

ID=34335489

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2003101100526A Pending CN1544577A (en) 2003-11-17 2003-11-17 Method for preparing green long-time afterglow luminescent powder

Country Status (1)

Country Link
CN (1) CN1544577A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100432184C (en) * 2005-03-25 2008-11-12 上海师范大学 Preparation of visible light -initiated nano superlong-persistence luminescent materials
CN101747895A (en) * 2009-12-14 2010-06-23 海洋王照明科技股份有限公司 Green luminescent material and preparation method thereof
CN107867825A (en) * 2017-11-02 2018-04-03 杭州显庆科技有限公司 A kind of mechanoluminescence transparent ceramic material and preparation method thereof
CN112010679A (en) * 2020-10-29 2020-12-01 佛山市东鹏陶瓷发展有限公司 Co-firing method-based luminescent ceramic tile preparation process and luminescent ceramic tile prepared by same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100432184C (en) * 2005-03-25 2008-11-12 上海师范大学 Preparation of visible light -initiated nano superlong-persistence luminescent materials
CN101747895A (en) * 2009-12-14 2010-06-23 海洋王照明科技股份有限公司 Green luminescent material and preparation method thereof
CN107867825A (en) * 2017-11-02 2018-04-03 杭州显庆科技有限公司 A kind of mechanoluminescence transparent ceramic material and preparation method thereof
CN112010679A (en) * 2020-10-29 2020-12-01 佛山市东鹏陶瓷发展有限公司 Co-firing method-based luminescent ceramic tile preparation process and luminescent ceramic tile prepared by same

Similar Documents

Publication Publication Date Title
CN1062887C (en) Long afterglow phosphorescent body and preparation method thereof
CN1775902A (en) Alkaline earth phosphate long afterglow luminous material and its preparing method
WO2008061436A1 (en) Waterproof multi-element co-activated long afterglow light-accumulating phosphors
CN1912049A (en) High brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder and its preparation method
WO2013074158A1 (en) Green and yellow aluminate phosphors
CN109666481A (en) A kind of long after glow luminous material and preparation method thereof
CN103396796B (en) Antimonate long-afterglow fluorescent powder and preparation method thereof
CN1208423C (en) Red luminescent powder mixed with europium and its method
EP2565253B1 (en) Silicate luminescent material and production method thereof
CN1544577A (en) Method for preparing green long-time afterglow luminescent powder
CN1221631C (en) Rear earth green long afterglow luminescent material and preparing process thereof
CN1810921A (en) Red long afterglow luminescent material and its prepn
CN108949173B (en) Cyan silicate ultra-long afterglow luminescent material and preparation method thereof
CN114058371B (en) Yellow light long afterglow luminescent material and preparation method and application thereof
CN1163569C (en) Fluorescent material with ultra-long afterglow and its preparing process and application
CN104629759A (en) Method for enhancing emission intensity of strontium aluminate fluorescent powder
CN101074372A (en) Silicate long-afterglow luminescent material and its production
CN106833643A (en) A kind of green emitting phosphor of ultraviolet/near ultraviolet excitation and preparation method thereof
CN1115779A (en) Multiple-ion activated long-decay photoluminescent alkaline-earth aluminate material and its prepn
CN1232609C (en) Long persistence luminescence material containing cadmium oxide and its preparing method
CN1063211C (en) Long-persistence and high-brightness luminous material and its prepn
CN1876756A (en) White light diode, synergistic light-transferring powder, fluorescent powder and fluorescent powder preparation method
CN104194781A (en) Long persistence luminescent material with single substrate and adjustable persistence colors and preparation method of long persistence luminescent material
CN1291634A (en) Aluminate-series light-accumulating luminous material
CN1246420C (en) Luminescent powder in user for LED with GaN as base and preparing method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication