CN1091793C - Coated rare earth-activated luminous alkali earth metal aluminate luminescent material and its preparation process - Google Patents
Coated rare earth-activated luminous alkali earth metal aluminate luminescent material and its preparation process Download PDFInfo
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- CN1091793C CN1091793C CN99112331A CN99112331A CN1091793C CN 1091793 C CN1091793 C CN 1091793C CN 99112331 A CN99112331 A CN 99112331A CN 99112331 A CN99112331 A CN 99112331A CN 1091793 C CN1091793 C CN 1091793C
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- earth metal
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Abstract
The present invention relates to a coated alkaline earth metal aluminate luminescent material activated by rare earth and a preparing technology thereof. The coated luminescent material is composed of a coating layer and a luminescent base body. The technology comprises the steps: the luminescent base body is presintered, pulverized, finely ground, mixed with coating materials and calcined in reducing atmosphere. Through surface modification and coating treatment, the present invention provides a luminescent material with the advantages of favorable fluidity and dispersivity, neutrality in water medium, high initial luminescent brightness, no radiation hazard and long persistence. The persistence time is as long as 12 hours, and the usage temperature reaches 1260 DEG C.
Description
The invention belongs to material science, particularly a kind of coated rare earth-activated luminous alkali earth metal aluminate luminescent material and preparation technology thereof.
About europkium-activated luminous alkali earth metal aluminate luminescent material more existing report and patent introductions.Chinese invention patent application publication number CN 1126746A has proposed Eu, Ce, Tb, Dy activated alkali earth metal aluminate long-afterglow photoluminescent; Chinese invention patent application publication number CN 1115779A has then proposed rare earth ion, and (Tb is Dy) with non-rare earth ion (Sb, Sn) coactivated polyion activated luminescent material for Eu, Ce; Chinese invention patent application publication number CN 1152018A discloses a kind of long Persistence and high brightness fluorescent materials and preparation method thereof, and the general expression of luminescent material is: M.N.AL
2-XB
XO
4, wherein M represents alkaline-earth metal, is generally strontium, N represents rare earth element, is generally europium, 0.1≤X≤1.Chinese invention patent application publication number CN 1132777A and United States Patent (USP) (US Patent 5686022) all disclose rare-earth activated luminous alkali earth metal aluminate luminescent material and preparation technology thereof.These patents think that except europium was made active element, one or more of other lanthanide series rare-earth elements such as cerium, neodymium, praseodymium, samarium, terbium, dysprosium, holmium, erbium, thulium, ytterbium etc. also can be used as active element; The alkaline-earth metal that is adopted comprises calcium, strontium, barium and magnesium.
But above-mentioned rare-earth activated luminous alkali earth metal aluminate luminescent material often is strong basicity in water medium, in many occasions, particularly is difficult to direct use in luminous paint, luminous ceramic glaze material, luminous enamel glaze material, luminescent plastics, luminous rubber.On the other hand, the heat resistance of above-mentioned luminescent material is poor, Chinese invention patent application publication number 1202472 disclosed energy storage luminous ceramic glaze materials for example, its luminescent material is rare-earth activated aluminate luminescent material, the use temperature in ceramic glaze is no more than 1050 ℃.
The objective of the invention is to overcome the deficiencies in the prior art, a kind of luminous alkali earth metal aluminate luminescent material and preparation technology thereof of coated is provided.The present invention handles by surface modification and parcel, and solving rare earth-activated luminous alkali earth metal aluminate luminescent material can not a direct applied difficult problem in many occasions, and improves the use temperature of luminescent material; Utilize the lapping and the material modified characteristics of luminescence that the characteristics of sensibilized are arranged simultaneously, improve the luminescent properties of luminescent material luminescent material.
The present invention realizes in the following manner:
Coated rare earth-activated luminous alkali earth metal aluminate luminescent material is made up of integument and alkali earth metal aluminate luminous substrate, and its weight percent (wt%) is: integument 1～20%, alkali earth metal aluminate luminous substrate 80～99%.
Luminescent material recited above, alkali earth metal aluminate luminous substrate wherein is made up of four parts, activator, alkaline earth metal oxide, aluminum oxide and properties-correcting agent.
Alkaline earth metal oxide comprises strontium oxide, barium oxide, calcium oxide and magnesium oxide, these alkaline earth metal oxides can be a kind of in luminescent material, also can be multiple, they are to introduce with the form of carbonate or vitriol, and the molecule mole number of alkaline earth metal oxide and aluminum oxide is respectively 0.15～2.5 and 1.Activator is: the oxide compound of europium, cerium, neodymium, praseodymium, samarium, terbium, dysprosium, holmium, erbium, thulium, ytterbium at least a or multiple.Its add-on is that the per-cent (mol%) of aluminum oxide molal weight is: 0.1～0.5.
Properties-correcting agent is at least a in silicon-dioxide, calcium phosphate, ammonium phosphate, secondary calcium phosphate, the potassiumphosphate, and its add-on is that the per-cent (mol%) of aluminum oxide molal weight is: 0.5～10.The purpose that adds properties-correcting agent is the bonding action that strengthens luminous substrate and integument, improves the state of luminous substrate in the aqueous solution, and promotes luminous.
Above-mentioned coated luminescent material, its feature are that also integument wherein is made of at least a institute in pure aluminium silicate, aluminum phosphate, calcium phosphate, yttrium phosphate, silicon oxide, zirconium white, the germanium oxide.
The coated rare earth-activated luminous alkali earth metal aluminate luminescent material that the present invention is prepared, the particle shape rule, dispersed, good fluidity, luminous initial brightness height, time of persistence is long, "dead" harm is neutral in water medium, can easily use in matrixes such as coating, ceramic glaze, frit for porcelain enamel, plastics, rubber.In silicate product, use maximum operation (service) temperature and can reach 1260 ℃.
The processing step for preparing above-mentioned coated rare earth-activated luminous alkali earth metal aluminate luminescent material is:
1) activator, alkaline earth metal carbonate or vitriol, aluminum oxide, modifier powder and a small amount of boric acid are made fusing assistant, by after the proportioning weighing, and thorough mixing, in the crucible of packing into then, under reducing atmosphere, pre-burning under 1000～1100 ℃ temperature; Pre-imitation frosted glass is pulverized preparation luminescent material matrix powder;
2) the luminescent material matrix powder is distributed in the solution of lapping and floods; Remove surplus solution with the supercentrifuge centrifugation, use deionized water wash, oven dry; Can repeatedly wrap up,, behind the parcel,, carry out the secondary parcel after the cooling for the first time 400 ℃ of left and right sides pre-burnings to improve parcel efficient;
3) during the powder after will drying is packed crucible into, under reducing atmosphere,, be incubated 2 hours in 1200～1350 ℃ temperature lower calcination; Then, will calcine material and pulverize, be prepared into the coated rare earth-activated luminous alkali earth metal aluminate luminescent material powder.
Provide embodiments of the invention below:
Embodiment 1
Take by weighing SrCO
3150 grams, Al
2O
3Fine powder 100 grams, Eu
2O
31 gram, Dy
2O
31 gram; Take by weighing silicon-dioxide 2 grams, boric acid 6 grams, thorough mixing;
Compound is packed in the crucible, under reducing atmosphere,, be incubated 1 hour in 1050 ℃ of pre-burnings; Pre-imitation frosted glass is pulverized, made the luminescent material matrix powder;
2) with luminescent powder base-material 100 grams, add the potassium silicate of 750mL0.1M and the KAl (SO of 750mL0.1M
4)
2Mixing solutions in, ultra-sonic dispersion flooded 20 minutes.Separate and use deionized water wash with supercentrifuge, dry;
3) during the powder after will drying is packed the aluminum oxide crucible into, under reducing atmosphere,, be incubated 2 hours in 1280 ℃ temperature lower calcination.To calcine material and pulverize, make coated luminescent powder material.
The coated rare earth-activated luminous alkali earth metal aluminate luminescent material that present embodiment is prepared has formed the protective membrane of the fine and close pure aluminium silicate of one deck at the luminescent material matrix surface.This luminescent material is yellow-green colour, is longer than time of persistence 12 hours, and luminescent spectrum λ max is 490nm, is neutral in the aqueous solution, can be used for the decoration of 1200 ℃ of ceramic glazes that burn till.
Embodiment 2
1) according among the embodiment 1 1) step prepare the luminescent material matrix; Luminescent material matrix powder 110 grams are distributed to the KAl (SO of 750mL0.08M
4)
2In the solution, flooded 20 minutes, then through high speed centrifugation separation removal KAl (SO
4)
2Solution, oven dry; Again this powder is distributed in the potassium silicate solution of 750mL0.1M, flooded 20 minutes.Powder separates and washing through high speed centrifugation, 400 ℃ of pre-burnings.
2) powder with pre-burning carries out the secondary coating according to aforesaid operations.
3) according among the embodiment 1 3) the step calcining, obtain wrapping up luminescent material.
In the silicate product that the luminescent material of this embodiment preparation can be used for burning till below 1260 ℃.
Embodiment 3
1) takes by weighing SrCO
3150 grams, Al
2O
3Fine powder 100 grams, Eu
2O
31 gram, Dy
2O
31 gram; Take by weighing Secondary ammonium phosphate 10 grams, boric acid 8 grams, thorough mixing;
Compound is packed in the crucible, under reducing atmosphere,, be incubated 1 hour in 1050 ℃ of pre-burnings; Pre-imitation frosted glass is pulverized, made the luminescent material matrix powder;
2), add the KAl (SO of 750mL0.1M with luminescent powder base-material 100 grams
4)
2Solution in, ultra-sonic dispersion flooded 20 minutes.Separate and use deionized water wash with supercentrifuge, dry; Again this powder is distributed in the disodium phosphate soln of 750 mL0.1M, flooded 20 minutes.Powder separates and washing through high speed centrifugation, 450 ℃ of pre-burnings.Powder with pre-burning carries out secondary parcel, oven dry again.
3) during the powder after will drying is packed the aluminum oxide crucible into, under reducing atmosphere,, be incubated 2 hours in 1350 ℃ temperature lower calcination.To calcine material and pulverize, make coated luminescent powder material.
The coated rare earth-activated luminous alkali earth metal aluminate luminescent material that present embodiment is prepared has formed the protective layer of the fine and close aluminum phosphate of one deck at the luminescent material matrix surface.It is blue green that this luminescent material is, and was longer than time of persistence 12 hours, and luminescent spectrum λ max is 520nm, is neutral in the aqueous solution, can be used for the decoration of 1260 ℃ of ceramic glazes that burn till.
Claims (3)
1. coated rare earth-activated luminous alkali earth metal aluminate luminescent material, it is characterized in that: it is made up of integument and rare-earth activated alkali earth metal aluminate luminous substrate; The weight percent of integument and rare-earth activated alkali earth metal aluminate luminous substrate (wt%) is: integument 1～20%, rare-earth activated alkali earth metal aluminate luminous substrate 80-99%; Integument is made of at least a institute in pure aluminium silicate, aluminum phosphate, calcium phosphate, yttrium phosphate, silicon oxide, zirconium white, the germanium oxide; The alkali earth metal aluminate luminous substrate is made up of activator, alkaline earth metal oxide, aluminum oxide, properties-correcting agent four parts, alkaline earth metal oxide be strontium oxide, calcium oxide, barium oxide, magnesian one or more, activator is oxide compound at least a or multiple of europium, cerium, neodymium, praseodymium, samarium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and properties-correcting agent is at least a in silicon-dioxide, calcium phosphate, ammonium phosphate, secondary calcium phosphate, the potassiumphosphate.
2. coated rare earth-activated luminous alkali earth metal aluminate luminescent material according to claim 1, its feature also is: the molecule mole number of alkaline earth metal oxide and aluminum oxide is respectively 0.15～2.5 and 1; The per-cent of the add-on of activator and aluminum oxide molal weight (mol%) is: 0.1～0.5; The per-cent of the add-on of properties-correcting agent and aluminum oxide molal weight (mol%) is: 0.5～10.
3. preparation technology based on claim 1,2, described coated rare earth-activated aluminate luminescent material is characterized in that may further comprise the steps:
1) activator, alkaline earth metal carbonate or vitriol, aluminum oxide, modifier powder and a small amount of boric acid are made fusing assistant, by after the proportioning weighing, thorough mixing, pack into then in the crucible, under reducing atmosphere, pre-burning under 1000-1100 ℃ temperature is pulverized pre-imitation frosted glass then, preparation luminescent material matrix powder;
2) the luminescent material matrix powder is distributed in the solution of lapping and floods; Remove surplus solution with the supercentrifuge centrifugation, use deionized water wash, oven dry;
3) during the powder after will drying is packed crucible into, under reducing atmosphere,, be incubated 2 hours in 1200～1350 ℃ temperature lower calcination; To calcine material and pulverize, be prepared into the coated rare earth-activated luminous alkali earth metal aluminate luminescent material powder.
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| CN99112331A CN1091793C (en) | 1999-07-23 | 1999-07-23 | Coated rare earth-activated luminous alkali earth metal aluminate luminescent material and its preparation process |
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|---|---|---|---|
| CN99112331A CN1091793C (en) | 1999-07-23 | 1999-07-23 | Coated rare earth-activated luminous alkali earth metal aluminate luminescent material and its preparation process |
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|---|---|
| CN1241612A CN1241612A (en) | 2000-01-19 |
| CN1091793C true CN1091793C (en) | 2002-10-02 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100553216B1 (en) * | 2003-12-23 | 2006-02-22 | 주식회사 엘지화학 | A new blue phosphor and a method of preparing the same |
| CN1304528C (en) * | 2005-07-21 | 2007-03-14 | 大连理工大学 | Ligand complex type rareearth activated alkaline earth aluminate long after glow luminous material |
| CN100363457C (en) * | 2005-11-04 | 2008-01-23 | 中国科学院长春应用化学研究所 | Low heat solid phase method for implementing nano-cladding on fluorescent pewder surface |
| CN100497518C (en) * | 2006-04-27 | 2009-06-10 | 昆明贵金属研究所 | Process for preparing aluminate luminescent materials |
| CN101182413B (en) * | 2007-12-07 | 2010-12-01 | 江苏苏博特新材料股份有限公司 | Method for preparing rare earth aluminate matrix fluorescent powder |
| CN101343535B (en) * | 2008-08-19 | 2011-03-16 | 暨南大学 | Method for coating alumine acid strontium long afterglow luminescent powder surface |
| CN105949947B (en) * | 2016-05-20 | 2019-02-12 | 林歆 | Fluorescent paint, preparation method and application |
| CN106277791B (en) * | 2016-08-13 | 2019-04-09 | 华南理工大学 | A kind of high temperature resistant silicon hydrochlorate luminous ceramic glaze and preparation method thereof |
| CN108659573B (en) * | 2017-03-29 | 2021-02-05 | 中国科学院包头稀土研发中心 | Rare earth pigment mixtures and methods |
| CN108395851A (en) * | 2018-05-21 | 2018-08-14 | 昆山玉寰包装材料有限公司 | Adhesive tape and preparation method thereof with anti-skidding and light-accumulated luminous performance |
| CN118324407B (en) * | 2024-06-14 | 2024-10-01 | 蒙娜丽莎集团股份有限公司 | Multilayer cladding luminescent material, luminescent decorative effect ceramic tile and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091149A (en) * | 1993-02-18 | 1994-08-24 | 三星电管株式会社 | Blue light-emitting fluorescent-lamp-use fluorescent material and with the luminescent lamp of this fluorescent material |
| CN1115779A (en) * | 1994-10-17 | 1996-01-31 | 肖志国 | Multiple-ion activated long-decay photoluminescent alkaline-earth aluminate material and its prepn |
-
1999
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091149A (en) * | 1993-02-18 | 1994-08-24 | 三星电管株式会社 | Blue light-emitting fluorescent-lamp-use fluorescent material and with the luminescent lamp of this fluorescent material |
| CN1115779A (en) * | 1994-10-17 | 1996-01-31 | 肖志国 | Multiple-ion activated long-decay photoluminescent alkaline-earth aluminate material and its prepn |
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