CN1891783A - 一种复合基质长余辉荧光材料及其制备方法 - Google Patents

一种复合基质长余辉荧光材料及其制备方法 Download PDF

Info

Publication number
CN1891783A
CN1891783A CNA2005100799000A CN200510079900A CN1891783A CN 1891783 A CN1891783 A CN 1891783A CN A2005100799000 A CNA2005100799000 A CN A2005100799000A CN 200510079900 A CN200510079900 A CN 200510079900A CN 1891783 A CN1891783 A CN 1891783A
Authority
CN
China
Prior art keywords
fluorescent material
raw material
afterglow fluorescent
overlength afterglow
combination
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.)
Granted
Application number
CNA2005100799000A
Other languages
English (en)
Other versions
CN100485013C (zh
Inventor
张明
张立
张小磊
张强
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.)
Sichuan Sunfor Light Co Ltd
Original Assignee
XINLI INDUSTRIAL GROUP Co Ltd SICHUAN
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
Priority to CNB2005100799000A priority Critical patent/CN100485013C/zh
Application filed by XINLI INDUSTRIAL GROUP Co Ltd SICHUAN filed Critical XINLI INDUSTRIAL GROUP Co Ltd SICHUAN
Priority to EP06761313A priority patent/EP1900789B1/en
Priority to DE602006018737T priority patent/DE602006018737D1/de
Priority to ES06761313T priority patent/ES2357275T3/es
Priority to PCT/CN2006/001428 priority patent/WO2007003102A1/zh
Priority to US11/993,574 priority patent/US7955523B2/en
Priority to AT06761313T priority patent/ATE491009T1/de
Publication of CN1891783A publication Critical patent/CN1891783A/zh
Priority to HK07107264.7A priority patent/HK1103302A1/xx
Application granted granted Critical
Publication of CN100485013C publication Critical patent/CN100485013C/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7795—Phosphates
    • C09K11/7796—Phosphates with alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7777—Phosphates
    • C09K11/7778—Phosphates with alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/446—Sulfides, tellurides or selenides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties
    • C04B2235/9661—Colour
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Luminescent Compositions (AREA)

Abstract

本发明涉及一种新型的超长余辉荧光材料及其制备方法，所述材料包括由aMS·bM3 (PO4) 2·cMSiO2·dMO·fAl2O3·xRO·yTR2O3·zMnO构成的荧光体，M为钙，镁，钡，锶，锌或其组合；R为铕，钐，镱，镨，钕或其组合；TR为镧，钇，钕，镝，铒，铥，铈，钬或其组合；a、b、c、d、f、x、y、z是摩尔数。所述的荧光材料具有优越的耐水性和耐温性。

Description

一种复合基质长余辉荧光材料及其制备方法
技术领域
本发明涉及一种复合基质的长余辉荧光材料及其制备方法，尤其是涉及具有高耐水性和高亮度的超长余辉荧光材料。
背景技术
长余辉荧光材料是一种经太阳光或其他光源照射后，例如ZnS:Cu(发绿光)或者CaS:Bi(发紫蓝光)或者ZnCdS:Cu(发黄——橙色光)。但是，这种硫化物的余辉时间极短，且性能不稳定，耐光性差，使用寿命短。基本上不能应于户外，即使用于钟表表盘，由于其余辉时间只有20-30分钟，也不能满足需要。
另一种过去开发的蓄光性荧光体含有放射性物质，这种材料可在很长时间内自行发光，但放射性物质是公认的危险污染源，对人体、环境均会产生严重的损害，所以，国际上已经严禁使用。
九十年代初，人们开发一种光激发的具有长余辉的荧光材料，例如CN1053807A公开了一种具有长余辉的荧光材料，其一般式为m(Sr1-xEux)O.nAl2O3.yB2O3，这种长余辉荧光材料的亮度和余辉时间都不高。
此外，美国专利5370303和424006以及日本特许号8-73845，8-127772公开了Eu2+激活的碱土金属铝酸盐长余辉荧光物质，显示出较高的亮度和余辉时间，但是，由于烧结温度过高，或者是引入过量硼酸降低了烧结温度，使烧结块难于破碎，导致粉体亮度降低很大。同时，由于采用的是N2+H2混合气体，使得操作的安全性不好，设备难度增大。又由于烧结温度过高对加热体的要求也更高，费用增加。
近年来，在人们的不懈努力下，以铝酸盐为基质的荧光材料的发光性能得到不断提高，但是，如以上所述的其生产工艺中温度高，产品块体硬度大，不易粉碎的问题一直困惑着人们。
CN1307082A教导了一种长余辉无机发光材料的制备方法，其中，公开了一种具有aMO·bN2O3·xRO·yTR2O3的稀土离子共激活的IIA、IIIA主族元素氧化物的无机发光材料，其中，M是选自Sr、Ca、Mg、Zn中的一种或多种元素，N是选自B、Al、Ga、Sc中的一种或多种元素，R是选自Eu、Sm、Yb中的一种或多种元素，TR是选自La、Pr、Y、Nd、Dy、Er、Tm、Ho中的一种或多种元素，并且，0.5≤a≤5，0.5≤b≤7，0.0001≤x≤0.5，0.0001≤y≤0.5。所述的方法是将经研细的对应氧化物的草酸盐、碳酸盐或氢氧化物与占物料总量0.1-1％(重量)的硫，通入NH3或加入碳粒，在1200-1400℃下灼烧2-5小时。所得到的材料可以进一步通过硅酸钠或硅酸钾处理，或者通过甲基硅油处理。具有所述通式并且按上述方法制备的无机发光材料具有在弱光下即可快速激发的特点，并且，由于灼烧温度比较低，所得到的材料易于粉碎，能够得到细颗粒的发光粉，并且，所述的材料具有良好的耐水性能，基本上能够满足制造水涂料的需要。但是，所得到的产品其荧光亮度和耐水性能仍然不能满足长时存放的需要。本发明针对以上不足，满足了水性涂料长时间放置不改变其发光性能。为此，本发明的目的在于提供一种在水中能够稳定更长时间、荧光亮度更高的超长余辉荧光材料。
发明内容
本发明的一个方面提供了一种超长余辉荧光材料，所述的超长余辉荧光材料包括由
aMS·bM3(PO4)2·cMSiO2·dMO·fAl2O3·xRO·yTR2O3·zMnO构成的荧光体，其中，
所述的M选自由钙，镁，钡，锶，锌组成的组中的一种或其组合；
所述的R选自由铕，钐，镱，镨和钕组成的组中的一种或其组合；
所述的TR选自由镧，钇，钕，镝，铒，铥，铈，钬组成的组中的一种或其组合；并且，a、b、c、d、f、x、y、z是摩尔数，其中，
0.01≤a≤8，优选为0.01≤a≤5；
0.01≤b≤6，优选为0.01≤b≤1.5；
0.01≤c≤2，优选为0.01≤c≤1；
0.01≤d≤7，优选为0.01≤d≤5；
0.01≤f≤7，优选为0.01≤f≤5；
0.0001≤x≤0.5，优选为0.0001≤x≤0.01；
0.0001≤y≤0.5，优选为0.001≤y≤0.01；
0.001≤z≤0.2，优选为0.001≤z≤0.1。
本发明的另一个方面提供了制备上述超长余辉荧光材料的方法，所述的方法包括：
1)以所述M的氧化物、碳酸盐、草酸盐、硝酸盐或氢氧化物作为M的原料；以单质硫作为硫的原料；以五氧化二磷、磷酸二氢氨作为磷的原料；以二氧化硅作为硅的原料；以氧化铝、氢氧化铝作为氧化铝的原料；
以R的氧化物作为RO的原料；
以TR对应元素的氧化物作为TR2O3的原料；
并使这些原料的重量比满足上述a、b、c、d、f、x、y、z的关系；以及，
尿素，尿素与M的摩尔比为0.1-1∶1；
LiCl，LiCl与M的摩尔比为0.0165-1∶1；
2)将上述原料充分混合后，通入氨气或加入碳粒，在1200-1450℃下灼烧1-4小时。
本发明的再一个方面提供了一种制品，所述的制品包含如上所述的超长余辉荧光材料。优选地，所述的制品是一种陶瓷制品，这种陶瓷制品是将上述的超长余辉荧光材料和陶瓷原料一起再500-1000℃的温度下烧制而得到的。
具体而言，制备所述超长余辉荧光材料的方法是将上述氧化物、氢氧化物或者硝酸盐、硫(精硫或升化硫)，同时添加尿素，经8-12小时的充分混合后，在1200-1450℃下采用 或C(碳)等还原环境下灼烧1-4小时。
将灼烧后的荧光材料自然冷却后，得到块体疏松的荧光材料烧结体，经鄂式破碎机、对辊机、气流粉碎机、超声波振动筛，得到粒径均匀(细度可达纳米级)的荧光材料粉体。之后在所得产物的表面进一步用浓度为0.1-2％(重量)的正硅酸乙酯或甲基硅油进行表面包膜处理。以此得到本发明所述的高亮度、超长余辉。且粒度均匀、耐水性优良的发光粉。
与常规方法相比，按照本发明的发光材料，块体疏松，易于粉碎，所得到的产品粒度均匀。另外，产品的弱光激发效果好，发光亮度高，余辉持续时间长。此外，本发明的产品耐水性好，实用性强。
本发明的超长余辉荧光材料是一种复合基质的无机发光材料，其发光性能优于以铝酸盐为基质的荧光材料。这种荧光材料具有多面体晶格，在弱光下即可快速激发(1-3秒)。另外，所得到的复合基质超长余辉荧光材料在粒径非常小(如纳米级)的情况下，仍然具有高亮度、超长余辉的性能，并且，这种材料具有优异的耐水性能。另外，本发明的多基质超长余辉荧光材料还具有良好的耐热性能，能够与陶瓷材料相结合，在500-1000℃下进行灼烧，生产出发光的陶瓷制品，且发光亮度不受影响。
具体实施方式
通过以下实例的方法详细说明本发明，但这些实例不用来限制本发明的范围。
在下例实例中，所用试剂的规格均为优先级纯，并且，S为精硫。
实施例1
原料：
  原料  用量(g)  用量(mol)   原料   用量(Kg)  用量(mol)
  SrCO3  57.8Kg  0.3915   Al2O3   37.6Kg  0.5013
  Eu2O3  2.8Kg  0.008   Dy2O3   3.1Kg  0.0083
  H3BO3  3.7Kg  0.0599   S   1.7Kg  0.05431
  P2O5  6.4Kg  0.0451   LiCl   0.7Kg  0.0163
  尿素  0.5Kg  0.0083   Ce2O3   0.7Kg  0.0021
  MnCO3  0.5Kg  0.0044   SiO2   12Kg  0.1997
方法：
将以上配比物料，经充分混合后，盛入刚玉坩锅中，在1450℃下通入氨气，在此环境下灼烧1.5小时。灼烧后，将所得到的物料采用气流粉碎机进行研磨到10-50um得到发光粉。该产品的通式基本上为0.05431SrS·0.027Sr3(PO4)2·0.1997SrSiO2·0.3915SrO·0.5013Al2O3·0.008EuO·0.0083Dy2O3·0.0021Ce2O3·0.0044MnO                    (1)
将所得发光粉放入盛有正硅酸乙酯∶乙醇＝100∶2的溶液中，充分搅拌，在200℃条件下烘干，过筛，得到耐水性优良、初始亮度高、余辉时间长的荧光材料。所得到的产品的发射峰为530nm，为黄绿色发光体。用200LX的光源激发，激发后亮度降到0.32mcd/m2的时间为70小时。主要性能与已知产品的比较列在表1中。
实施例2
原料：
  原料  用量(g)  用量(mol)   原料   用量(Kg)  用量(mol)
  SrCO3  56.2  0.3807   Al2O3   32  0.3137
  Eu2O3  2.2  0.00625   Dy2O3   2.7  0.00723
  H3BO3  3.2  0.0517   S   3.2  0.1
  P2O5  5  0.0352   LiCl   0.4  0.0094
  尿素  0.2  0.003   Ce2O3   0.5  0.00152
  MnCO3  0.6  0.00174   SiO2   9  0.149
方法：
重复实施例1中的方法，不同之处在于灼烧是在1400℃下进行2小时。由此得到的发光粉，其通式基本上为0.1SrS·0.0176Sr3(PO4)2·0.149SrSiO2·0.3807SrO·0.3137Al2O3·0.0625EuO·0.00723Dy2o3·0.00152Ce2O3·0.00174MnO              (2)
进一步按实施例1的方法进行正硅酸乙酯：乙醇＝100∶2的处理。
所得到的产品的发射峰为530nm，为黄绿色发光体。用200LX的光源激发，激发后亮度降到此为0.32mcd/m2的时间为66小时。主要性能与已知产品的比较列在表1中。
实施例3
原料：
  原料  用量(g)  用量(mol)   原料   用量(Kg)   用量(mol)
  SrCO3  57.5  0.3895   Al2O3   37   0.3627
  Eu2O3  1.98  0.0056   Dy2O3   2.65   0.0071
  H3BO3  4  0.0647   S   14   0.4375
  P2O5  8  0.05635   LiCl   0.35   0.00825
  尿素  0.5  0.008   Ce2O3   0.5   0.001513
  MnCO3  0.6  0.00522   SiO2   7   0.1165
方法：
重复实施例1的方法，不同之处在于灼烧是在1400℃下灼烧3小时。由此得到的发光粉，其通式基本上为：0.4375SrS·0.02817Sr3(PO4)2·0.0582SrSiO2·0.3895SrO·0.3627Al2O3·0.0056EuO·0.0071Dy2O3·0.001513Ce2O3·0.00522MnO            (3)
进一步按实施例1的方法进行正硅酸乙酯∶乙醇＝100∶2的处理。
所得到的产品的发射峰为530nm，为黄绿色发光体。用200LX的光源激发，激发后亮度降到此为0.32mcd/m2的时间为65小时。主要性能与已知产品的比较列于表1中。
实施例4
原料：
  原料  用量(g)  用量(mol)   原料   用量(Kg)  用量(mol)
  SrCO3  34  0.233   Al2O3   58.5  0.5735
  Eu2O3  1.44  0.00409   Dy2O3   3.1  0.00831
  H3BO3  3.7  0.5986   S   1.7  0.053
  P2O5  6.4  0.045   LiCl   0.7  0.0165
  尿素  0.5  0.008   Ce2O3   0.7  0.00213
  MnCO3  0.5  0.00435   SiO2   12  0.2
方法：
重复实施例1的方法，不同之处在于灼烧是在1450℃下进行3小时。得到的发光粉其通式基本上为：0.053SrS·0.0275Sr3(PO4)2·0.2SrSiO2·0.233SrO·0.5735Al2O3·0.004EuO·0.00873Dy2O3·0.00217Ce2O3·0.00435MnO             (4)
进一步按实施例1的方法进行正硅酸乙酯∶乙醇＝100∶2的处理。
得到的产品为蓝色发光体。用200LX的光源激发，激发后亮度降到此为0.32mcd/m2的时间为70小时。主要性能与已知产品的比较列于表1中。
实施例5
原料：
  原料  用量(g)  用量(mol)   原料   用量(Kg)  用量(mol)
  SrCO3  24  0.1625   Al2O3   53.7  0.5264
  Eu2O3  1.8  0.0051   Dy2O3   2.7  0.00723
  H3BO3  3.2  0.05177   S   3.2  0.1
  P2O5  5  0.0352   LiCl   0.4  0.0094
  尿素  0.2  0.0033   Ce2O3   0.5  0.00435
  MnCO3  0.6  0.00522   SiO2   6  0.1
方法：
重复实施例1的方法，不同之处在于灼烧是在1400℃下进行3小时。得到的发光粉其通式基本上为：0.1625SrS·0.0176Sr3(PO4)2·0.1SrSiO2·0.1625SrO·0.5264Al2O3·0.0051EuO·0.00723Dy2O3·0.00435Ce2O3·0.6MnO                (5)
进一步按实施例1的方法进行正硅酸乙酯∶乙醇＝100∶2的处理。
得到的产品为蓝色发光体。用200LX的光源激发，激发后亮度降到此为0.32mcd/m2的时间为66小时。主要性能与已知产品的比较列在表1中。
实施例6
原料：
  原料  用量(g)   用量(mol)   原料   用量(Kg)  用量(mol)
  SrCO3  33   0.2235   Al2O3   59  0.5784
  Eu2O3  1.68   0.005317   Dy2O3   2.65  0.0071
  H3BO3  4   0.0647   S   9  0.281
  P2O5  8   0.0564   LiCl   0.35  0.00825
  尿素  0.5   0.00833   Ce2O3   0.5  0.00435
  MnCO3  0.6   0.00423   SiO2   7  0.1167
方法：
重复实施例1的方法，不同之处在于灼烧是在1400℃下进行3小时。得到的发光粉其通式基本上为：0.281SrS·0.0282Sr3(PO4)2·0.1167SrSiO2·0.1235SrO·0.5784Al2O3·0.005317EuO·0.0071Dy2O3·0.1167Ce2O3·0.6MnO                      (6)
进一步按实施例1的方法进行正硅酸乙酯∶乙醇＝100∶2的处理。
得到的产品的发射峰为530nm，为黄绿色发光体。用200LX的光源激发，激发后亮度降到此为0.32mcd/m2的时间为65小时。主要性能与已知产品的比较列在表1中。
实施例7
原料：
  原料  用量(g)  用量(mol)   原料   用量(Kg)  用量(mol)
  CaCO3  33  0.33   Al2O3   59  0.5784
  Pr6O11  1.68  0.00165   Dy2O3   2.65  0.0071
  H3BO3  4  0.0647   S   9  0.281
  P2O5  8  0.0564   LiCl   0.35  0.00825
  尿素  0.5  0.00833   Ce2O3   0.5  0.00435
  MnCO3  0.6  0.00423   SiO2   7  0.1167
方法：
重复实施例1的方法，不同之处在于灼烧是在1400℃下进行3小时。得到的发光粉其通式基本上为：0.281CaS·0.0286Ca3(PO4)2·0.1167CaSiO2·0.33CaO·0.5764Al2O3·0.00165PrO·0.0071Dy2O3·0.1157Ce2O3·0.6MnO                   (7)
进一步按实施例1的方法进行正硅酸乙酯∶乙醇＝100∶2的处理。
得到的产品为紫色发光体。用200LX的光源激发，激发后亮度降到此为0.32mcd/m2的时间为65小时。主要性能与已知产品的比较列在表1中。
实施例8
原料：
  原料  用量(g)  用量(mol)   原料   用量(Kg)  用量(mol)
  MgCO3  37  0.4404   Al2O3   59  0.5784
  Nd2O3  1.68  0.00291   Dy2O3   2.65  0.0071
  H3BO3  4  0.0647   S   9  0.281
  P2O5  8  0.0564   LiCl   0.35  0.00825
  尿素  0.5  0.00833   Ce2O3   0.5  0.00435
  MnCO3  0.6  0.00423   SiO2   7  0.1167
方法：
重复实施例1的方法，不同之处在于灼烧是在1400℃下进行3小时。得到的发光粉其通式基本上为：0.281MgS·0.0282Mg3(PO4)2·0.1167MgSiO2·0.4404MgO·0.5784Al2O3·0.00291NdO·0.0071Dy2O3·0.1167Ce2O3·0.6MnO                                       (8)
进一步按实施例1的方法进行正硅酸乙酯∶乙醇＝100∶2的处理。
得到的产品为蓝绿色发光体。用200LX的光源激发，激发后亮度降到此为0.32mcd/m2的时间为65小时。主要性能与已知产品的比较列在表1中。
实施例9
原料：
  原料  用量(g)   用量(mol)   原料   用量(Kg)  用量(mol)
  BaCO3  36.5   0.2235   Al2O3   59  0.5784
  Eu2O3  1.68   0.005317   Tm2O3   2.65  0.0071
  H3BO3  4   0.0647   S   9  0.281
  P2O5  8   0.0564   LiCl   0.35  0.00825
  尿素  0.5   0.00833   Ce2O3   0.5  0.00435
  MnCO3  0.6   0.00423   SiO2   7  0.1167
方法：
重复实施例1的方法，不同之处在于灼烧是在1400℃下进行3小时。得到的发光粉其通式基本上为：0.281BaS·0.0282Ba3(PO4)2·0.1167BaSiO2·0.2235BaO·0.5784Al2O3·0.005317EuO·0.0071Tm2O3·0.1167Ce2O3·0.6MnO                                     (9)
进一步按实施例1的方法进行正硅酸乙酯∶乙醇＝100∶2的处理。
得到的产品的发射峰为530nm，为绿色发光体。用200LX的光源激发，激发后亮度降到此为0.32mcd/m2的时间为65小时。主要性能与已知产品的比较列在表1中。
表1
由此可见，与已有的产品相比，本发明产品的发光亮度及发光时间已经有明显提高，就水稳定性方面，本发明的产品在经高分子材料处理后，能有效的与水性涂料、油墨等相结合，提高应用领域。
实施例10
表2显示本发明产品和CN1307082A与陶瓷釉结合时的耐温性能。由表2可见，在过去的发明中，与陶瓷釉结合时，因其发光材料的产品特性，在烧制陶瓷制品时，因其耐温性不佳，故其发光性随着温度的上升，发光性能随降低。而本发明所生产发光材料，热稳定性优越，与陶瓷釉相结合，所制成在的发光陶瓷制品，发光性能受温影响不大。
表2
          温度℃   500   700   800   900   1000   1100   1200
  发光性能下降率   本发明   2％   5％   12％   17％   22％   30％   50％
  CN1307082A 2％ 5％ 17％ 27％ 40％ 60％ 80％

Claims (10)

1.一种超长余辉荧光材料，包括由
aMS·bM3(PO4)2·cMSiO2·dMO·fAl2O3·xRO·yTR2O3·zMnO构成的荧光体，其中，
所述的M选自由钙，镁，钡，锶，锌组成的组中的一种或其组合；
所述的R选自由铕，钐，镱，镨和钕组成的组中的一种或其组合；
所述的TR选自由镧，钇，钕，镝，铒，铥，铈，钬组成的组中的一种或其组合；并且，a、b、c、d、f、x、y、z是摩尔数，其中，
0.01≤a≤8；
0.01≤b≤6；
0.01≤c≤2；
0.01≤d≤7；
0.01≤f≤7；
0.0001≤x≤0.5；
0.0001≤y≤0.5；
0.001≤z≤0.2。
2.如权利要求1所述的超长余辉荧光材料，其中，所述的a、b、c、d、f、x、y、z分别为：
0.01≤a≤5；
0.01≤b≤1.5；
0.01≤c≤1；
0.01≤d≤5；
0.01≤f≤5；
0.0001≤x≤0.01；
0.001≤y≤0.01；
0.001≤z≤0.1。
3.如权利要求1所述的超长余辉荧光材料，其中，所述的超长余辉荧光材料为：0.05431SrS·0.027Sr3(PO4)2·0.1997SrSiO2·0.3915SrO·0.5013Al2O3·0.008EuO·0.0083Dy2O3·0.0021Ce2O3·0.0044MnO；0.1SrS·0.0176Sr3(PO4)2·0.149SrSiO2·0.3807SrO·0.3137Al2O3·0.0625EuO·0.00723Dy2O3·0.00152Ce2O3·0.00174MnO；0.4375SrS·0.02817Sr3(PO4)2·0.0582SrSiO2·0.3895SrO·0.3627Al2O3·0.0056EuO·0.0071Dy2O3·0.001513Ce2O3·0.00522MnO；0.053SrS·0.0275Sr3(PO4)2·0.2SrSiO2·0.233SrO·0.5735Al2O3·0.004EuO·0.00873Dy2O3·0.00217Ce2O3·0.00435MnO；0.1625SrS·0.0176Sr3(PO4)2·0.1SrSiO2·0.1625SrO·0.5264Al2O3·0.0051EuO·0.00723Dy2O3·0.00435Ce2O3·0.6MnO；0.281SrS·0.0282Sr3(PO4)2·0.1167SrSiO2·0.1235SrO·0.5784Al2O3·0.005317EuO·0.0071Dy2O3·0.1167Ce2O3·0.6MnO；0.281CaS·0.0286Ca3(PO4)2·0.1167CaSiO2·0.33CaO·0.5764Al2O3·0.00165PrO·0.0071Dy2O3·0.1157Ce2O3·0.6MnO；0.281MgS·0.0282Mg3(PO4)2·0.1167MgSiO2·0.4404MgO·0.5784Al2O3·0.00291NdO·0.0071Dy2O3·0.1167Ce2O3·0.6MnO；或者0.281BaS·0.0282Ba3(PO4)2·0.1167BaSiO2·0.2235BaO·0.5784Al2O3·0.005317EuO·0.0071Tm2O3·0.1167Ce2O3·0.6MnO。
4.一种制备超长余辉荧光材料的方法，所述的荧光材料包括由
aMS·bM3(PO4)2·cMSiO2·dMO·fAl2O3·xRO·yTR2O3·zMnO构成的荧光体，其中，
所述的M选自由钙，镁，钡，锶，锌组成的组中的一种或其组合；
所述的R选自由铕，钐，镱，镨和钕组成的组中的一种或其组合；
所述的TR选自由镧，钇，钕，镝，铒，铥，铈，钬组成的组中的一种或其组合；并且，a、b、c、d、f、x、y、z是摩尔数，其中，
0.01≤a≤8；
0.01≤b≤6；
0.01≤c≤2；
0.01≤d≤7；
0.01≤f≤7；
0.0001≤x≤0.5；
0.0001≤y≤0.5；
0.001≤z≤0.2；
所述的方法包括：
1)以所述M的氧化物、碳酸盐、草酸盐、硝酸盐或氢氧化物作为M的原料；以单质硫作为硫的原料；以五氧化二磷、磷酸二氢氨作为磷的原料；以二氧化硅作为硅的原料；以氧化铝、氢氧化铝作为氧化铝的原料；
以R的氧化物作为RO的原料；
以TR对应元素的氧化物作为TR2O3的原料；
并使这些原料的重量比满足上述a、b、c、d、f、x、y、z的关系；以及，
尿素，尿素与M的摩尔比为0.1-1∶1；
LiCl，LiCl与M的摩尔比为0.0165-1∶1；
2)将上述原料充分混合后，通入氨气或加入碳粒，在1200-1450℃下灼烧1-4小时。
5.如权利要求4所述的方法，其中，所述的a、b、c、d、f、x、y、z分别为：
0.01≤a≤5；
0.01≤b≤1.5；
0.01≤c≤1；
0.01≤d≤5；
0.01≤f≤5；
0.0001≤x≤0.0；
0.001≤y≤0.01；
0.001≤z≤0.1。
6.如权利要求4所述的方法，其中，所述的超长余辉荧光材料为：0.05431SrS·0.027Sr3(PO4)2·0.1997SrSiO2·0.3915SrO·0.5013Al2O3·0.008EuO·0.0083Dy2O3·0.0021Ce2O3·0.0044MnO；0.1SrS·0.0176Sr3(PO4)2·0.149SrSiO2·0.3807SrO·0.3137Al2O3·0.0625EuO·0.00723Dy2O3·0.00152Ce2O3·0.00174MnO；0.4375SrS·0.02817Sr3(PO4)2·0.0582SrSiO2·0.3895SrO·0.3627Al2O3·0.0056EuO·0.0071Dy2O3·0.001513Ce2O3·0.00522MnO；0.053SrS·0.0275Sr3(PO4)2·0.2SrSiO2·0.233SrO·0.5735Al2O3·0.004EuO·0.00873Dy2O3·0.00217Ce2O3·0.00435MnO；0.1625SrS·0.0176Sr3(PO4)2·0.1SrSiO2·0.1625SrO·0.5264Al2O3·0.0051EuO·0.00723Dy2O3·0.00435Ce2O3·0.6MnO；0.281SrS·0.0282Sr3(PO4)2·0.1167SrSiO2·0.1235SrO·0.5784Al2O3·0.005317EuO·0.0071Dy2O3·0.1167Ce2O3·0.6MnO；0.281CaS·0.0286Ca3(PO4)2·0.1167CaSiO2·0.33CaO·0.5764Al2O3·0.00165PrO·0.0071Dy2O3·0.1157Ce2O3·0.6MnO；0.281MgS·0.0282Mg3(PO4)2·0.1167MgSiO2·0.4404MgO·0.5784Al2O3·0.00291NdO·0.0071Dy2O3·0.1167Ce2O3·0.6MnO；或者0.281BaS·0.0282Ba3(PO4)2·0.1167BaSiO2·0.2235BaO·0.5784Al2O3·0.005317EuO·0.0071Tm2O3·0.1167Ce2O3·0.6MnO。
7.如权利要求4所述的方法，其中，进一步包括将灼烧得到的超长余辉荧光材料粉碎，再用浓度为0.1-2％(重量)的正硅酸乙酯或甲基硅油溶液进行处理。
8.如权利要求7所述的方法，其中，所述的灼烧得到的超长余辉荧光材料被粉碎到纳米级。
9.一种制品，包含如权利要求1-3之一所述的超长余辉荧光材料或者如权利要求4-8之一的方法所制备的超长余辉荧光材料。
10.如权利要求9所述的制品，其中，所述的制品为陶瓷制品，并且，所述的制品是通过将所述的超长余辉荧光材料和陶瓷原料一起在500-1000℃下烧制后制备的。
CNB2005100799000A 2005-07-01 2005-07-01 一种复合基质长余辉荧光材料及其制备方法 Active CN100485013C (zh)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CNB2005100799000A CN100485013C (zh) 2005-07-01 2005-07-01 一种复合基质长余辉荧光材料及其制备方法
DE602006018737T DE602006018737D1 (de) 2005-07-01 2006-06-22 Lang nachglühendes lumineszierendes material mit konfektionierten substraten und seine herstellungsverfahren
ES06761313T ES2357275T3 (es) 2005-07-01 2006-06-22 Material luminescente de larga persistencia con sustratos compuestos y su método de fabricación.
PCT/CN2006/001428 WO2007003102A1 (fr) 2005-07-01 2006-06-22 Materiau luminescent a remanence elevee comportant des substrats composes et son procede de fabrication
EP06761313A EP1900789B1 (en) 2005-07-01 2006-06-22 Long afterglow luminescent material with compounded substrates and its preparation method
US11/993,574 US7955523B2 (en) 2005-07-01 2006-06-22 Long afterglow luminescent material with compounded substrates and its preparation method
AT06761313T ATE491009T1 (de) 2005-07-01 2006-06-22 Lang nachglühendes lumineszierendes material mit konfektionierten substraten und seine herstellungsverfahren
HK07107264.7A HK1103302A1 (en) 2005-07-01 2007-07-06 Long afterglow luminescent material with compounded matrix and its preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005100799000A CN100485013C (zh) 2005-07-01 2005-07-01 一种复合基质长余辉荧光材料及其制备方法

Publications (2)

Publication Number Publication Date
CN1891783A true CN1891783A (zh) 2007-01-10
CN100485013C CN100485013C (zh) 2009-05-06

Family

ID=37596986

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005100799000A Active CN100485013C (zh) 2005-07-01 2005-07-01 一种复合基质长余辉荧光材料及其制备方法

Country Status (8)

Country Link
US (1) US7955523B2 (zh)
EP (1) EP1900789B1 (zh)
CN (1) CN100485013C (zh)
AT (1) ATE491009T1 (zh)
DE (1) DE602006018737D1 (zh)
ES (1) ES2357275T3 (zh)
HK (1) HK1103302A1 (zh)
WO (1) WO2007003102A1 (zh)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008061403A1 (fr) * 2006-11-20 2008-05-29 Sichuan Sunfor Light Co., Ltd. Matière photoluminescente à longue émission rémanente coactivée contenant plusieurs métaux du groupe des terres rares
CN101403475B (zh) * 2008-11-13 2011-08-17 北京航空航天大学 一种蓄能发光石及其制备方法
US8506843B2 (en) 2010-12-17 2013-08-13 General Electric Company White emitting persistent phosphor
US8404153B2 (en) 2010-12-17 2013-03-26 General Electric Company White persistent phosphor blend or layered structure
CN102515704B (zh) * 2011-12-27 2014-07-02 淄博华光陶瓷科技文化有限公司 华青瓷及其制备方法
CN103263889A (zh) * 2013-05-16 2013-08-28 漳州师范学院 一种具有自清洁功能的长余辉发光活性炭雕材料的制备方法
CN104199496B (zh) * 2014-08-02 2016-09-07 浙江明辉发光科技有限公司 一种太阳能长余辉发光系统的激发方法
CN104974757B (zh) * 2015-07-20 2016-11-16 浙江工贸职业技术学院 一种可制氧的荧光材料及其制备方法

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US424006A (en) 1890-03-25 davies
CN1053807A (zh) 1991-03-09 1991-08-14 复旦大学 长余辉磷光材料及其制备
US5370303A (en) 1993-04-14 1994-12-06 International Paper Co. One piece grape box
JP2543825B2 (ja) 1993-04-28 1996-10-16 根本特殊化学株式会社 蓄光性蛍光体
US5376303A (en) 1994-06-10 1994-12-27 Nichia Chemical Industries, Ltd. Long Decay phoaphors
JP3232548B2 (ja) 1994-06-29 2001-11-26 日亜化学工業株式会社 残光性蛍光体
JP3232549B2 (ja) 1994-09-29 2001-11-26 日亜化学工業株式会社 残光性蛍光体
JP3456553B2 (ja) 1994-11-01 2003-10-14 根本特殊化学株式会社 蓄光性蛍光体
JP2979984B2 (ja) * 1994-11-29 1999-11-22 日亜化学工業株式会社 残光性蛍光体
JP3405049B2 (ja) 1995-05-29 2003-05-12 日亜化学工業株式会社 残光性ランプ
AU5396798A (en) * 1997-03-26 1998-10-20 Zhiguo Xiao Silicate phosphor with a long afterglow and manufacturing method thereof
JP3268761B2 (ja) 1998-08-18 2002-03-25 株式会社リード 耐熱・耐候性に優れた高輝度・長残光性アルミン酸塩蓄光体
CA2290340C (en) 1999-10-07 2003-09-09 Matsui Shikiso Chemical Co., Ltd. Process for preparing water resistant luminous pigments
CN1117134C (zh) * 2000-01-25 2003-08-06 四川新力实业集团有限公司 长余辉无机发光材料的制备方法
GB2374602B (en) * 2001-04-18 2003-04-23 Shandong Lunbo Ind & Comm Grou Alkali earth aluminate-silicate photoluminescent pigment which is activated by rare-earth elements
CN1152114C (zh) * 2001-10-26 2004-06-02 中国科学院长春应用化学研究所 蓝紫色、绿色硅铝锌体系长余辉发光材料的制备方法
WO2004024444A1 (ja) 2002-09-12 2004-03-25 Nippon Sheet Glass Company, Limited 発光膜被覆物品
US6953536B2 (en) * 2003-02-25 2005-10-11 University Of Georgia Research Foundation, Inc. Long persistent phosphors and persistent energy transfer technique
CN1228415C (zh) * 2003-04-17 2005-11-23 中国科学院长春应用化学研究所 长余辉发光材料磷酸锌的制备方法
FR2855169B1 (fr) 2003-05-23 2006-06-16 Rhodia Elect & Catalysis Composes precurseurs d'aluminates d'alcalino-terreux ou de terre rare, leur procede de preparation et leur utilisation comme precurseur de luminophore notamment
CN100560688C (zh) * 2005-09-23 2009-11-18 大连路明发光科技股份有限公司 长余辉发光材料及其制造方法
WO2008061403A1 (fr) 2006-11-20 2008-05-29 Sichuan Sunfor Light Co., Ltd. Matière photoluminescente à longue émission rémanente coactivée contenant plusieurs métaux du groupe des terres rares

Also Published As

Publication number Publication date
HK1103302A1 (en) 2007-12-14
EP1900789A4 (en) 2009-09-09
EP1900789A1 (en) 2008-03-19
US7955523B2 (en) 2011-06-07
WO2007003102A1 (fr) 2007-01-11
CN100485013C (zh) 2009-05-06
DE602006018737D1 (de) 2011-01-20
ES2357275T3 (es) 2011-04-20
ATE491009T1 (de) 2010-12-15
EP1900789B1 (en) 2010-12-08
US20090014684A1 (en) 2009-01-15

Similar Documents

Publication Publication Date Title
EP2554629B1 (en) Method for producing sialon-based acid nitride phosphor, and sialon-based acid nitride phosphor
CN1062887C (zh) 长余辉磷光体及其制备方法
KR100816693B1 (ko) 형광체 및 이 형광체를 이용한 발광 기구
KR101168173B1 (ko) 형광체와 그 제조방법
CN1180052C (zh) 发光二极管用波长变换白光发光材料
CN1891783A (zh) 一种复合基质长余辉荧光材料及其制备方法
CN1908116A (zh) 蓝光无机发光材料及使用该材料的发光器件
CN1942553A (zh) 白色发光二极管
CN1775902A (zh) 一种碱土磷酸盐长余辉发光材料及制备方法
KR101215342B1 (ko) 사이알론 형광체, 그 제조방법 및 이를 이용한 발광소자 패키지
CN105331361B (zh) 一种β‑SiAlON∶Eu2+绿色荧光粉及其合成方法
CN101067082A (zh) 一种白光led用荧光粉及其制备方法
CN1117134C (zh) 长余辉无机发光材料的制备方法
CN1210370C (zh) 一种彩色等离子平板显示用蓝色荧光粉及其制造方法
JP6973716B2 (ja) 焼成型の蛍光材の製造方法
CN101747892A (zh) 一种白光led用红色荧光粉及其制备方法
CN101029227A (zh) 一种超细荧光粉的制造方法
KR101227647B1 (ko) 비가시 발광체 및 그 제조방법
JP3559449B2 (ja) 斜方晶系水酸化物蓄光体及びその製造法
CN1403533A (zh) 长余辉磷光材料及其制备方法
CN1212365C (zh) 一种人工合成的长余辉高亮度发光粉及其制备方法
CN1203208A (zh) 陶瓷发光材料及其制造工艺
KR101340034B1 (ko) 진공 자외선 여기용 녹색 형광체 및 이의 제조방법
CN1788069A (zh) 含有硅酸盐荧光性磷光体的发光装置
CN1727434A (zh) 硼酸钇钆铽稀土绿色荧光体及其制造方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C41 Transfer of patent application or patent right or utility model
TA01 Transfer of patent application right

Effective date of registration: 20070817

Address after: The new road in Chengdu city of Sichuan province high tech Zone No. 2

Applicant after: Sichuan Sunfor Lighting Co., Ltd.

Address before: No. 32, glorious North Road, Chengdu, Sichuan

Applicant before: Xinli Industrial Group Co., Ltd., Sichuan

REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1103302

Country of ref document: HK

C14 Grant of patent or utility model
GR01 Patent grant
REG Reference to a national code

Ref country code: HK

Ref legal event code: GR

Ref document number: 1103302

Country of ref document: HK

PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: Composite substrate long-afterglow fluorescent material, and its preparing method

Effective date of registration: 20100817

Granted publication date: 20090506

Pledgee: Chengdu hi tech credit Company limited by guarantee

Pledgor: Sichuan Sunfor Lighting Co., Ltd.

Registration number: 2010990000846

C56 Change in the name or address of the patentee
CP01 Change in the name or title of a patent holder

Address after: The new 611731 Chengdu Road, Sichuan province high tech Zone No. 2

Patentee after: Sichuan Sunfor Light Co., Ltd.

Address before: The new 611731 Chengdu Road, Sichuan province high tech Zone No. 2

Patentee before: Sichuan Sunfor Lighting Co., Ltd.

PLDC Enforcement, change and cancellation of contracts on pledge of patent right or utility model
PM01 Change of the registration of the contract for pledge of patent right

Change date: 20130516

Registration number: 2010990000846

Pledgee after: Chengdu high investment financing Company limited by guarantee

Pledgee before: Chengdu hi tech credit Company limited by guarantee

Change date: 20130516

Registration number: 2010990000846

Pledgor after: Sichuan Sunfor Light Co., Ltd.

Pledgor before: Sichuan Sunfor Lighting Co., Ltd.

PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20140313

Granted publication date: 20090506

Pledgee: Chengdu high investment financing Company limited by guarantee

Pledgor: Sichuan Sunfor Light Co., Ltd.

Registration number: 2010990000846

PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: Composite substrate long-afterglow fluorescent material, and its preparing method

Effective date of registration: 20140313

Granted publication date: 20090506

Pledgee: Chengdu high investment financing Company limited by guarantee

Pledgor: Sichuan Sunfor Light Co., Ltd.

Registration number: 2014990000156

PLDC Enforcement, change and cancellation of contracts on pledge of patent right or utility model
PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20151102

Granted publication date: 20090506

Pledgee: Chengdu high investment financing Company limited by guarantee

Pledgor: Sichuan Sunfor Light Co., Ltd.

Registration number: 2014990000156

PLDC Enforcement, change and cancellation of contracts on pledge of patent right or utility model