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WO1999050372A1 - Phosphores a longue remanence photoluminescents - Google Patents

Phosphores a longue remanence photoluminescents Download PDF

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Publication number
WO1999050372A1
WO1999050372A1 PCT/CN1998/000051 CN9800051W WO9950372A1 WO 1999050372 A1 WO1999050372 A1 WO 1999050372A1 CN 9800051 W CN9800051 W CN 9800051W WO 9950372 A1 WO9950372 A1 WO 9950372A1
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WO
WIPO (PCT)
Prior art keywords
phosphors
alkaline earth
long afterglow
activator
photoluminescent
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.)
Ceased
Application number
PCT/CN1998/000051
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English (en)
Inventor
Chunxiang Fang
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Individual
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Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to PCT/CN1998/000051 priority Critical patent/WO1999050372A1/fr
Priority to AU64938/98A priority patent/AU6493898A/en
Publication of WO1999050372A1 publication Critical patent/WO1999050372A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09K11/7797—Borates
    • 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
    • C09K11/7792—Aluminates

Definitions

  • This invention relates to photoluminescent long afterglow phosphors, particularly to long afterglow phosphors comp ⁇ sed of alkaline earth metal aluminates activated by rareearth and enhanced by oxygen vacanc) , and a method of making such long afterglow phosphors.
  • Phosphor is a substance that produces luminescence after absorbing radiant energy or other types of energy. Phosphorescence is distinguished from fluorescence in that it continues even after the radiation causing it has ceased. The luminescence is caused by electrons that are excited by the radiation and trapped in potential troughs, from which they are freed by the thermal motion within the crystal. As they fall back to a lower energy level, they emit energy in the form of light.
  • Phosphors with a long afterglow such as zinc sulfides are well known and have been in application for decades.
  • zinc sulfide phosphors have their inherent defects: chemical instability, quick declme of the luminosity, limited brightness and graying effects due to exposure to UV light m the presence of moisture.
  • radioactive elements were added. As the health hazard became apparent, radioactive materials were no longer allowed to be added to phosphors and replacement was needed for applications where longer and brighter phosphoresce is called for.
  • rare-earth activated alkaline earth metal aluminate phosphors become the natural target of research interest.
  • alkaline earth metal aluminate phosphors showed remarkable improvements in afterglow intensity, afterglow time and chemical stability as compared with the zinc sulfide type of phosphors.
  • the present inventor takes due note of these improvements and he has taken a new approach.
  • oxygen vacancies in ceramics may possibly change the crystal structure, physical and chemical properties.
  • the present inventor has conducted various experiments on the effect of oxygen vacancies on the physical, chemical and optical properties of rare earth activated alkaline earth phosphors and discovered that the oxygen vacancies can improve the phosphorescence without jeopardizing the chemical stability and photo-resistance of rare earth activated alkaline earth aluminate phosphors.
  • Crystallography has it that the luminescent properties of phosphors are the result of defects in crystals.
  • the approaches of the prior art are designed to add "impurities" and/or disrupt the stoichiometric ratios to create defects in crystals while the approach of this invention is to create defects b ⁇ taking some oxygen away, a process completely different from the p ⁇ or art
  • Rare earth activated alkaline earth aluminate phosphors of the prior art are all synthesized in a reducing atmosphere which is intended only to reduce europium to be divalent and thus too mild to create any oxygen vacancies.
  • all the defects in the prior art belong to the category of ' solid solution " which are caused by foreign matters.
  • the synthetic process is subject to a highly reducing atmosphere which not only reduces the europium to divalent, but also creates additional oxygen vacancies in the crystal structure. These defects are caused by a specific synthetic condition (physical process).
  • the desired amount of oxygen vacancies is achieved by manipulating the parameters of reductiveness of atmosphere, the flow rate of atmosphere, firing temperature and firing time. From the practical and economical pomt of view, the best atmosphere is the mixture of hydrogen and nitrogen in the ratio of three H 2 to one N 2 . This mixture can be easily obtained by decomposing ammonia, a gas readily available at a low price and liquidizable at a low pressure, thus making its storage, handling and transportation an easy task.
  • Table 1 shows the test result of an oxygen-enhanced phosphor in comparison with a phosphor with no oxygen vacancy. The tests are carried out according to DI 67510, part 1.
  • Fig 1 shows the comparam e afterglow intensity of oxygen enhanced phosphor and phosphor with no vacancy intensifiers measured according to DI 67510, part 1 .
  • Fig. 2 shows the spectral distribution of Sr - ⁇ O . ⁇ E, oxygen vacancy enhanced.
  • M is at least one alkaline earth selected from alkaline earth group consisting of Mg, Ca, Sr and Ba, and RE represents divalent europium and at least one additional lanthanide which serve as activator or co- activator(s).
  • M may be doped by divalent metal or metals consisting of Mn, Zr, Nb, Bi, Sn and Zn.
  • a green-yellow emitting long afterglow phosphor is prepared by starting from a mixture of the following materials of A.R. grade:
  • the materials are first fired between 800 and 1000°C to burn out carbon dioxide from strontium carbonate, water in boric acid and possibly some other impurities. They are fired again for about 4 hours around 1300°C in a highly reducing atmosphere of hydrogen-nitrogen gas (in the ratio of three H 2 to one N 2 ). The temperature, firing time and atmosphere are so adjusted as to obtain the desired level of oxygen vacancy. Thereafter, the resultant materials were cooled to room temperature, ground and sieved to obtain the alkaline earth aluminate phosphor.
  • the phosphor has a peak wavelength about 520 nm with very high initial brightness.
  • a blue-green emitting long afterglow phosphor can be prepared by starting from a mixture of the following materials of A.R. grade:
  • the materials are treated in the same way as Example 1.
  • the phosphor has a peak wavelength about 490 nm. Though the initial brightness is lower than the phosphor according to Example 1 , it decays at a much lower rate, thus luminance can last longer.
  • the two stage of firing can also be combined into one stage by firing in strongly reducing atmosphere around 1300°C for 4-6 hours.
  • the ' present invention can be employed in following applications:
  • this phosphors are good for both indoors and outdoors applications.

Landscapes

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

Abstract

L'invention concerne des phosphores à longue rémanence photoluminescents qui comprennent des aluminates alcalino-terreux activés par des éléments des terres rares et améliorés par des phosphores de formule M1-x(A11-yBy)2O4-x-z:RE dans laquelle M représente au moins un métal alcalino-terreux sélectionné dans le groupe alcalino-terreux constitué de Ca, Sr, Ba et Mg et où -1≤x≤0,90, 0≤y≤0,5, 0∫z∫2, et dans laquelle RE représente un europium et au moins un lanthanide servant d'activateur et de co-activateur(s).
PCT/CN1998/000051 1998-03-27 1998-03-27 Phosphores a longue remanence photoluminescents Ceased WO1999050372A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN1998/000051 WO1999050372A1 (fr) 1998-03-27 1998-03-27 Phosphores a longue remanence photoluminescents
AU64938/98A AU6493898A (en) 1998-03-27 1998-03-27 Photoluminescent long afterglow phosphors

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN1998/000051 WO1999050372A1 (fr) 1998-03-27 1998-03-27 Phosphores a longue remanence photoluminescents

Publications (1)

Publication Number Publication Date
WO1999050372A1 true WO1999050372A1 (fr) 1999-10-07

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN1998/000051 Ceased WO1999050372A1 (fr) 1998-03-27 1998-03-27 Phosphores a longue remanence photoluminescents

Country Status (2)

Country Link
AU (1) AU6493898A (fr)
WO (1) WO1999050372A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009076202A1 (fr) 2007-12-12 2009-06-18 General Electric Company Luminophore persistant
WO2012082675A1 (fr) * 2010-12-17 2012-06-21 General Electric Company Luminophore persistant émettant dans le blanc
US8333907B2 (en) 2007-01-17 2012-12-18 Utc Fire & Security Corporation Articles using persistent phosphors
US8545723B2 (en) 2007-12-12 2013-10-01 General Electric Company Persistent phosphor
CN104532385A (zh) * 2014-12-16 2015-04-22 上海洋帆实业有限公司 一种稀土发光纤维的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0622440A1 (fr) * 1993-04-28 1994-11-02 Nemoto & Co., Ltd. Matériau phosphorescent
CN1115779A (zh) * 1994-10-17 1996-01-31 肖志国 多离子激活的碱土铝酸盐光致长余辉发光材料及制造方法
JPH0873845A (ja) * 1994-06-29 1996-03-19 Nichia Chem Ind Ltd 残光性蛍光体
EP0710709A1 (fr) * 1994-11-01 1996-05-08 Nemoto & Co., Ltd. Matériau phosphorescent
WO1996032457A1 (fr) * 1995-04-14 1996-10-17 Kabushiki Kaisha Tokyo Kagaku Kenkyusho Composition a phosphorescence persistante

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0622440A1 (fr) * 1993-04-28 1994-11-02 Nemoto & Co., Ltd. Matériau phosphorescent
JPH0873845A (ja) * 1994-06-29 1996-03-19 Nichia Chem Ind Ltd 残光性蛍光体
CN1115779A (zh) * 1994-10-17 1996-01-31 肖志国 多离子激活的碱土铝酸盐光致长余辉发光材料及制造方法
EP0710709A1 (fr) * 1994-11-01 1996-05-08 Nemoto & Co., Ltd. Matériau phosphorescent
WO1996032457A1 (fr) * 1995-04-14 1996-10-17 Kabushiki Kaisha Tokyo Kagaku Kenkyusho Composition a phosphorescence persistante

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8333907B2 (en) 2007-01-17 2012-12-18 Utc Fire & Security Corporation Articles using persistent phosphors
WO2009076202A1 (fr) 2007-12-12 2009-06-18 General Electric Company Luminophore persistant
JP2011506684A (ja) * 2007-12-12 2011-03-03 ゼネラル・エレクトリック・カンパニイ 持続性蛍光体
US7959827B2 (en) 2007-12-12 2011-06-14 General Electric Company Persistent phosphor
US8545723B2 (en) 2007-12-12 2013-10-01 General Electric Company Persistent phosphor
WO2012082675A1 (fr) * 2010-12-17 2012-06-21 General Electric Company Luminophore persistant émettant dans le blanc
US8506843B2 (en) 2010-12-17 2013-08-13 General Electric Company White emitting persistent phosphor
CN103249804A (zh) * 2010-12-17 2013-08-14 通用电气公司 白色发光持久磷光体
CN103249804B (zh) * 2010-12-17 2015-06-17 通用电气公司 白色发光持久磷光体
CN104532385A (zh) * 2014-12-16 2015-04-22 上海洋帆实业有限公司 一种稀土发光纤维的制备方法

Also Published As

Publication number Publication date
AU6493898A (en) 1999-10-18

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