CN1275153A - 发光材料的涂覆方法 - Google Patents

发光材料的涂覆方法 Download PDF

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CN1275153A
CN1275153A CN99801332.3A CN99801332A CN1275153A CN 1275153 A CN1275153 A CN 1275153A CN 99801332 A CN99801332 A CN 99801332A CN 1275153 A CN1275153 A CN 1275153A
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luminescent material
luminescent
discharge lamp
aqeous suspension
sequestering agent
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CN1218013C (zh
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T·于斯特尔
J·梅里克希
H·尼科尔
C·R·隆达
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Koninklijke Philips NV
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    • 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
    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
    • C09K11/592—Chalcogenides
    • C09K11/595—Chalcogenides with zinc or cadmium
    • 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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/666—Aluminates; Silicates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/38—Devices for influencing the colour or wavelength of the light
    • H01J61/42—Devices for influencing the colour or wavelength of the light by transforming the wavelength of the light by luminescence
    • H01J61/44—Devices characterised by the luminescent material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/38—Devices for influencing the colour or wavelength of the light
    • H01J61/42—Devices for influencing the colour or wavelength of the light by transforming the wavelength of the light by luminescence
    • H01J61/46—Devices characterised by the binder or other non-luminescent constituent of the luminescent material, e.g. for obtaining desired pouring or drying properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Vessels And Coating Films For Discharge Lamps (AREA)
  • Formation Of Various Coating Films On Cathode Ray Tubes And Lamps (AREA)

Abstract

本发明涉及用M2O3金属氧化物层涂覆发光材料的方法,其中金属M选自Y、Al和La。根据本发明,向发光材料的悬浮液中加入M与有机螯合剂的配合物的水溶液,此后分离、干燥并烧制发光材料。

Description

发光材料的涂覆方法
本发明涉及用M2O3金属氧化物层涂覆发光材料的方法，所述金属M选自Y、Al和La，其中通过从水溶液均质沉淀方式将M的化合物沉积在该发光材料上。
本发明还涉及经此方法获得发光材料，并涉及装有发光屏的放电灯，该发光屏含此发光材料。
WO 96/05265公开了如第一段所述的方法。被涂覆的发光材料在灯具生产过程中使用的水性浆料中显示较高的稳定性，以及一种改良的光输出连续性。现有技术的缺点之一是许多发光材料(例如，有硅酸盐主晶格的材料)在较低pH值发生均质沉淀时易于水解。另外，还经发现，在水中不水解的其它发光材料例如反射率和量子效率的光学性能受到低pH值的伤害。
本发明的目的是提供靠从水溶液中均质沉淀，使金属氧化物涂覆发光材料的方法，其中从很大程度上防止了发光材料水解和其光学性能劣化。
按照本发明，如第一段中所述的方法适于此目的，其特征在于，依次地，制备发光材料水悬浮液，向该水悬浮液中添加含有M与有机螯合剂的配合物的水溶液，从该水悬浮液中分离出该发光材料并进行干燥和加热。
已经发现，有机螯合剂阻止了M(OH)3的沉淀。其结果是，能够在较高pH值下发生均质沉淀。因此，强烈抑制了发光材料的水解和劣化。
用乙二胺、三吡唑基硼酸盐、二甘醇二甲醚、苯甲酸、冠醚、多磷酸盐和三环辛亚胺(triazacyclononane)作为有机螯合剂，已取得了良好的结果。尤其是用乙二胺四乙酸盐取得了更好的结果。
水悬浮液的pH值范围为8～10以及水溶液的pH值范围为6.5～7.5的情形下，也已取得良好结果。依靠本发明方法所获得的发光材料的精细粒状涂层一般由直径小于30纳米的球形Me2O3纳米粒子的薄层组成。用扫描电子显微镜或透射电子显微镜分析可以将此涂层与依靠CVD施加的涂层区分开来。此涂层的性能还通过肉眼可观察到的无机发光材料(phosphor)的特性得到体现，例如与CVD方法涂覆的涂层相比，由于表面更清洁使散射更高而导致略有增强的光输出。
本发明的方法尤其适于涂覆具有硅酸盐主晶格(silicate host lattice)的发光材料，因为这些发光材料在较低pH值的水溶液中非常容易水解。特别是已经证实，此方法非常适于用La2O3涂覆以铅活化的BaSi2O5，以铝活化的(Ba，Sr)2MgSi2O7和以锰活化的Zn2SiO4。
已发现，按照本发明方法涂覆的发光材料非常适用于放电灯的发光屏，特别是低压汞放电灯的发光屏。
现在将通过描述3个实施方案来举例说明本发明。
第一个实施方案中，用La2O3涂覆用铅活化的BaSi2O5(BSP)。向250毫克La2O3溶于50毫升软化水所成的溶液中加入125毫克乙二胺四乙酸盐(EDTA)。加入Ba(OH)2将此溶液的pH值调节到大约7。
将Ba(OH)2加入另一50毫升的软化水中，直至pH值为大约9.5。此后，向此溶液中加入10克BSP。将LA(EDTA)溶液滴加到BSP悬浮液中。在向BSP悬浮液中加入全部LA(EDTA)溶液后，再次加入Ba(OH)2将该悬浮液的pH值调节到大约9.5。然后搅拌该悬浮液2小时，并且接着过滤分离涂覆的BSP。最后，用碱性水洗涤此无机发光材料，在80℃下干燥并于900℃烧制2小时。涂覆的BSP的发射光谱与未涂覆的BSP的基本一致(λmax＝350nm；FVMM＝38nm)。254纳米和350纳米辐射的反射系数也几乎一致(未涂覆的BSP分别为20％和96％，涂覆的BSP分别为19％和95％)。然而，令人惊讶的是，发现涂覆的BSP的254纳米辐射的量子效率比未涂覆的BSP的高6％(分别为94％和88％)。
第二个实施方案中，用La2O3涂覆用铅活化的(Ba，Sr)2MgSi2O7(SMS)。所用的涂覆方法与此前所述BSP的涂覆方法一致，但用Sr(OH)2代替Ba(OH)2。涂覆和未涂覆的SMS的发射光谱基本一致(λmax＝360nm：FVMM＝60nm)。发现涂覆和未涂覆的SMS的254纳米辐射的量子效率为75％。未涂覆的SMS的254纳米和350纳米辐射的反射系数分别为8％和96％，涂覆的SMS的分别为10％和95％。
第三个实施方案中，用La2O3涂覆用锰活化的Zn2SiO4(ZSM)。所用的涂覆方法与此前所述BSP的涂覆方法一致，但用NaOH代替Ba(OH)2。涂覆和未涂覆的ZSM的发射光谱基本一致(λmax＝520nm；FVMM＝41nm)。发现涂覆和未涂覆的ZSM的量子效率分别为79％和80％。未涂覆的ZS和涂覆的ZSM的254纳米辐射的反射系数分别为94％和93％。

Claims (13)

1.一种用M2O3金属氧化物层涂覆发光材料的方法，其中金属M选自Y、Al和La，其中M的化合物通过均质沉淀沉积在该发光材料上，其特征在于，依次地，制备发光材料水悬浮液，向该水悬浮液中添加含有M与有机螯合剂的配合物的水溶液，从该水悬浮液中分离出该发光材料并进行干燥和加热。
2.按照权利要求1的方法，其中该有机螯合剂选自乙二胺、三吡唑基硼酸盐、二甘醇二甲醚、苯甲酸、冠醚、多磷酸盐和三环辛亚胺及乙二胺四乙酸盐。
3.如权利要求2中所述的方法，其中有机螯合剂为乙二胺四乙酸盐。
4.如权利要求1、2或3中所述的方法，其中该水悬浮液的pH值在8～10的范围内。
5.如前述权利要求中一项或多项所述的方法，其中该水溶液的pH值在6.5～7.5的范围内。
6.用M2O3金属氧化物层涂覆的发光材料，其中金属M选自Y、Al和La，该材料按照前述权利要求中一项或多项所述的方法获得。
7.按照权利要求6的发光材料，含有硅酸盐主晶格。
8.按照权利要求7的发光材料，含有用铅活化的BaSi2O5。
9.按照权利要求7的发光材料，含有用铅活化的(Ba，Sr)2MgSi2O7。
10.按照权利要求7的发光材料，含有用锰活化的Zn2SiO4。
11.按照权利要求6、7、8、9或10的发光材料，其中M为La。
12.装有发光屏的放电灯，该发光屏包含按照权利要求6～11一项或多项的发光材料。
13.按照权利要求12的放电灯，其中该放电灯为低压汞放电灯。
CN99801332.3A 1998-08-25 1999-08-23 发光材料的涂覆方法 Expired - Fee Related CN1218013C (zh)

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Cited By (1)

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CN1295297C (zh) * 2005-02-25 2007-01-17 东南大学 氧化铝包膜荧光粉及其膜包覆方法

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US6761971B2 (en) * 2001-09-26 2004-07-13 Osram Sylvania Inc. Protective spinel coating for aluminate phosphors
DE102004063217A1 (de) * 2004-12-29 2006-07-13 Giesecke & Devrient Gmbh Sicherheitsmerkmal für Wertdokumente
JP5850539B2 (ja) * 2010-07-13 2016-02-03 コーニンクレッカ フィリップス エヌ ヴェＫｏｎｉｎｋｌｉｊｋｅ Ｐｈｉｌｉｐｓ Ｎ．Ｖ． 放電ランプ、使用方法及びシステム
CN103275708B (zh) * 2013-02-28 2016-06-15 福建省长汀金龙稀土有限公司 一种灯用bam荧光粉的表面包膜方法

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EP1047750A1 (en) 2000-11-02
US6833160B2 (en) 2004-12-21
WO2000011104A1 (en) 2000-03-02
CN1218013C (zh) 2005-09-07
US6472811B1 (en) 2002-10-29
EP1047750B1 (en) 2005-04-06
DE69924601T2 (de) 2006-03-02
JP2002523551A (ja) 2002-07-30
US20020127329A1 (en) 2002-09-12

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