CN1298434A - 长余辉的发红光磷光体 - Google Patents
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
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- 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
- C09K11/7784—Chalcogenides
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Abstract
由一种二价稀土如铕活化的并基于硫化锶的发红色和橙红色光的长余辉磷光体可在一种卤化铵或三价稀土存在下加热制得。用卤化铵作熔剂,发红色光磷光体可模制成所需要的形状。利用卤化铵和粉末状氧化铝,发红光磷光体可直接作成粉末。在一种三价稀土盐存在下且在有硫和含碳原料存在下加热由一种稀土(Eu)活化的硫化锶,可制得细粒径的发红色光磷光体。
Description
本申请要求于1998年3月31日递交的临时申请60/079,959的申请日的优先权。
本申请涉及长余辉的发红光磷光体及其制备方法。更详细地说，本发明涉及由一种二价稀土活化的硫化锶基磷光体。
背景技术
能发出绿色、蓝绿色和蓝色的长余辉磷光体为人们所知已有一段时间。它们包括由稀土活化的硫化锌基磷光体和铝酸锶磷光体。
然而发橙色光和红色光的磷光体最近才有公布，而且它们在使用时有几个严重的缺陷。比如，Royce等人的US5650094，公布了稀土活化的二价钛酸盐磷光体，如CaTiO3或Ca-Zn-Mg-TiO3，但是它们只能发几分钟可见光。Lindmayer在US5043096中报道了一种以其稀土氧化物形式掺入三种稀土的且与一种卤化物如LiF混熔的硫化锶基磷光体。然而这种焙烧后的氟化物磷光体是被高度烧结的，必须粉碎以得到有用的粉末原料。然而粉碎使其发光能力减弱，因此该磷光体必须加热或退火以修补结晶缺陷。然而其发光能力无法完全恢复。据称，这些磷光体适用于油漆配方中的添加剂。
发红光磷光体是非常受欢迎的，因为它们在黑暗中，特别是发生停电事故时容易看见，比如用于漆黑剧院中的“出口”标志，标识消防设备，使其它安全装置及呼吸面具，消防栓等容易看见。上述安全装置和标志一直使用红色，因此它们对大多数人来说都很熟悉。另外，还可用于装饰和小物件上，比如玩具、汽车毂盖、体育用品等，红色也是一种非常受欢迎的鲜艳的颜色。
因此一直在寻求一种持久发红光的磷光体。
发明综述
我们已发现由二价铕活化和由一种卤化物如氯或溴，或由一种三价稀土共活化的硫化锶(SrS)焙烧后形成持久的发鲜红色光的磷光体。一种含卤化物的固体颗粒烧结的发红光磷光体在焙烧过程中可直接模制成所需要的形状，或者如果与三氧化二铝粉末混合，可直接制得磷光体粉末。用另外，把一种掺有任意三价稀土离子如钬(Ho)、铒(Er)、钕(Nd)等的SrS∶Eu放在硫蒸汽中焙烧，该硫蒸汽与含碳原料接触或从其上面流过，产生一种SC2气氛。这种方法也直接得到粉末。
附图的简要说明
此图是一张用于制取本发明中的粉末稀土磷光体的燃烧炉的简图。
发明详述
本发明的持久发红光磷光体选自于下列通式：SrS∶Eu∶X和SrS∶Eu∶M，其中，X可以是氯或溴，M是一种三价稀土，包括镨(Pr)、钕(Nd)、钐(Sm)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)和镥(Lu)。它们都由下文描述的几种方法制得。
长余辉磷光体指的是磷光体材料的光谱发射，这种材料在用光激发后，移走光源后，发射几个小时红色或橙红色光线。
硫化锶中掺入二价铕作为主活化剂。加入的铕(Eu)的量为硫化物的0.01到2.0原子百分比，优选地约为0.1原子百分比。次要的一种卤化物和稀土的共活化剂可以几种方式加入。
一种制备卤化物磷光体的方法，包括把卤化铵NH4X加入到铕活化的硫化锶中，其中X是氯或溴，然后在约900℃到1500℃的温度下加热，优选地约为1000℃到1300℃。在此高温下硫化锶通过下列方程式转变到氯化物中
由于氯化锶在约900℃熔融，在烧结之后，SrS∶Eu∶X形成烧结容器的形状。因此通过合理选择容器，可制得所需形状的固体磷光体。将模制的磷光体包裹以防潮，使用时固定到自行车、胶底运动鞋、夹克衫、墙壁等上以吸引注意力到由此标示的该物体上。这些磷光体具有持久的橙红色。
另外，SrS∶Eu原料在与卤化铵焙烧前可与重量百分比约为20％到60％的粉末状氧化铝混合。在这种情况下，氧化铝粉末延缓了磷光体的烧结，其产物仍旧是粉末原料。因此根本不需要会减弱磷光体发光能力的粉碎加工过程。最终得到的磷光体粉末可容易地加入一种基质中，如一种粉末或熔融塑料、纤维等中，这些塑料和纤维可把磷光体密封或包裹起来以抵御对其敏感的湿气。
在另一个实施方案中，可通过先制得SrS∶Eu∶M，然后把该磷光体在硫蒸汽存在下在约1200℃温度下焙烧制得这种长余辉的发红光磷光体，其中硫蒸汽从一种含碳原料上流过。硫蒸汽和碳在焙烧过程中形成一种低浓度的CS2气体。最终的原料没有烧结，但形成一种具有细粒径的长余辉磷光体。通过传统的硫化氢焙烧方式不能得到粉末状的磷光体。这种磷光体也具有浓的橙红色。
在一种方法中，SrS∶Eu∶M在浓缩的CS2气氛中焙烧，这种气氛在磷光体上留下一层碳的涂层。这层碳的涂层在硫蒸汽中焙烧可除去，而制得发红光的长余辉SrS∶Eu∶M磷光体。
在此实施方案中，碳酸锶在硝酸中溶解，得到硝酸锶溶液。相应的硫酸锶与硫酸铵沉积。不可溶的硫酸盐从溶液中析出与铕的硝酸盐溶液以及一种及一种以上三价稀土硝酸盐如Er(NO3)3形成悬浮液。把这种悬浮液烘干，在1000℃到1200℃温度下在将成形气氛中(N2和H2的混合气体)焙烧约三个小时，然后在约1000℃到1150℃温度下在硫化氢中焙烧三个小时制得一种硫化锶磷光体，如SrS∶Eu∶Er。其中稀土元素的每种元素重量含量为0.005-5％，优选为0.05-0.5％。
这种产品在如图1所示的一个半封闭体系中加热以制得长余辉磷光体。
参照图1，体系10由两个管12和14组成，每一个都一端开口，管12足够小以致于可插入管14中。把一种合适的磷光体，如上面所制备的SrSs∶Eu∶Er装在较小管12中，连同其中的元素硫，其量约为磷光体前体以及一种碳原料如糖碳的2-10重量％，。把管12和14组装在一起，放置在一个开炉16里，其中有惰性气体如氮气和氩气流过炉子且气流保持在箭头所指方向。组件通过燃烧炉盘管18的方式在约1150℃温度下加热。体系1能保持一个大气压的硫蒸汽，硫蒸汽可通过管12和14的开口端逸出。
冷却后就得到一种能持续发几个小时红光的长余辉粉末磷光体。通过在图1的炉子中加热，磷光体前体和硫制得的磷光体粉末粒径约为20到40微米。
一般而言，本发明中的发红光磷光体发射610nm的光线。这些磷光体要在红光到橙红光范围的日光中至少激发一小时才会发光。也可通过在近紫外光范围如365nm的光线获得激发。
由于磷光体在湿气存在下会降解，因此它们必须预定型，或涂上一层抗水渗透的透明涂层，比如一种合适的塑料涂层，或把磷光体粉末与一种抗水渗透的原料如一种油漆混合。
本发明的磷光体与各种耐湿的载体，如环氧、聚氨酯、玻璃纤维、粘胶和密封胶等相混合后可用作涂层。模制原料可以形成所需要形状，密封在一种耐湿的载体或涂层里直接使用。
这些磷光体的很多用途是显而易见的，包括用在安全标志、门把手、牌照、安全反光板、夜间用途、铁轨、楼梯、开关板、马桶座以及其它物件上，为了能在黑暗中看得见，除此以外，还用于体育用品，如球拍、球、铁环、自行车、高尔夫杆及棒球杆，粘贴到衣服上使在暗处可看见穿此衣服的人，用于玩具和小物品，用于如手提电话、BP机、照相机以及VCR和电视机遥控器这些装置的控制按钮或开关。这只是一些例子，对于那些本领域中熟练人员还有更多的用途显而易见的。
尽管上面参照具体实施方案对磷光体及其制备方法进行了阐述，但对于活化剂，前体盐及制备方法等方面所做出的那些本领域熟练人员显而易见的变化也将包括其中。本发明的范围仅受所附权利要求书限制。
Claims (12)
1、一种硫化锶的发红光磷光体，其含有一种二价活化剂且选自于通式为SrS∶Eu+2∶X和SrS∶Eu+2∶M的磷光体，其中X是一种为氯或溴的卤素，M是一种三价稀土。
2、如权利要求1所述的方法制得的发红光磷光体，其中所述磷光体通式为SrS∶Eu∶X。
3、如权利要求1所述的方法制得的发红光磷光体，其中所述磷光体通式为SrS∶Eu∶M。
4、如权利要求3所述的方法制得的一种发红光磷光体，其中M选自于镨、钕、钐、钆、铽、镝、钬、铒、铥和镥。
5、一种制备一种固体硫化锶基发红光磷光体的方法，其包括：把一种二价活化剂中加入硫化锶中，并在卤化铵存在下在约1100℃到1300℃温度下加热。
6、如权利要求5所述的方法，其中磷光体在一个模具里铸制成。
7、如权利要求5所述的方法，其中二价活化剂是铕。
8、一种制备粉末状硫化锶基发红光磷光体，其包括：把硫化锶和一种二价活化剂与粉末状氧化铝混合，并在卤化铵存在下在约1200℃温度下加热。
9、如权利要求8所述的方法，其中活化剂是铕。
10、一种制备硫化锶基发红光磷光体的方法，其包括：把二价铕和一种三价稀土加入硫化锶粉末中，并在硫和含碳原料存在下在900℃到1500℃温度下焙烧。
11、如权利要求10所述的方法，其中三价稀土的用量约为硫化锶的0.01-2原子百分比。
12、如权利要求10所述的方法，其中三价稀土从镨、钕、钐、钆、铽、镝、钬、铒、铥和镥。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
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| US7995998P | 1998-03-31 | 1998-03-31 | |
| US60/079,959 | 1998-03-31 | ||
| US09/098,221 | 1998-06-16 | ||
| US09/098,221 US6071432A (en) | 1998-03-31 | 1998-06-16 | Long persistence red phosphors |
Publications (1)
| Publication Number | Publication Date |
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| CN1298434A true CN1298434A (zh) | 2001-06-06 |
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| CN99805249A Pending CN1298434A (zh) | 1998-03-31 | 1999-03-31 | 长余辉的发红光磷光体 |
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| US (1) | US6071432A (zh) |
| EP (1) | EP1070106A4 (zh) |
| JP (1) | JP2002510743A (zh) |
| KR (1) | KR20010042358A (zh) |
| CN (1) | CN1298434A (zh) |
| WO (1) | WO1999051703A1 (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713601A (zh) * | 2016-03-31 | 2016-06-29 | 华南理工大学 | 一种硫化物近红外长余辉发光材料及其制备方法和应用 |
| CN106398685A (zh) * | 2016-09-05 | 2017-02-15 | 大连工业大学 | 一种光致发光复合材料及其制备方法 |
| US11400468B2 (en) | 2018-12-25 | 2022-08-02 | Jiangsu University | Gas-liquid two-phase flow atomizing nozzle |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6419854B1 (en) * | 1998-06-16 | 2002-07-16 | Sarnoff Corporation | Long persistence red phosphors and method of making |
| US6351069B1 (en) * | 1999-02-18 | 2002-02-26 | Lumileds Lighting, U.S., Llc | Red-deficiency-compensating phosphor LED |
| US6680569B2 (en) | 1999-02-18 | 2004-01-20 | Lumileds Lighting U.S. Llc | Red-deficiency compensating phosphor light emitting device |
| US6379584B1 (en) * | 1999-03-24 | 2002-04-30 | Sarnoff Corporation | Long persistence alkaline earth sulfide phosphors |
| CA2393713A1 (en) * | 1999-12-07 | 2001-07-05 | Global Products Sales And Marketing, Llc | Long persistent phosphor incorporated within a non-settable material |
| AU4714801A (en) * | 1999-12-07 | 2001-06-18 | Global Products Sales And Marketing, Llc. | Long persistent phosphor incorporated within a settable material |
| AU4714701A (en) * | 1999-12-07 | 2001-06-18 | Global Products Sales And Marketing, Llc. | Long persistent phosphor incorporated within a fabric material |
| WO2003042327A1 (en) * | 2001-11-14 | 2003-05-22 | Sarnoff Corporation | Red photoluminescent phosphors |
| US6926972B2 (en) * | 2002-01-10 | 2005-08-09 | Basf Corporation | Method of providing an electroluminescent coating system for a vehicle and an electroluminescent coating system thereof |
| US20040087698A1 (en) * | 2002-10-15 | 2004-05-06 | Schott Corporation | Products incorporating luminescent sealants |
| US20030173540A1 (en) * | 2003-02-19 | 2003-09-18 | Mortz Bradford K | Long persistent phosphor incorporated within a settable material |
| US20030155553A1 (en) * | 2003-02-19 | 2003-08-21 | Mortz Bradford K. | Long persistent phosphor incorporated within a non-settable material |
| KR20060122836A (ko) * | 2003-10-07 | 2006-11-30 | 이화이어 테크놀로지 코포레이션 | 설파이드 박막 증착용 폴리설파이드 열 증기 소오스 |
| US20050179008A1 (en) * | 2004-02-18 | 2005-08-18 | Zhiguo Xiao | Light-storage self-luminescent glass and the process for producing the same |
| US8075801B2 (en) * | 2005-04-29 | 2011-12-13 | Defense Holdings, Inc. | Photoluminescent (PL) applications on moveable equipment |
| TWI435927B (zh) * | 2006-02-10 | 2014-05-01 | Mitsubishi Chem Corp | 螢光體及其製造方法，含螢光體之組成物，發光裝置，暨影像顯示裝置及照明裝置 |
| JP6103695B2 (ja) * | 2013-03-07 | 2017-03-29 | 学校法人日本大学 | 蛍光体 |
| CN103627387B (zh) * | 2013-12-23 | 2015-12-30 | 淮海工学院 | 高亮度超长红色长余辉发光材料及其制备方法 |
| EP4108736A1 (en) * | 2021-06-22 | 2022-12-28 | Karlsruher Institut für Technologie | Photonic markers enabling security marking, product identification, and material sorting using low frame rate cameras |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2979467A (en) * | 1958-06-30 | 1961-04-11 | Ibm | Infrared stimulable phosphors |
| US4857228A (en) * | 1984-04-24 | 1989-08-15 | Sunstone Inc. | Phosphors and methods of preparing the same |
| US4755324A (en) * | 1985-11-15 | 1988-07-05 | Quantex Corporation | Thermoluminescent material |
| US4818434A (en) * | 1985-11-15 | 1989-04-04 | Quantex Corporation | Thermoluminescent material including fusible salt |
| US5043096A (en) * | 1985-11-15 | 1991-08-27 | Quantex Corp. | Thermoluminescent material including lanthanum, europium and cerium dopants |
| US4725344A (en) * | 1986-06-20 | 1988-02-16 | Rca Corporation | Method of making electroluminescent phosphor films |
| EP0339895A1 (en) * | 1988-04-29 | 1989-11-02 | Sunstone, Inc. | Red and red-orange afterglow phosphors |
| US5650094A (en) * | 1995-06-06 | 1997-07-22 | Royce; Martin R. | Red emitting long decay phosphors |
-
1998
- 1998-06-16 US US09/098,221 patent/US6071432A/en not_active Expired - Fee Related
-
1999
- 1999-03-31 CN CN99805249A patent/CN1298434A/zh active Pending
- 1999-03-31 KR KR1020007010923A patent/KR20010042358A/ko not_active Application Discontinuation
- 1999-03-31 JP JP2000542417A patent/JP2002510743A/ja active Pending
- 1999-03-31 WO PCT/US1999/007083 patent/WO1999051703A1/en not_active Application Discontinuation
- 1999-03-31 EP EP99916227A patent/EP1070106A4/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713601A (zh) * | 2016-03-31 | 2016-06-29 | 华南理工大学 | 一种硫化物近红外长余辉发光材料及其制备方法和应用 |
| CN106398685A (zh) * | 2016-09-05 | 2017-02-15 | 大连工业大学 | 一种光致发光复合材料及其制备方法 |
| US11400468B2 (en) | 2018-12-25 | 2022-08-02 | Jiangsu University | Gas-liquid two-phase flow atomizing nozzle |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999051703A1 (en) | 1999-10-14 |
| US6071432A (en) | 2000-06-06 |
| EP1070106A1 (en) | 2001-01-24 |
| EP1070106A4 (en) | 2001-10-10 |
| JP2002510743A (ja) | 2002-04-09 |
| KR20010042358A (ko) | 2001-05-25 |
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