CN1112420C - Red phosphor powder for high pressure mercury lamp - Google Patents
Red phosphor powder for high pressure mercury lamp Download PDFInfo
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- CN1112420C CN1112420C CN98107675A CN98107675A CN1112420C CN 1112420 C CN1112420 C CN 1112420C CN 98107675 A CN98107675 A CN 98107675A CN 98107675 A CN98107675 A CN 98107675A CN 1112420 C CN1112420 C CN 1112420C
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- pressure mercury
- alkaline earth
- earth metal
- mercury lamp
- powder
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- 239000000843 powder Substances 0.000 title claims abstract description 18
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 16
- 239000012190 activator Substances 0.000 claims abstract description 5
- 229910000316 alkaline earth metal phosphate Inorganic materials 0.000 claims abstract description 3
- 230000004907 flux Effects 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 230000005284 excitation Effects 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052712 strontium Inorganic materials 0.000 abstract description 11
- 238000009877 rendering Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000001795 light effect Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- -1 (Sr Chemical compound 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- SYJBLFMEUQWNFD-UHFFFAOYSA-N magnesium strontium Chemical compound [Mg].[Sr] SYJBLFMEUQWNFD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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Abstract
一种高压汞灯用红色荧光粉，是碱土金属磷酸盐的改进，是由M3(PO4)2·nB2O3∶Ce∶Mn表示的一类化合物晶体粉末发光体，M可以是Ca、Sr或Ba中的一种或多种，B作为助熔剂，Ce、M为激活剂。本发明的发光体在200-300℃下有较常规发光体更好的光效和显色性。
A red fluorescent powder for high-pressure mercury lamps, which is an improvement of alkaline earth metal phosphate, and is a compound crystal powder luminescent body represented by M 3 (PO 4 ) 2 ·nB 2 O 3 : Ce: Mn, and M can be Ca One or more of , Sr or Ba, B as a flux, Ce, M as an activator. The luminous body of the invention has better light effect and color rendering than conventional luminous bodies at 200-300°C.
Description
本发明属于灯用发光材料技术领域。The invention belongs to the technical field of luminescent materials for lamps.
目前，国内外用于自镇流高压汞灯的荧光粉主要是以二价锡激活的磷酸锌、锶(镁)，即：(Sr，Zn)3(PO4)2∶Sn或(Sr，Mg)3(PO4)2∶Sn等。使用此种荧光粉的高压汞灯由于涂灯配制粉浆时需球磨80小时以上，破坏了荧光粉的发光性能。在工作温度300℃左右时，荧光粉产生猝灭，使汞灯的光效、显示性下降。At present, the phosphors used in self-ballasted high-pressure mercury lamps at home and abroad are mainly zinc phosphate and strontium (magnesium) activated by divalent tin, namely: (Sr, Zn) 3 (PO 4 ) 2 : Sn or (Sr, Mg ) 3 (PO 4 ) 2 : Sn, etc. The high-pressure mercury lamp using this fluorescent powder needs ball milling for more than 80 hours when coating the lamp and preparing the slurry, which destroys the luminescent performance of the fluorescent powder. When the working temperature is about 300°C, the phosphor is quenched, which reduces the light efficiency and display of the mercury lamp.
本发明的目的是通过锰、铈共激活碱土金属硼磷酸盐的应用，改进荧光粉(体)的发光性能和显色性。The purpose of the present invention is to improve the luminous performance and color rendering of the fluorescent powder (body) through the application of manganese and cerium co-activating alkaline earth metal borophosphate.
本发明长波紫外3650A激发下的荧光粉，是由下式表示的化合物，M3(PO4)2·nB2O3:Ce∶Mn。The phosphor powder excited by the long-wave ultraviolet 3650A of the present invention is a compound represented by the following formula, M 3 (PO 4 ) 2 ·nB 2 O 3 :Ce:Mn.
其中M是由选自Ca、Sr、Ba中的一种或全部金属元素合成的化合物制成的晶体粉末发光材料；Wherein M is a crystalline powder luminescent material made of a compound synthesized from one or all metal elements selected from Ca, Sr, Ba;
添加Al、Na、Li、K、Si、Cl、B等多种金属、非金属元素构成的M3(PO4)2·nB2O3∶Ce∶Mn晶体粉末发光材料；M 3 (PO 4 ) 2 ·nB 2 O 3 :Ce:Mn crystal powder luminescent material composed of Al, Na, Li, K, Si, Cl, B and other metal and non-metal elements;
激活剂Mn的加入量为相当于M表示的金属元素的0.001摩尔％至10摩尔％；The addition amount of the activator Mn is 0.001 mol% to 10 mol% of the metal element represented by M;
稀土激活剂Ce的加入量为相当于M表示的金属元素的0.001摩尔％至10摩尔％；The amount of the rare earth activator Ce is equivalent to 0.001 mol% to 10 mol% of the metal element represented by M;
作为助熔剂加入的1-10％重量的硼酸、氯化物如Na、K、Li、NH4等的氯化物。1-10% by weight of boric acid, chlorides such as chlorides of Na, K, Li, NH 4 etc. added as flux.
本发明所述的由M3(PO4)2·nB2O3∶Ce∶Mn表示的荧光粉其制备方法如下述：The preparation method of the fluorescent powder represented by M 3 (PO 4 ) 2 ·nB 2 O 3 : Ce: Mn in the present invention is as follows:
1、称取计算量的各组分氧化物或盐类；1. Weigh the calculated amount of oxides or salts of each component;
2、均匀混合后经研磨放入Al2O3坩埚中1000℃空气中烧结1小时；2. After uniform mixing, put it into an Al 2 O 3 crucible and sinter in air at 1000°C for 1 hour after grinding;
3、取出冷却后，研细装入Al2O3坩埚中；3. After taking it out and cooling it, grind it finely and put it into an Al 2 O 3 crucible;
4、在物料上加入定量的活性碳粒后，加盖入炉1160℃恒温1-1.5小时；4. After adding a certain amount of activated carbon particles to the material, cover it and put it into the furnace at 1160 ° C for 1-1.5 hours;
5、取出后冷却至室温得到白色固体，经粉碎过筛后即得本发明的荧光体。5. Take it out and cool to room temperature to obtain a white solid, which can be crushed and sieved to obtain the phosphor of the present invention.
本发明公开的以M3(PO4)2·nB2O3∶Ce∶Mn表示的化合物，M选自钙、锶、钡中至少一种以上金属元素，并添加了定量的氯化物(金属或非金属)构成的碱土金属磷酸盐荧光粉在3650A紫外线激发下发射6300A波长的红色光，由于制浆时仅球磨10小时，用在汞灯上在300℃左右时比(Sr，Zn)3(PO4)2∶Sn或(Sr，Mg)3(PO4)2∶Sn提高30％以上的发光强度，改善了灯的光效和显色性。In the compound represented by M 3 (PO 4 ) 2 ·nB 2 O 3 : Ce: Mn disclosed by the present invention, M is selected from at least one metal element in calcium, strontium and barium, and a certain amount of chloride (metal or non-metal) alkaline earth metal phosphate phosphor emits red light with a wavelength of 6300A under the excitation of 3650A ultraviolet rays. Since the pulping process is only ball milled for 10 hours, when used in a mercury lamp at about 300 ° C, the ratio (Sr, Zn) 3 (PO 4 ) 2 :Sn or (Sr, Mg) 3 (PO 4 ) 2 :Sn increases the luminous intensity by more than 30%, and improves the light efficiency and color rendering of the lamp.
附图1为本发明荧光粉与(Sr，Zn)3(PO4)2∶Sn荧光粉(常规)相对发光强度与时间关系的曲线。Accompanying drawing 1 is the curve of relative luminous intensity versus time of the phosphor powder of the present invention and (Sr, Zn) 3 (PO 4 ) 2 : Sn phosphor powder (conventional).
从图中可见，本发明荧光粉在高于250℃发光强度非旦不下降反而呈上升趋势，在200-300℃有相当于室温下2倍的发光强度，而低压汞灯恰恰是工作在300℃左右。It can be seen from the figure that the luminous intensity of the phosphor powder of the present invention does not decrease but rises when it is higher than 250°C, and has a luminous intensity equivalent to twice that at room temperature at 200-300°C, while the low-pressure mercury lamp works at 300°C. ℃ or so.
下表为本发明荧光体与(Sr，Zn)3(PO4)2∶Sr荧光体温度特性对比表，从表中可见本发明荧光体在300℃以上相对亮度不下降，反而上升。The following table is a comparison table of the temperature characteristics of the phosphor of the present invention and (Sr, Zn) 3 (PO 4 ) 2 :Sr phosphor. It can be seen from the table that the relative brightness of the phosphor of the present invention does not decrease above 300°C, but increases instead.
在使用于自镇流高压汞灯(125W)时，本发明荧光粉M3(PO4)2·nB2O3∶Ce∶Mn经涂灯后测得的显色指数为Ra＝53.7，而(Sr，Zn)3(PO4)2∶Sn或(Sr，Mg)3(PO4)2∶Sn经涂灯后测得的显色指数为Ra＝40。When used in a self-ballasted high-pressure mercury lamp (125W), the color rendering index of the phosphor powder M 3 (PO 4 ) 2 ·nB 2 O 3 : Ce: Mn of the present invention measured after being coated with the lamp is Ra=53.7, while The color rendering index of (Sr, Zn) 3 (PO 4 ) 2 :Sn or (Sr, Mg) 3 (PO 4 ) 2 :Sn measured after being coated with a lamp is Ra=40.
本发明荧光体M3(PO4)2·nB2O3∶Ce∶Mn温度特性
本发明实施例如下：Embodiments of the present invention are as follows:
实施例1：Example 1:
按下列重量称取物料：Weigh the material by the following weights:
SrCO3 73.8克SrCO 3 73.8 g
CaCO3 41.0克CaCO 3 41.0 g
(NH4)2HPO4 105.6克(NH 4 ) 2 HPO 4 105.6 g
CeO 8.66克CeO 8.66 grams
MnCO3 3.44克MnCO 3 3.44 g
H3BO4 12.4克 H3BO4 12.4 g
NH4Cl 35克NH 4 Cl 35 g
将上述物料经均匀混合研磨后，装入Al2O3坩埚中1000℃空气中烧结1小时，取出冷却后研细装入Al2O3坩埚中，在物料上加定量的活性碳粒后加盖入炉1160℃恒温1-1.5小时，取出后冷却至室温即得到白色固体发光物质，经粉碎，过筛后得到M3(PO4)2·nB2O3∶Ce∶Mn白色结晶发光粉末。After the above materials are uniformly mixed and ground, put them into an Al 2 O 3 crucible and sinter in air at 1000°C for 1 hour, take them out and cool them, grind them finely and put them into an Al 2 O 3 crucible, add a certain amount of activated carbon particles on the materials and then add Cover it in the furnace at 1160°C for 1-1.5 hours, take it out and cool it to room temperature to obtain a white solid luminescent substance, which can be crushed and sieved to obtain M 3 (PO 4 ) 2 ·nB 2 O 3 :Ce:Mn white crystalline luminescent powder .
实施例2：Example 2:
物料组成为：The material composition is:
SrCO3 73.8克SrCO 3 73.8 g
BaCO3 81.29克BaCO 3 81.29 g
(NH4)2HPO4 105.6克(NH 4 ) 2 HPO 4 105.6 g
CeO 8.66克CeO 8.66 grams
MnCO3 3.44克MnCO 3 3.44 g
H3BO4 12.4克 H3BO4 12.4 g
NH4Cl 35克NH 4 Cl 35 g
烧制步骤条件同实施例1Firing step condition is the same as embodiment 1
实施例3：Example 3:
物料组成为：The material composition is:
SrCO3 73.8克SrCO 3 73.8 g
CaCO3 30克CaCO 3 30 g
BaCO3 23克BaCO 3 23 g
(NH4)2HPO4 105.6克(NH 4 ) 2 HPO 4 105.6 g
CeO 8.66克CeO 8.66 grams
MnCO3 3.44克MnCO 3 3.44 g
H3BO4 12.4克 H3BO4 12.4 g
NH4Cl 35克NH 4 Cl 35 g
烧制步骤条件同实施例1Firing step condition is the same as embodiment 1
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98107675A CN1112420C (en) | 1998-04-24 | 1998-04-24 | Red phosphor powder for high pressure mercury lamp |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98107675A CN1112420C (en) | 1998-04-24 | 1998-04-24 | Red phosphor powder for high pressure mercury lamp |
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| Publication Number | Publication Date |
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| CN1233642A CN1233642A (en) | 1999-11-03 |
| CN1112420C true CN1112420C (en) | 2003-06-25 |
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| CN98107675A Expired - Fee Related CN1112420C (en) | 1998-04-24 | 1998-04-24 | Red phosphor powder for high pressure mercury lamp |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7056451B2 (en) * | 2004-01-21 | 2006-06-06 | General Electric Company | Phosphors containing boron and rare-earth metals, and light sources incorporating the same |
| CN100356503C (en) * | 2004-08-06 | 2007-12-19 | 于首成 | Electronic energy-saving health-care fluoresent lamp |
| CN101649200B (en) * | 2009-09-03 | 2014-05-28 | 常熟市江南荧光材料有限公司 | Synthesis method of luminescent material for insect-killing trapping lamp |
| CN106905967B (en) * | 2017-02-20 | 2019-04-09 | 中国计量大学 | A kind of borophosphate green phosphor and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152018A (en) * | 1995-07-17 | 1997-06-18 | 北京市丰台区宏业涂装辅料厂 | Long-persistence and high-brightness luminous material and its prepn |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1152018A (en) * | 1995-07-17 | 1997-06-18 | 北京市丰台区宏业涂装辅料厂 | Long-persistence and high-brightness luminous material and its prepn |
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