CN1117135C - Long-afterglow blue fluorescent body - Google Patents
Long-afterglow blue fluorescent body Download PDFInfo
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- CN1117135C CN1117135C CN 99100846 CN99100846A CN1117135C CN 1117135 C CN1117135 C CN 1117135C CN 99100846 CN99100846 CN 99100846 CN 99100846 A CN99100846 A CN 99100846A CN 1117135 C CN1117135 C CN 1117135C
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- China
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- long
- fluorescent body
- afterglow fluorescent
- afterglow
- activator
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Abstract
The present invention provides a blue long-afterglow fluophor and a manufacture method thereof. The chemical structural formula of the fluophor is MAl12O19, wherein M is a metal element selected from the mixture of Ca, Mg, Sr, Ba and Zn, and more than 2 elements in the lanthanide can be added as activating agents and coactivating agents.
Description
The present invention relates to a kind of fluor, particularly relates to a kind of long-afterglow blue fluorescent body.
After long-afterglow fluorescent body leaves light source, can be luminous in considerable time, as this long afterglow luminous property fluor, that has known has a CaS:Bi (sending purplish blue coloured light), CaSrS:Bi (coloured light turns blue), ZnS:Cu (glow green), ZnCdS:Cu (jaundice look-orange-colored light) sulfides fluor, sulphide phosphor can prepare twinkler (the Luminescent Materials of the whole visible-range of covering from the blue light to ruddiness; KarlA.Franz, Wolfgang G.Kehr.Alfred Siggel, J ü rgen Wielzoreck, Germany (Chap.1)), we can claim that they are first-generation long-afterglow fluorescent body.The limitation of this class fluor is that chemical property is all unstable, and photostabilization is poor, crosses the UV radiation at the malaria back warp and is decomposed and lost efficacy, and the material body colour blackening of Containing Sulfur zinc has zinc element to separate out; Fluorescent lifetime is short, and environment is had pollution, so this class fluorescent material uses out of doors and is subjected to great restriction.Simultaneously, because the easy deliquescence reaction of this class material produces hydrogen sulfide, the deleterious material of a kind of stench has also seriously limited their uses aspect family and indoor decorating.
S-generation fluor is with Eu
2+Deng rare earth ion is the aluminates system long after glow luminous material of activator, its minute subexpression MAl
2O
4Expression, M represents Ca, Mg, Ba, alkaline-earth metal such as Sr, Eu
2+, Dy
2+, Ce
2+Deng rare earth ion as activator and coactivator (Mater.Soveshch, Lyumin. (Kristallofostory) .21st Meeting Date 1973-16 Edited by:Fridman, S.A.Vses.Nauch-Issled.Inst.Lyuminoforov Osobo.Chrst.Veshchestv:Stavropol USSR.), compare with the metallic sulfide system, this s-generation fluor has characteristics (Liu Yingliang such as anti-UV radiation and luminosity height, the long non-toxic and non-radioactive of fluorescent lifetime, chemical property be stable, Li Yuan English, stone Chun-shan Mountain etc., Eu
2+Synthetic and the performance study of two kinds of new luminous hosts of activated, luminous journal, 1994,15 (1) 74-77.)。But the distinct disadvantage of this class long-afterglow fluorescent body is not water-fast and the soda acid aqueous solution, is easily lost efficacy by the slow decomposing oxidation of water.
In addition, present MAl
2O
4The type fluor all is a yellow-green colour, and the color that can provide is relatively more dull, can not satisfy the demand.
Therefore In view of the foregoing, the object of the present invention is to provide a kind of, more high brightness and more steady persistence time more stable, compare MAl than sulphide phosphor
2O
4The type fluor is more water-fast and the chemical property of acid-base solution Phosphorscent phosphor better, that fluor decay of afterglow speed is slower, time of persistence is longer.
The objective of the invention is to reach like this:
The invention provides a kind of long-afterglow fluorescent body, described fluor is to use MAl
12O
19The parent crystallization that the compound of expression is made, M is selected from least a above metallic element in calcium, magnesium, strontium, barium and the zinc, and, also contain europium and be selected from two or more at least element coactivators in lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium with containing as activator, the amount of described activator or coactivator is equivalent to the 0.001mol% to 15mol% of the metallic element represented with M, preferred 0.1mol% to 8mol%.
In one embodiment of the invention, provide a kind of Sr of using
0.95Ca
0.05Al
12O
19: Eu, the long-afterglow fluorescent body that Dy, Er represent.
In another embodiment of the invention, provide a kind of BaAl of using
12O
19: Eu, the long-afterglow fluorescent body that Nd, Er represent.
Described long-afterglow fluorescent body, use the ultraviolet ray and radiation of visible light of 200～450nm at normal temperatures after, send blue aura at the dark place.
The present invention further provides the method for the aforesaid long-afterglow fluorescent body of preparation, that is, contain the rare earth oxide of activator and coactivator element, carbonate and the Al of M by the stoichiometry uniform mixing
2O
3, with resulting mixture (H: N=95: 5～3: under nitrogen-hydrogen reduction atmosphere 1 (volume ratio)) in 1350～1500 ℃ of calcinings down.
Preferably, in above-mentioned mixture, also add boron-containing compound as fusing assistant; Preferred described boron-containing compound is selected from boric acid, boron oxide or alkaline earth borate, and its add-on is the 0.001mol%～15mol% of the metallic element represented of M, preferred 0.1mol%～8mol%.
Long afterglow luminous property fluor provided by the present invention can be used to be coated in the various products surface, can make water-borne coatings.Also can be mixed in plastics, rubber, or use in the enamel.Can be used for purposes such as timepiece dial, secure ID, artwork, porcelain tool, clothes, because it has high brightness, long twilight sunset, be again oxide type, chemical property is stable, anti-UV, have excellent water-resistance, so can on the basis of purposes in the past, expand use range.
Thus, another aspect of the present invention has provided the application of a kind of above-mentioned long-afterglow fluorescent body in preparation coating, particularly water-based.
Long-afterglow fluorescent body provided by the present invention has overcome problems of the prior art fully, and described fluor can provide as all looking luminescent coating or the printing ink of seeing in the night, especially is fit to make the coating of water-based, more meets environmental protection and health requirements.Below, to ZnS:Cu fluor, Mal
2O
4Type fluor and MAl of the present invention
12O
19The characteristics of type fluor compare:
ZnS：Cu MAl
2O
4 MAl
12O
19
Luminosity is low high
1 hour time of persistence is more than 12 hours more than 12 hours
Rate of decay speed is slower
Water resistance is good poor excellent
Anti-UV difference is excellent
By MAl more of the present invention
12O
19Every performance all be best.So its application than preceding two kinds more extensive.
MAl
12O
19The structure of structure fluor still belongs to hexagonal crystal etc., and this structure once was used for lamp phosphor very early, but has tangible steady persistence effect then never to see reported in literature under specific circumstances.
The luminous behavior of long-persistence luminous body is depended on the character of active ions itself to be subjected to the influence of surrounding environment simultaneously in essence.Eu
2+The ionic VISIBLE LIGHT EMISSION mainly comes from its 4f
65d to 4f
7Induced transition because the 5d electronics is in the not outer naked state of shielding, so be subjected to the strong influence of surrounding environment.Other rare earth ion such as Dy
3+, Tb
3+, Ce
2+And Sm
2+Also respectively with Eu
2+Produce coactivation.Make luminous intensity and time stronger longer, the intensity of while crystal field, covalent linkage and cationic size are to luminous all influential (Song Qingmei, Huang Jinfei, Wu Maojun, Chen Ji jumps, the synthetic and luminescence studies of strontium europium aluminate, luminous journal, 1991,12 (2) 144-149.)。
MAl of the present invention
12O
19The preparation method of structure fluor is the rare earth oxide that top grade is pure, carbonate and alkaline-earth metal Sr, Ca, Mg and Al
2O
3With the accurate weighing of stoichiometric ratio, ball milling evenly places electric furnace then in the ball milling cylinder, under nitrogen hydrogen reduction atmosphere (H: N=95: 5～3: 1), 1350～1500, general under 1400 ℃ temperature enure 3 hours, then cool to room temperature was pulverized 200 mesh sieves with sample.Obtain the fluor of blue light-emitting, resulting fluor has the luminosity height, and the rate of decay is slow, soaking-resistant does not decompose characteristics such as not influencing luminosity, anti-UV radiation.
Below exemplify example MAl of the present invention is described
12O
19Long-afterglow fluorescent body, but can not think limitation of the present invention.
Embodiment 1:Sr
0.95Ca
0.05Al
12O
19: Eu, Dy, the synthetic and characteristic of Er fluor
At the pure Strontium carbonate powder 69.8g (0.475mol) of top grade, lime carbonate 2.5g (0.025mol) and Al
2O
3Among the 102g (1mol), adding is as europium sesquioxide 0.88g (0.0025mol), coactivator dysprosium oxide 0.93g (0.0025mol), the Erbium trioxide 0.76g (0.0025mol) of activator europium, and then adding is as the boric acid 5g (0.08mol) of fusing assistant, after using the ball mill thorough mixing, this sample is put into electric furnace, under nitrogen-hydrogen reduction atmosphere, 1400 ℃ of calcinings 3 hours, then cool to room temperature is crossed 200 mesh sieves with the compound powder that obtains.
With the crystalline texture of D/max-RB type X-ray diffractometer parsing synthetic fluor, the result can see the fluor SrAl that obtains from the characteristic of diffraction peak
12O
19Hexagonal system structure: parameter a=b () C () α=β γ SrAl
12O
195.585 22.07 90 ℃ 120 ℃
The fluorescence emission spectrum emission peak that obtains with PELS-50B type fluorescence spectrophotometer is 410～425nm and 490nm.
Embodiment 2:BaAl
12O
19: Eu, Nd, the synthetic and characteristic of Er fluor
At top grade pure barium carbonate 98.5g (0.5mol) and Al
2O
3Among the 102g (1mol), adding is as europium sesquioxide 0.88g (0.0025mol), coactivator Neodymium trioxide 0.67g (0.0025mol) and the Erbium trioxide 0.76g (0.0025mol) of activator europium, and then adding is as the boric acid 5g (0.08mol) of fusing assistant, after using the ball mill thorough mixing, this sample is put into electric furnace, under nitrogen-hydrogen reduction atmosphere, 1400 ℃ of calcinings 3 hours, then cool to room temperature is crossed 200 mesh sieves with the compound powder that obtains.Obtain the fluor of blue light-emitting, emission peak is 440nm.
Embodiment 3: the preparation of water-borne coatings
The water-borne acrylic resin of solid content 25%, the dispersion agent MS-1 that accounts for gross weight 1%, the fluor of 30% embodiment 1 preparation, 3% anti-sedimentation agent M-5 were mixed 5 minutes in the high speed dispersion agent of 1000rpm, obtain uniform mixture, resulting mixture by 120 order silk screen filter, is obtained finished product.
Prepared finished product ADHESION OF PAINTS power and shock resistance meet GB1720-79 and GB1732-79 respectively.
Finished product deposited one month in water after, fluor luminous unaffected.
Claims (10)
1, a kind of long-afterglow fluorescent body is characterized in that, described fluor is to use MAl
12O
19The parent crystallization that the compound of expression is made, M is selected from least a above metallic element in calcium, magnesium, strontium, barium and the zinc, and, also contain europium and be selected from lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium two or more at least elements as coactivator as activator and containing, the amount of described activator or coactivator is equivalent to the 0.001mol% to 15mol% of the metallic element represented with M.
2, long-afterglow fluorescent body as claimed in claim 1 is characterized in that, the amount of described activator or coactivator is equivalent to the 0.1mol% to 8mol% of the metallic element represented with M.
3, long-afterglow fluorescent body as claimed in claim 1 or 2 is characterized in that, described long-afterglow fluorescent body is Sr
0.95Ca
0.05Al
12O
19: Eu, Dy, Er.
4, long-afterglow fluorescent body as claimed in claim 1 or 2 is characterized in that, described long-afterglow fluorescent body is BaAl
12O
19: Eu, Nd, Er.
5, long-afterglow fluorescent body as claimed in claim 1 or 2 is characterized in that, described long-afterglow fluorescent body sends blue aura at the dark place after using the ultraviolet ray and radiation of visible light of 200～450nm at normal temperatures.
6, preparation is characterized in that as the method for the long-afterglow fluorescent body of claim 1 or 2, contains the rare earth oxide of activator and coactivator element, carbonate and the Al of M by the stoichiometry uniform mixing
2O
3, be under nitrogen-hydrogen reduction atmosphere of 95: 5～3: 1 with resulting mixture in 1350～1500 ℃ of calcinings down in the volume ratio of hydrogen and nitrogen.
7, method as claimed in claim 6 is characterized in that, also adds the boron-containing compound as fusing assistant in described mixture.
8, method as claimed in claim 7 is characterized in that, described boron-containing compound is selected from boric acid, boron oxide or alkaline earth borate, and its add-on is the 0.001mol%～15mol% of the metallic element represented of M.
9, the application of long-afterglow fluorescent body as claimed in claim 1 or 2 in preparation coating.
10, application as claimed in claim 9 is characterized in that, described coating is water-borne coatings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99100846 CN1117135C (en) | 1999-02-25 | 1999-02-25 | Long-afterglow blue fluorescent body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99100846 CN1117135C (en) | 1999-02-25 | 1999-02-25 | Long-afterglow blue fluorescent body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1264727A CN1264727A (en) | 2000-08-30 |
| CN1117135C true CN1117135C (en) | 2003-08-06 |
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ID=5270218
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99100846 Expired - Fee Related CN1117135C (en) | 1999-02-25 | 1999-02-25 | Long-afterglow blue fluorescent body |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344715C (en) * | 2003-07-02 | 2007-10-24 | 张贵洲 | Aqueous environmental protection mark paint |
| DE102012021570A1 (en) | 2012-11-02 | 2014-05-22 | Merck Patent Gmbh | Eu-activated phosphors |
| CN103013507A (en) * | 2012-12-26 | 2013-04-03 | 广州有色金属研究院 | Ultrafine rare-earth aluminate long-persistence luminescent material and preparation method thereof |
| CN103468015A (en) * | 2013-08-08 | 2013-12-25 | 南通时瑞塑胶制品有限公司 | Fiber reinforced plastic grid with automatic luminescence function, and production process thereof |
| CN105925261B (en) * | 2016-05-10 | 2018-11-27 | 河北大学 | A kind of long-afterglow material, its application and the method for adjusting sunlight using it |
| CN107828412B (en) * | 2017-11-02 | 2018-12-04 | 宁波朗格照明电器有限公司 | A kind of blue long afterflow fluorescent powder and preparation method thereof |
| CN111423881B (en) * | 2020-04-28 | 2021-06-22 | 中国科学院长春应用化学研究所 | Cr (chromium)3+Doped near-infrared luminescent material and preparation method thereof |
-
1999
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| CN1264727A (en) | 2000-08-30 |
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| CB03 | Change of inventor or designer information |
Address after: Tsinghua University Beijing Huaye building 6 floor Applicant after: Beijing Qinghua Industry Development Institute Inventor after: Dai Youyuan Inventor after: Qiu Yong Inventor after: Zhu Dequan Inventor after: Dai Dongxiu Inventor after: Sun Haitao Address before: Beijing Beijing Tsinghua University Museum of works Applicant before: Yongchang Chemical Co., Ltd., Qinghua Univ. Beijing Inventor before: Chang Yaohui Inventor before: Qiu Yong Inventor before: Sun Haitao Inventor before: Zhu Dequan |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: BEIJING TSINGHUA YONGCHANG CHEMICAL PRODUCTS CO., LTD TO: TSINGHUA INDUSTRIAL R+D INSTITUTE, BEIJING |
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Granted publication date: 20030806 |