CN1163569C - Fluorescent material with ultra-long afterglow and its preparing process and application - Google Patents
Fluorescent material with ultra-long afterglow and its preparing process and application Download PDFInfo
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- CN1163569C CN1163569C CNB00102924XA CN00102924A CN1163569C CN 1163569 C CN1163569 C CN 1163569C CN B00102924X A CNB00102924X A CN B00102924XA CN 00102924 A CN00102924 A CN 00102924A CN 1163569 C CN1163569 C CN 1163569C
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Abstract
The present invention relates to ultralong persistence luminescent material, a preparing method thereof and application to paint preparation. The luminescent material has a general formula of (Me<II>O)3. M2<III>2O3. (M<IV>O2)3. xRO. yTR2O3, wherein Me<II> is selected from Mg, Ca, Sr and Zn, M<III> is selected from Al, V, Ga and B, M<IV> is selected from Si, Zr, Ti and Hf, R is selected from Eu, Sm, Yb and Sn, and TR is selected from La, Nd, Ce, Er, Ho, Y, Gd, Bi, Sc, Pr, Sb and Tb; 0.0001</=x</=1, and 0.0001</=y</=10.
Description
The present invention relates to phosphor, especially relate to and in a plurality of hours, continuing luminous fluorescent material behind the excitation light irradiation, or be referred to as to store up luminescent material, and preparation method and application.
First-generation long after glow luminous material is based on CaS.Bi or ZnS.Cu, and these material weathering resistancies and resistance to hydrolysis are relatively poor, so very fast meeting is decomposed in air.
The known luminescent material of the s-generation is the aluminate type, and its basic substance is MeO and Al
2O
3, wherein, Me is Ca, Sr, Ba.This system rare earth element co-activation, its inner redox reaction that takes place, as
, can under the situation of the concentration [Eu]=1～5% of europium, preserve luminous energy, excite luminous 10～40 hours of back in irradiation.But this s-generation luminophore has following deficiency:
-poor water resistance;
-too responsive to the spectrum of exciting light;
-responsive to envrionment temperature.
In addition, the preparation temperature of s-generation luminescent material is generally all greater than 1350 ℃, and will prepare under the reducing atmosphere of sealing, so improved the cost of product.What generally admit in the prior art is to add some light constituents, as B
2O
3, P
2O
5Deng not solving above-mentioned deficiency fully.
The objective of the invention is to overcome the deficiencies in the prior art, a kind of strong point that can keep all luminescent powders to possess be provided, possess the fluorescent material of the characteristic of overlength afterglow again, and preparation method thereof and in the application of preparation in the water-borne coatings.
In order to realize above-mentioned goal of the invention, one aspect of the present invention has provided a kind of novel fluorescent material, and its general formula is:
(Me
IIO)
3·M
III 2O
3·(M
IVO
2)
3·xRO·yTR
2O
3 [I]
Wherein,
Described Me
IIFor being selected from Mg, Ca, Sr, the element of one or more among the Zn;
Described M
IIIFor being selected from Al, V, Ga, the element of one or more among the B;
Described M
IVFor being selected from Si, Zr, Ti, the element of one or more among the Hf;
Described R is for being selected from Eu, Sm, Yb, the element of one or more among the Sn;
Described TR is for being selected from La, Nd, Ce, Er, Ho, Y, Gd, Bi, Sc, Pr, Sb, the element of one or more among the Tb;
X and y are mole number, and, 0.0001≤x≤1,0.0001≤y≤10.
In the general formula of above-mentioned fluorescent material with ultra-long afterglow, work as M
IVBe Zr, Si, M
IIIDuring for Al, the general formula of described fluorescent material is:
(Me
IIO)
3·2ZrO
2·Al
2O
3·SiO
2·xRO·yTR
2O
3 [II]。
And work as M
IVBe Si, M
IIIDuring for V, the general formula of described fluorescent material is:
(Me
IIO)
3·V
2O
3·(SiO
2)
3·xRO·yTR
2O
3 [III]。
The above-mentioned structure of matter is the cubic crystalline structure, lattice dimensions a=12.46 , and melt temperature is lower, is 1850 ℃.
The IIA family positively charged ion that contains heavy ion particle diameter and small ion particle diameter among fluorescent material provided by the present invention special points out to be to form, as Ca ion (1 ), Sr ion (1.18 ), Mg ion (0.72 ), these ions exist with the silicate form, have guaranteed the water tolerance of material.In preferred embodiments, Mg, the mol ratio of Ca and three kinds of elements of Sr is 1: 4: 5～1: 2: 7.
Another characteristics of fluorescent material provided by the present invention are to have reduced in a large number to appraise at the current rate and the concentration of permanent valency activation rare earth element (R and TR), can only account for 0.1～0.4% of gross weight ratio, that is to say, than the SrOAl of routine
2O
3The content of such rare earth element reduces 2～5 times in the type luminescent material.Simultaneously, the ratio between valence variation element R and the permanent valency element T R can change in very wide scope, from [R
+ 2] weight be 0.3% [R
+ 2]: [TR
+ 3]=1: 1 changes to weight percent [R
+ 2[the R of]=0.6% o'clock
+ 2]: [TR
+ 3]=3: 1.In preferred embodiments, aforesaid x is 1: 1～3: 1 with the ratio of y.
In the compound of general formula (II), smaller or equal to the ZrO of 0.5mol
2Can be by TiO
2Replace.As part ZrO
2By TiO
2During replacement, luminous meeting is moved to the shortwave direction.
Further also find, in the compound of general formula (II), smaller or equal to the SiO of 0.5mol
2Can be by GeO
2Replace.As part Si O
2Be replaced by GeO
2The time, can cause luminously moving to the long wave direction.
Also found in the compound of general formula (II), smaller or equal to the ZrO of 0.5mol
2Can be by HfO
2Replace.As part ZrO
2By HfO
2During replacement, then can excite storage lot of energy down at X ray or gamma-rays.
In order to obtain the fluorescent material of above-mentioned characteristic, another aspect of the present invention has provided a kind of method for preparing above-mentioned fluorescent material, and this method comprises, by oxide compound, the oxide compound of TR, the Me of stoichiometry uniform mixing R
IICarbonate and M
IIIAnd M
IVHypochlorite or oxide compound, at 1250～1360 ℃ down with CO and/or H
2Reduction.Wherein, described CO and H
2Be the CO that produces by carbon granules and raw material
2And H
2The O reaction is produced.
The material of the present invention that luminescent properties and energy storage capacity are all very high------overlength afterglow luminescent powder is to carry out synthetic well, requires as follows to purity of raw materials:
CaCO
3 99.99％ ZrOCl
2·8H
2O 99.985％
SrCO
3 99.99％ Eu
2O
3，Sm
2O
3，Yb
2O
3 99.99％
MgCO
3 99.95％ Gd
2O
3，Y
2O
3，Ho
2O
3，Er
2O
3 99.95％
Al
2O
3 99.99％
SiO
2 99.999％
Concrete preparation procedure comprises: by the metered proportions desired raw material of weighing, ground and mixed in detail packs 1500 or the corundum crucible of 2000ml into, and the gac of the some amount of packing in each crucible is used for producing H by following chemical reaction
2And CO:
In each crucible, cause reducing atmosphere thus, be used to finish following reaction:
Reducing atmosphere is by inner CO and the H that oneself generates of each crucible
2Cause, than at whole furnace chamber H
2Or NH
3Protect cheap many.
Fluorescent material provided by the present invention has superior performance, can store 10 in 3～16 hours
20Photon/cm
3Luminous energy; And, have excellent water tolerance, the aqueous solution of luminescent powder in addition under the situation of ebuillition of heated its pH value also remain unchanged.This class fluorescent material also has very high light stability and thermostability, and the highest heat-resisting interval can reach 350K～400K, and frequency factor is 10
10～10
12Second.Although add the ZrO of a little
2And HfO
2Can cause a little raising of luminescent powder cost, but the raising that has brought the luminescent powder performance thus, range of application further enlarges, as can be applicable to (1) road sign, bridge mark, shield, line of delimitation, pavement, lamppost etc.; (2) fire and emergent sign; (3) weaponry, ship's deck, harbour sign, oil well sign etc.; (4) special clothes.
Because material provided by the present invention is to X-ray, gamma-rays sensitivity, so material of the present invention also can be used for the sign of various goods, luggage, mail etc.; Utilize the enhanced water resistance of material of the present invention, and make exterior coating, paint of usefulness such as various buildingss etc.
Describe the present invention by the following examples in detail, but be not used for limiting the present invention.In the following embodiments, used raw material is the purity more than 99.9%.
Embodiment 1
Luminescent powder 1:(CaO)
3Al
2O
32ZrO
2SiO
20.02EuO0.005Y
2O
3
Mix 3mol CaCO
3, 2mol ZrOCl
28H
2O, 1mol SiO
2With 1mol Al
2O
3, 0.01mol Eu
2O
3, 0.005mol Y
2O
3, then with the abundant ground and mixed of ball mill, after the oven dry, pack into 2 liters corundum crucible of furnace charge, tamp to density be 1.2g/cm
3, add the activated carbon about 10g then in the crucible, build lid, add in the stove that is preheated to 500 ℃, with 10 ℃ of/minute intensifications, under 1320 ℃, kept 120 minutes then.Stove is cooled to 700 ℃ then, and the band material crucible cool to room temperature of taking-up with distilled water flushing crucible once, is separated twinkler in the crucible that takes out under ultra violet lamp with dark green and light green luminous component and atrament, obtain luminescent powder 1.
The crucible twinkler that takes out was put into ball mill grinding 2 hours, and the ratio between twinkler and the mill ball is 1: 3, measures diameter of particle then on specific equipment.For the first time exciting light is with the optical excitation of 200 luxs 5 minutes, enough luminous 16 hours of energy stored.
The water tolerance experiment is that the luminescent powder that makes is put into water, and measures this pH value of aqueous solution, and in 10 hours time, pH can maintain between the 6.6-7.0; And known aluminate type luminescent powder, as SrOAl
2O
3EuDy melts in water, and the pH value will reach 13, can dissolving in 1 hour.
Embodiment 2
Luminescent powder 2:(Ca
1.5Mg
0.5Sr) O
3Al
2O
32ZrO
2SiO
20.01EuO0.005Nd
2O
3Mix 1.5mol CaCO
3, 0.5mol MgCO
3, 1mol SrCO
3, 2mol ZrOCl
28H
2O, 1molSiO
2With 1mol Al
2O
3, 0.005mol Eu
2O
3, 0.005mol Nd
2O
3, mixture is through 2 hours ground and mixed, furnace charge pack into the silicon carbide crucible and the 8g gac of packing in crucible.Heated 3 hours, and made temperature reach 1350 ℃, under this temperature, kept 1 hour.
Treat that stove is chilled to 800 ℃, take out band material crucible and be cooled to room temperature,, and under ultra violet lamp, peel off atrament, obtain luminescent powder 2 furnace charge cancellation in 5 ℃ water.Levigate through disperseing then, cross 200 mesh sieves, after exciting through standard, the jaundice green glow, and, can in 2 hours, keep 40mcd/m
2Brightness.
Embodiment 3
Luminescent powder 3:(Ca
2Mg
0.4Sr
0.6) O
3Al
2O
32ZrO
2SiO
20.02EuO0.004Ho
2O
3Mix 2mol CaCO
3, 0.4mol MgCO
3, 0.6mol SrCO
3, 2mol ZrOCl
28H
2O, 1molSiO
2, 1mol Al
2O
3, 0.01mol Eu
2O
3, 0.004mol Ho
2O
3, the method for repetition embodiment 2 obtains luminescent powder 3, after this luminescent powder excites through standard, and the jaundice green glow, and, can in 2 hours, keep 40mcd/m
2Brightness.
Embodiment 4
Luminescent powder 4:(Ca
1.5Mg
0.5Sr) O
3Al
2O
32ZrO
2SiO
20.02EuO0.004Ho
2O
3Mix 1.5mol CaCO
3, 0.5mol MgCO
3, 1mol SrCO
3, 2mol ZrOCl
28H
2O, 1molSiO
2With 1mol Al
2O
3, 0.01mol Eu
2O
3, 0.004mol Ho
2O
3, the method for repetition embodiment 2 obtains luminescent powder 4, after this luminescent powder excites through standard, and the jaundice green glow, and, can in 2 hours, keep 40mcd/m
2Brightness.
Embodiment 5
Luminescent powder 5:(Ca
2Mg
0.4Sr
0.6) O
3Al
2O
32ZrO
2SiO
20.01EuO0.005Nd
2O
3Mix 2mol CaCO
3, 0.4mol MgCO
3, 0.6mol SrCO
3, 2mol ZrOCl
28H
2O, 1molSiO
2, 1mol Al
2O
3, 0.005mol Eu
2O
3, 0.005mol Nd
2O
3, the method for repetition embodiment 2 obtains luminescent powder 5, after this luminescent powder excites through standard, and the jaundice green glow, and, can in 2 hours, keep 40mcd/m
2Brightness.
Embodiment 6
Luminescent powder 6:(Ca
0.1Mg
0.1Sr
2.8) O
30.92Al
2O
30.08B
2O
32ZrO
2SiO
20.02EuO0.004Ho
2O
3Mix 2.8mol SrCO
3, 0.1mol MgCO
3, 0.1mol CaCO
3, 2mol ZrO
2, 1mol SiO
2, 0.92mol Al
2O
3, 0.08mol B
2O
3, and 0.01mol Eu
2O
3, 0.004mol Ho
2O
3, mixed grinding is with embodiment 2, and sintering temperature is 1340 ℃, and the time is 2 hours, then, will burn back furnace charge flowing water cancellation after drying, and grind and sieve after 4 hours (40 μ), obtains luminescent powder 6.After 5 minutes, luminescent powder can reach brightness L=4000mcd/m with the optical excitation of Ф=200 luxs
2Yellow green light, and just drop to 1mcd/m after reaching 12 hours
2, lowering speed is pressed the hyperbolic line rule.
Press embodiment 1, obtain being soaked in the water after, the pH of water is 6.8.
Embodiment 7-10
Adopt the raw material in the table 1, repeat the synthetic following 4 kinds of luminescent powders (luminescent powder 7-10) of method of embodiment 1, the situation of luminous situation and the maintenance twilight sunset after standard excites is listed in the table 2.
Table 1
| Numbering | Chemical formula | Raw material |
| 7 | (Mg 1.3Ca 0.2Sr 1.5)O 3·Al 2O 3·2ZrO 2·0.9SiO 2·0.1GeO 2·0.005EuO· 0.005Tm 2O 3 | 1.3mol MgCO 3，0.2mol CaCO 3，1.5mol SrCO 3，2mol ZrO 2，1mol Al 2O 3，0.9mol SiO 2，0.1mol GeO 2，0.0025 Eu 2O 3， 0.005mol Tm 2O 3 |
| 8 | (Mg 1.3Ca 0.2Sr 1.5)O 3· Al 2O 3·1.8ZrO 2· 0.2TiO 2·SiO 2· 0.01EuO·0.005Tm 2O 3 | 1.3mol MgCO 3，0.2mol CaCO 3，1.5mol SrCO 3，1.8mol ZrO 2，0.2mol TiO 2，1mol SiO 2，1mol Al 2O 3，0.005 Eu 2O 3，0.005mol Tm 2O 3 |
| 9 | (Ca 1.6Mg 0.4Sr)O 3·Al 2O 3·1.8ZrO 2· 0.2HfO 2·SiO 2·0.01EuO· 0.005Nd 2O 3 | 0.4mol MgCO 3，1.6mol CaCO 3，1mol SrCO 3，1.8mol ZrO 2，0.2mol HfO 2，1mol SiO 2，1mol Al 2O 3，0.005 Eu 2O 3，0.005mol Nd 2O 3 |
| 10 | (Ca 1.6Mg 0.6Sr 0.8)O 3·Al 2O 3· 1.5ZrO 2·0.5HfO 2·SiO 2· 0.005EuO·0.005Nd 2O 3 | 0.6mol MgCO 3，1.6mol CaCO 3，0.8mol SrCO 3，1.5mol ZrO 2，0.5mol HfO 2，1mol SiO 2，1mol Al 2O 3，0.0025 Eu 2O 3， 0.005mol Nd 2O 3 |
Table 2
| Numbering | Glow color | The twilight sunset situation |
| 7 | Orange | 12 hours |
| 8 | Sea blue look | 12 hours |
| 9 | Yellow-green colour | 12 hours |
| 10 | Yellow-green colour | 12 hours |
Above-mentioned experimental result shows, when with the part Si O in the raw material
2Replace to GeO
2The time, can cause luminously moving to the long wave direction, and part ZrO
2Replace to TiO
2The time, luminous meeting is moved to the shortwave direction; And if in component, add section H fO
2, then can excite the big energy of storage down at X ray or gamma-rays.
Embodiment 11-14
Adopt the raw material in the table 3, ball milling mixes, oven dry, and the furnace charge corundum crucible of packing into was 1300 ℃ of following sintering 2 hours.Treat that stove is cooled to 700 ℃, take out crucible, be cooled to room temperature, wash with water, after the drying, ball milling 4 hours, mistake 200 mesh sieves, the optical excitation of usefulness Ф 200 luxs 5 minutes, luminescent powder brightness all reaches 4cd/m
2, luminous more than 12 hours.
Table 3
| Numbering | Chemical formula | Raw material |
| 11 | (Sr 0.9Ca 0.1) 3V 2Si 3O 12： 0.01Eu，0.005Nd | 0.9mol SrCO 3，0.1mol CaCO 3，1mol V 2O 5，3mol SiO 2，0.005mol Eu 2O 3，0.0025mol Nd 2O 3 |
| 12 | (Sr 0.9Ca 0.1) 3V 2Si 3O 12： 0.01Eu，0.005Tm | 0.9mol SrCO 3，0.1mol CaCO 3，1mol V 2O 5，3mol SiO 2，0.005mol Eu 2O 3，0.0025mol Tm 2O 3 |
| 13 | (Sr 0.8Ca 0.2) 3V 2Si 3O 12： 0.01Yb，0.005Nd | 0.8mol SrCO 3，0.2mol CaCO 3，1mol V 2O 5，3mol SiO 2，0.005mol Yb 2O 3，0.0025mol Nd 2O 3 |
| 14 | (Sr 0.8Ca 0.2) 3V 2Si 3O 12： 0.01Yb，0.005Tm | 0.8mol SrCO 3，0.2mol CaCO 3，1mol V 2O 5，3mol SiO 2，0.005mol Yb 2O 3，0.0025mol Tm 2O 3 |
Embodiment 15
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 1-14 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 1～14 respectively.
Resulting finished product 1～14 is deposited three months respectively in water after, the luminous not influence of fluor.
Claims (15)
1, a kind of fluorescent material with ultra-long afterglow is characterized in that, the general formula of described fluorescent material is
(Me
IIO)
3·M
III 2O
3·(M
IVO
2)
3·xRO·yTR
2O
3
Wherein,
Described Me
IIFor being selected from Mg, Ca, Sr, the element of one or more among the Zn;
Described M
IIIFor being selected from Al, V, Ga, the element of one or more among the B;
Described M
IVFor being selected from Si, Zr, Ti, the element of one or more among the Hf;
Described R is for being selected from Eu, Sm, Yb, the element of one or more among the Sn;
Described TR is for being selected from La, Nd, Ce, Er, Ho, Y, Gd, Bi, Sc, Pr, Sb, the element of one or more among the Tb;
X and y are mole number, and the selection of x and y makes the concentration of R and TR account for 0.1～0.4% of material gross weight ratio.
2, fluorescent material with ultra-long afterglow as claimed in claim 1, wherein, the general formula of described fluorescent material is (Me
IIO)
32ZrO
2Al
2O
3SiO
2XROyTR
2O
3
3, fluorescent material with ultra-long afterglow as claimed in claim 1, wherein, the general formula of described fluorescent material is (Me
IIO)
3V
2O
3(SiO
2)
3XROyTR
2O
3
4, fluorescent material with ultra-long afterglow as claimed in claim 2, wherein, described material is to be selected from the compound of following general formula one or more:
(CaO)
3·Al
2O
3·2ZrO
2·SiO
2·0.02EuO·0.005Y
2O
3；
(Ca
1.5Mg
0.5Sr)O
3·Al
2O
3·2ZrO
2·SiO
2·0.01EuO·0.005Nd
2O
3；
(Ca
2Mg
0.4Sr
0.6)O
3·Al
2O
3·2ZrO
2·SiO
2·0.02EuO·0.004Ho
2O
3；
(Ca
1.5Mg
0.5Sr)O
3·Al
2O
3·2ZrO
2·SiO
2·0.02EuO·0.004Ho
2O
3；
(Ca
2Mg
0.4Sr
0.6) O
3Al
2O
32ZrO
2SiO
20.01EuO0.005Nd
2O
3And
(Ca
0.1Mg
0.1Sr
2.8)O
3·0.92Al
2O
3·0.08B
2O
3·2ZrO
2·SiO
2·0.02EuO·0.004Ho
2O
3。
5, fluorescent material with ultra-long afterglow as claimed in claim 2, wherein, smaller or equal to the ZrO of 0.5mol
2By TiO
2Replace.
6, fluorescent material with ultra-long afterglow as claimed in claim 5, the general formula of described fluorescent material are (Mg
1.3Ca
0.2Sr
1.5) O
3Al
2O
31.8ZrO
20.2TiO
2SiO
20.01EuO0.005Tm
2O
3
7, fluorescent material with ultra-long afterglow as claimed in claim 2, wherein, smaller or equal to the ZrO of 0.5mol
2By HfO
2Replace.
8, fluorescent material with ultra-long afterglow as claimed in claim 7, the general formula of described fluorescent material are (Ca
1.6Mg
0.4Sr) O
3Al
2O
31.8ZrO
20.2HfO
2SiO
20.01EuO0.005Nd
2O
3, perhaps (Ca
1.6Mg
0.6Sr
0.8) O
3Al
2O
31.5ZrO
20.5HfO
2SiO
20.005EuO0.005Nd
2O
3
9, fluorescent material with ultra-long afterglow as claimed in claim 2, wherein, smaller or equal to the SiO of 0.5mol
2By GeO
2Replace.
10, fluorescent material with ultra-long afterglow as claimed in claim 9, the general formula of described fluorescent material are (Mg
1.3Ca
0.2Sr
1.5) O
3Al
2O
32ZrO
20.9SiO
20.1GeO
20.005EuO0.005Tm
2O
3
11, fluorescent material with ultra-long afterglow as claimed in claim 3, wherein, described fluorescent material is to be selected from the compound of following general formula one or more:
(Sr
0.9Ca
0.1)
3V
2Si
3O
12：0.01Eu，0.005Nd；
(Sr
0.9Ca
0.1)
3V
2Si
3O
12：0.01Eu，0.005Tm；
(Sr
0.8Ca
0.2)
3V
2Si
3O
12: 0.01Yb, 0.005Nd; And
(Sr
0.8Ca
0.2)
3V
2Si
3O
12：0.01Yb，0.005Tm。
12, a kind of preparation comprises as the method for the described fluorescent material with ultra-long afterglow of one of claim 1 to 11, by oxide compound, the oxide compound of TR, the Me of stoichiometry uniform mixing R
IICarbonate and M
IIIAnd M
IVHypochlorite or oxide compound, at 1250～1360 ℃ down with CO and/or H
2Reduction.
13, as the method for claim 12, wherein, described CO is the CO that is produced by carbon granules and raw material
2And H
2The O reaction is produced.
14, as the application of the described fluorescent material with ultra-long afterglow of one of claim 1 to 11 in preparation coating.
15, as the application of claim 14, wherein, described coating is water-borne coatings.
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| CN101705095B (en) * | 2009-09-21 | 2011-08-10 | 四川新力光源有限公司 | Yellow light afterglow material and preparation method thereof as well as LED illuminating device using same |
| CN104178153A (en) * | 2013-05-23 | 2014-12-03 | 海洋王照明科技股份有限公司 | Europium terbium-doped hafnium oxide-based light-emitting film and preparation method thereof and electroluminescent device |
| CN106147767B (en) * | 2016-07-14 | 2018-12-28 | 厦门大学 | A kind of long after glow luminous material and preparation method thereof |
| CN106381141A (en) * | 2016-08-31 | 2017-02-08 | 广州珠江光电新材料有限公司 | Boron-containing aluminosilicate long afterglow phosphor and preparation method thereof |
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2000
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