CN1150296C - Light-accumulation long-afterglow luminous material - Google Patents
Light-accumulation long-afterglow luminous material Download PDFInfo
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- CN1150296C CN1150296C CNB001184377A CN00118437A CN1150296C CN 1150296 C CN1150296 C CN 1150296C CN B001184377 A CNB001184377 A CN B001184377A CN 00118437 A CN00118437 A CN 00118437A CN 1150296 C CN1150296 C CN 1150296C
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- 239000000463 material Substances 0.000 title claims abstract description 78
- 238000009825 accumulation Methods 0.000 title description 2
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 15
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 11
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 10
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 10
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229910052788 barium Inorganic materials 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 9
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 7
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 5
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 230000002688 persistence Effects 0.000 abstract description 12
- 239000004615 ingredient Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 15
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 238000010189 synthetic method Methods 0.000 description 8
- 239000011701 zinc Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000005132 Calcium sulfide based phosphorescent agent Substances 0.000 description 3
- 101150027751 Casr gene Proteins 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- -1 europium ion Chemical class 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical class [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a long persistence luminescent material which has a chemical formula of aMe delta. BLn2 delta'3. cR: EUx, Rey, wherein the Me is one or more elements from Mg, Ca, Sr, Ba, Zn, Mn and Cd; the Ln is one or more elements from Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; the delta and the delta' are one or two elements of O and S and can not be O simultaneously; the R is one or more ingredients from B2O3, MCl, M2O and P2O5; the M is one or more elements from Li, Na, K, NH4<+> and H; the a, the b, the c, the x and the y are mole coefficients and are respectively 0.00001 to 1.5, 0.00001 to 1.5, 0.1 to 2.5, 0 to 0.4 and 0 to 0.8. The present invention has a preparation method that elemental simple substances or compounds in the chemical formula are uniformly mixed and are sintered at 1100 to 1400 DEG C, and the material has a strong persistence phenomenon after irradiated by visible light.
Description
Technical field
What the present invention relates to is long after glow luminous material, particularly relates to metallic sulfide, oxysulfide long after glow luminous material and manufacture method thereof.
Background technology
Traditional zinc sulphide series long-afterglow material is since invention in 19 end of the centurys, through constantly development, several typical products have been formed, as ZnS:Cu (green emitting), (CaSr) S:Bi (blue look luminous), (CaSr) S:Eu (emitting red light), the shortcoming of these materials is easily to decompose in air and luminous intensity is low, time of persistence short, generally has only 0.5-2 hour.Particularly the long-afterglow material of emitting red light has only (CaSr) S:Eu at present, and this material is shorter with respect to other two kinds of long-afterglow material fluorescent lifetimes, and generally in 0.5 hour, and chemical property is extremely unstable, meets water decomposition easily.Can strengthen luminosity and prolong time of persistence though in this class material, add radioelement, because the pollution of radioelement makes its application be subjected to very big restriction.
The nineties from the beginning of, people have invented aluminates system and silicate systems two big class long-afterglow materials successively, as Chinese patent ZL92110744.7 and Special China Issue publication number CN1194292.This two classes long-afterglow material luminosity, time of persistence, stable aspect all more aforementioned sulfide series long-afterglow material improve a lot, but the glow color of this two classes long-afterglow material is generally royal purple, indigo plant or yellowish green, does not have the emitting red light phenomenon.
The CaS:Eu of research such as W.Lehmann
2+, CaS:Ce
3+Red long afterglow material calculates (J.Electrochem.Soc vol 118 N23,477-481 (1971)) with microsecond time of persistence.The CaS:Eu that Xiang Junhui etc. make, the twilight sunset of Cl red long-afterglow powder is clock (luminous journal vol 17 supplementary issues, 147-148 (1996.8)) in a measure also.Red or the orange red long-afterglow material of MS:Eu, the Tm that EP0339895A1 proposes, also have only dozens of minutes time of persistence, do not reach service requirements.The MS:Eu that CN1202513A proposes
x, A
y, B
zRed or orange long afterglow material, obvious improvement is arranged than the former afterglow intensity and time.
Y
2O
2S:Eu and (Y, Gd)
2O
2S:Eu has extensive use as the negative ray material, and its glow color is red, but does not see the report that it has red long afterglow material.
Summary of the invention
At above-mentioned the deficiencies in the prior art, the invention provides a kind of glow color for red, orange, stability and water resistance are good, luminous intensity height, the sulfide that time of persistence is long, oxysulfide system long-afterglow material.
The present invention's aluminate that continues, another new long-afterglow material after the silicate systems long-afterglow material, it is with sulfide, and oxysulfide is a matrix, with the europium ion is that dominant activator, multiple other ion are the luminescent material of time activator, has realized from orange to emitting red light.
1, long after glow luminous material of the present invention is to be matrix with sulfide, and activator contains europium and other active ions.Its chemical constitution expression is:
aMeδ·bLn
2δ·δ′
2·cR:Eu
x，Re
y
Wherein:
Me is Mg, Ca, Sr, Ba, Zn, Mn, the combination of one or more elements among the Cd;
Ln is Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, the combination of one or more elements among the Lu;
δ, δ ' they are O, the combination of one or both elements among the S, but δ and δ ' they can not be O simultaneously;
R is B
2O
3, MCl, M
2O, P
2O
5In the combination of one or more compositions;
M is Li, Na, K, NH
+ 4, one or both elements among the H or ionic combination;
Re is Si, Al, Ga, Ge, In, Sn, Pb, Sb, Bi, Ti, Zr, Mo, W, Cu, Ag, the combination of one or more elements among the V;
A, b, c, x, y are mole coefficient; 0.00001≤a≤1.5; 0.00001≤b≤1.5; 0.1≤c≤2.5; 0＜x≤0.4; 0≤y≤0.8.
Its main crystalline structure expression formula is MeLn
2S
4Or Ln
2O
2S.
2, a kind of implementation as long after glow luminous material as described in 1 is:
Me is for being selected from Mg, Ca, Sr, Ba, Zn, the combination of one or more elements among the Mn;
Ln is for being selected from Sc, Y, La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, Lu, Yb, the combination of one or more elements among the Gd;
0.8≤a≤1.2；0.8≤b≤1.2；0.4≤c≤1.5；0.001≤x≤0.3；
0≤y≤0.4。
This long after glow luminous material has the twilight sunset phenomenon of emitting red light after rayed.Its main crystalline structure expression formula is MeLn
2S
4, as Me=Ca, Ln=La, this material has emitting red light after burning till, and through X-ray diffraction analysis, its crystalline structure composition mainly is CaLa
2S
4
3, a kind of implementation as long after glow luminous material as described in 1 is:
Me is for being selected from Mg, Ca, Sr, Ba, the combination of one or more elements among the Zn;
Ln is for being selected from Sc, Y, La, Lu, Yb, the combination of one or more elements among the Gd;
0.0001≤a≤0.2；0.8≤b≤1.2；0.4≤c≤1.5；0.001≤x≤0.3；y＝0。
This long after glow luminous material has the twilight sunset phenomenon of emitting red light after rayed.Its main crystalline structure expression formula is Ln
2O
2S, as Me=Ca, Ln=Y, Gd, this material has emitting red light after burning till, and through X-ray diffraction analysis, its crystalline structure composition mainly is (Y, Gd)
2O
2S.
4, the another kind of implementation method as 1 described long after glow luminous material is:
Me is for being selected from Mg, Ca, Sr, Ba, the combination of one or more elements among the Zn;
Ln is for being selected from Sc, Y, La, Lu, Yb, Gd, Tm, Er, Ho, the combination of one or more elements among the Sm;
Re is for being selected from Si, Al, Sn, Ti, Zr, the combination of one or more elements among the Pb;
0.0001≤a≤0.2；0.8≤b≤1.2；0.4≤c≤1.5；0.001≤x≤0.3；0.001≤y≤0.6。
Me, Ln, the variation of x value can cause this material glow color difference.X, the variation of y value in quite on a large scale the time this material still can send stronger ruddiness.Its main crystalline structure expression formula is Ln
2O
2S, when Ln=Y, this material is through X-ray diffraction analysis, and its crystalline structure major ingredient is Y
2O
2S, the material luminous intensity height that wherein has is MS:Eu
x, A
y, B
zMore than 3 times of material; MS:Eu especially, more than 10 times of Tm material (10 minutes brightness values) reach 7 hours time of persistence.
The manufacture method of above-mentioned long-afterglow material adopts the pyroreaction method, concrete grammar is: will contain the compound of above-mentioned element or simple substance and take by weighing by the mol ratio of product chemical expression requirement, porphyrize also mixes, and forms through 1100--1400 ℃ of one or many calcining in High Temperature Furnaces Heating Apparatus.
If raw materials used employing compound can be the oxide compound that contains these elements, carbonate, oxalate, vitriol, nitrate, oxyhydroxide, halogenide etc.
The present invention is that sample is placed diameter 50mm to the method that sample carries out luminous afterglow measurement, in the disk of dark 5m, keeps more than 10 hours in the darkroom.Place at last under the D65 standard light source 1000LX illumination, use its time dependent luminous intensity of glorious degrees instrumentation behind the irradiation 10min.
This material sends orange to emitting red light after illumination, can be used as a kind of additive and is uniformly distributed in the various transparent media, makes various luminous paints, printing ink, and printing paste, plastics, rubber, paper, film etc., and can not change raw-material performance.Also can be applicable in the current consumption product, as clothes, shoes and hats, stationery, clock dial, switch, label, fishing gear, ornament, artwork and sports goods, at building decoration, transportation means, military installations, ship's repairs ﹠ maintenance facilities, fields such as fire-fighting indication have good indicative function.Be particularly suitable for the manufacturing of safety product, as the caution label, the fire-fighting indication, escape route is imported and exported indication mechanisms such as sign.In addition, because this material sends orangely to red light, also can be used for fields such as agricultural, biology, medical treatment.
Description of drawings
Brief Description Of Drawings
Fig. 1 is the X-ray diffractogram of example 8 materials
Fig. 2 is the X-ray diffractogram of example 10 materials
Fig. 3 is the excitation spectrum (a) and the emmission spectrum (b) of example 8 materials
Fig. 4 is the excitation spectrum (a) and the emmission spectrum (b) of example 9 materials
Fig. 5 (a) is the persistence characteristic curve of example 8 materials
Fig. 5 (b) is contrast sample SrS:Eu, Y, Tm, the persistence characteristic curve of Na (send out orange light)
Fig. 5 (c) is the persistence characteristic curve (glowing) of contrast sample CaS:Eu
Fig. 6 is the X-ray diffractogram of example 2 materials
Specific embodiments
In order to illustrate in greater detail the present invention, be described in detail below in conjunction with example.
Example 1
Me＝Ca，Ln＝Y，Yb，R＝NH
4Cl，Na
2CO
3
a＝0.004，b＝0.9945，c＝0.81
x＝0.0015，y＝0
Composition of raw materials
| Material name | The element mole number | Molecular weight | Weight (gram) |
| CaCO 3 | 0.004 | 100.00 | 0.40 |
| Y 2O 3 | 0.99 | 225.82 | 223.56 |
| Yb 2O 3 | 0.0045 | 394 | 1.77 |
| NH 4Cl | 0.2 | 53.5 | 10.7 |
| Eu 2O 3 | 0.0015 | 352 | 0.53 |
| Na 2CO 3 | 0.61 | 106 | 64.66 |
| S | 2.03 | 32 | 64.96 |
| C | 0.2 | 12 | 2.4 |
After above-mentioned raw materials put into the careful porphyrize mixing of mortar, put into corundum crucible, at 1200 ℃ logical 98%N
2/ 2%H
2Reduction furnace in sintering 4 hours, cooling back porphyrize, water carefully washs the back oven dry and promptly gets the embodiment sample.It is orange red luminous that this material is.
Example 2
Me＝Ca，Ln＝La，R＝Li
3PO
4，K
2CO
3 Re＝Si
a＝1.0，b＝0.994，c＝0.9
x＝0.001，y＝0.001
Composition of raw materials
| Material name | The element mole number | Molecular weight | Weight (gram) |
| CaO | 1.0 | 56 | 56 |
| La 2O 3 | 0.998 | 325.8 | 325.14 |
| Li 3PO 4 | 0.1 | 101.9 | 10.19 |
| Eu 2O 3 | 0.001 | 352 | 0.35 |
| SiO 2 | 0.001 | 60.1 | 0.06 |
| K 2CO 3 | 0.8 | 138.2 | 110.56 |
| S | 2.03 | 32 | 65 |
Synthetic method makes material and is orange red luminous with example 1.
Example 3
Me＝Mg，Ln＝Y，R＝K
3PO
4，Na
2CO
3 Re＝Al，Ti
a＝0.005，b＝0.994，c＝0.9
x＝0.001，y＝0.02
Composition of raw materials
| Material name | The element mole number | Molecular weight | Weight (gram) |
| MgO | 0.005 | 40.3 | 0.20 |
| Y 2O 3 | 0.994 | 225.82 | 224.47 |
| K 3PO 4 | 0.1 | 212.3 | 21.2 |
| Eu 2O 3 | 0.001 | 352 | 0.35 |
| Al 2O 3 | 0.001 | 103 | 0.10 |
| TiO 2 | 0.019 | 79.9 | 1.52 |
| Na 2CO 3 | 0.8 | 106 | 84.8 |
| S | 2.03 | 32 | 65 |
After above-mentioned raw materials put into the careful porphyrize mixing of mortar, put into corundum crucible, sintering is 1 hour in 1200 ℃ High Temperature Furnaces Heating Apparatus, cooling back porphyrize, and water carefully washs the back oven dry and promptly gets the embodiment sample.It is orange red luminous that this material is.
Example 4
Me＝Sr，Ln＝Y，R＝Na
2CO
3，K
3PO
4 Re＝Sn，Ti
a＝0.004，b＝0.994，c＝0.9
x＝0.001，y＝0.02
Composition of raw materials
| Material name | The element mole number | Molecular weight | Weight (gram) |
| SrCO 3 | 0.005 | 147.62 | 0.74 |
| Y 2O 3 | 0.994 | 225.82 | 224.47 |
| K 3PO 4 | 0.1 | 212.3 | 21.23 |
| Eu 2O 3 | 0.001 | 352 | 0.35 |
| SnO 2 | 0.001 | 150.7 | 0.15 |
| TiO 2 | 0.019 | 79.9 | 1.52 |
| Na 2CO | 0.8 | 106 | 84.8 |
| S | 2.03 | 32 | 65 |
After above-mentioned raw materials put into the careful porphyrize mixing of mortar, put into corundum crucible, at 1200 ℃ logical N
2Neutral stove in sintering 2 hours, cooling back porphyrize, water carefully washs the back oven dry and promptly gets the embodiment sample.It is orange red luminous that this material is.
Example 5
Me＝Ba，Ln＝Y，R＝Na
2CO
3，K
3PO
4 Re＝Pb，Ti
a＝0.005，b＝0.994，c＝0.9
x＝0.001，y＝0.02
Composition of raw materials
| Material name | The element mole number | Molecular weight | Weight (gram) |
| BaCO 3 | 0.005 | 197 | 0.99 |
| Y 2O 3 | 0.994 | 225.82 | 224.47 |
| K 3PO 4 | 0.1 | 212.3 | 21.2 |
| Eu 2O 3 | 0.001 | 352 | 0.35 |
| PbO | 0.001 | 223.2 | 0.22 |
| TiO 2 | 0.019 | 79.9 | 1.52 |
| Na 2CO | 0.8 | 106 | 84.8 |
| S | 2.03 | 32 | 65 |
Synthetic method makes material and is orange red luminous with example 1.
Example 6
Me＝Pb，Mg，Ln＝Lu，R＝Na
2CO
3，K
3PO
4 Re＝Si，Ti
a＝0.005，b＝0.997，c＝0.8
x＝0.002，y＝0.03
Composition of raw materials
| Material name | The element mole number | Molecular weight | Weight (gram) |
| PbO | 0.001 | 223.2 | 0.22 |
| MgF 2 | 0.004 | 62.3 | 0.25 |
| Lu 2O 3 | 0.997 | 398 | 396.81 |
| K 3PO 4 | 0.10 | 212.3 | 21.23 |
| Eu 2O 3 | 0.002 | 352 | 0.704 |
| SiO 2 | 0.001 | 30 | 0.06 |
| TiO 2 | 0.019 | 79.9 | 1.52 |
| Na 2CO 3 | 0.7 | 106 | 74.2 |
| S | 2.03 | 32 | 65.0 |
Synthetic method makes material and takes on a red color luminous with example 1.
Example 7
Me＝Zn，Mg，Ln＝Gd，R＝Na
2CO
3，K
3PO
4 Re＝Si，Ti
a＝0.005，b＝0.997，c＝0.8
x＝0.002 y＝0.03
Composition of raw materials
| Material name | The element mole number | Molecular weight | Weight (gram) |
| ZnO | 0.001 | 81.4 | 0.08 |
| MgO | 0.004 | 40.3 | 0.16 |
| Gd 2O 3 | 0.997 | 362.4 | 361.51 |
| K 3PO 4 | 0.1 | 212.3 | 21.33 |
| Eu 2O 3 | 0.002 | 352 | 0.704 |
| SiO 2 | 0.001 | 60 | 0.06 |
| TiO 2 | 0.019 | 79.9 | 1.52 |
| Na 2CO 3 | 0.7 | 106 | 74.2 |
| S | 2.03 | 32 | 65.0 |
Synthetic method makes material and is orange red luminous with example 1.
Example 8
Me＝Mg，Zn，Ln＝Y，La R＝LiCl，Na
2CO
3 Re＝Al，Ti
a＝0.003，b＝0.967，c＝0.92
x＝0.003，y＝0.02
Composition of raw materials
| Material name | The element mole number | Weight (gram) |
| MgO | 0.025 | 1.01 |
| ZnO | 0.005 | 0.41 |
| Y 2O 3 | 0.95 | 214.53 |
| La 2O 3 | 0.017 | 5.54 |
| LiCl | 0.3 | 12.72 |
| Eu 2O 3 | 0.003 | 1.06 |
| Al 2O 3 | 0.005 | 0.51 |
| TiO 2 | 0.015 | 1.20 |
| Na 2CO 3 | 0.62 | 65.72 |
| S | 2.03 | 64.96 |
Synthetic method is with example 1.It is orange red luminous that this material is.
By aforementioned afterglow measurement method, difference practical measuring examples 8, SrS:Eu, Y, Tm, Na (example among the Chinese patent publication number CN1202513A) and commercially available (Ca, Sr) S:Eu, the twilight sunset value of Tm product, as shown in table 1.
Table 1
| Material | Luminous after-glow brightness value (mcd/m 2) | ||||||||||
| 1min | 2min | 3min | 5min | 8min | 10min | 20min | 30min | 40min | 50min | 60min | |
| Example 8 | 736 | 418 | 283 | 166 | 97 | 76 | 28 | 16 | 9 | 7 | 6 |
| SrS:Eu、Y、 Tm、Na | 249 | 157 | 87 | 50 | 29 | 22.6 | |||||
| (Ca、Sr) S:Eu，Tm | 120 | 38 | 19 | 7 | 3.2 | 2 | |||||
Synthetic method is with example 1.
Above-mentioned measuring result is plotted the bilogarithmic graph (as accompanying drawing 5) of luminous twilight sunset and time, and as seen the red twilight sunset material luminosity of selling exceeds tens of times number on the relative market of this material.
Example 9
Me＝Mn，Mg，Ln＝Y，R＝K
3PO
4·3H
2O，Na
2CO
3 Re＝Pb，Ti
a＝0.02，b＝0.92，c＝0.665
x＝0.06，y＝0.01
Composition of raw materials
| Material name | The element mole number | Weight (gram) |
| MnCO 3 | 0.001 | 0.12 |
| MgF 2 | 0.019 | 1.18 |
| Y 2O 3 | 0.92 | 207.75 |
| K 3PO 4·3H 2O | 0.045 | 11.98 |
| Eu 2O 3 | 0.06 | 21.12 |
| PbO | 0.0018 | 0.4 |
| TiO 2 | 0.0082 | 0.66 |
| Na 2CO | 0.62 | 65.72 |
| S | 2.03 | 64.96 |
Synthetic method is with example 1.This material takes on a red color luminous.
Example 10
Me＝Mg，Zn，Ln＝Y，Gd R＝K
3PO
4·3H
2O，K
2CO
3 Re＝Bi，Ti，Sn
a＝0.02，b＝0.9979，c＝0.665
x＝0.001，y＝0.46
Composition of raw materials
| Material name | The element mole number | Weight (gram) |
| MgO | 0.018 | 0.72 |
| ZnCO 3 | 0.002 | 0.25 |
| Y 2O 3 | 0.5 | 112.91 |
| Gd 2O 3 | 0.4779 | 172.29 |
| K 3PO 4·3H 2O | 0.045 | 11.98 |
| Eu 2O 3 | 0.001 | 0.35 |
| Bi 2O 3 | 0.005 | 2.33 |
| TiO 2 | 0.45 | 36 |
| SnO 2 | 0.005 | 0.75 |
| K 2CO 3 | 0.62 | 85.68 |
| S | 2.03 | 64.96 |
| C 6H 12O 6 | 0.07 | 12.6 |
Synthetic method is with example 1.It is orange red luminous that this material is.
Claims (7)
1, long after glow luminous material is characterized in that with sulfide being matrix, and activator contains europium and other active ions, and its chemical constitution expression is:
aMeδ·bLn
2δ·δ′
2·cR:Eu
x，Re
y
Wherein:
Me is Mg, Ca, Sr, Ba, Zn, Mn, the combination of one or more elements among the Cd;
Ln is Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, the combination of one or more elements among the Lu;
δ, δ ' are O, the combination of one or both elements among the S; δ, δ ' can not be 0 simultaneously;
R is B
2O
3, MCl, M
2O, P
2O
5In the combination of one or more compositions;
M is Li, Na, K, NH
+ 4, one or both elements among the H or ionic combination;
Re is Si, Al, Ga, Ge, In, Sn, Pb, Sb, Bi, Ti, Zr, Mo, W, Cu, Ag, the combination of one or more elements among the V;
A, b, c, x, y are mole coefficient, 0.00001≤a≤1.5; 0.00001≤b≤1.5;
0.1≤c≤2.5; 0＜x≤0.4; 0≤y≤0.8; Its main crystalline structure expression formula is MeLn
2S
4Or Ln
2O
2S, twilight sunset is red, orange after the illumination.
2, long after glow luminous material as claimed in claim 1 is characterized in that:
Me is for being selected from Mg, Ca, Sr, Ba, Zn, the combination of one or more elements among the Mn;
Ln is for being selected from Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, the combination of one or more elements among the Lu;
0.8≤a≤1.2；0.8≤b≤1.2；0.4≤c≤1.5；0.001≤x≤0.3；0≤y≤0.4。
3, long after glow luminous material as claimed in claim 1 is characterized in that:
Me is for being selected from Mg, Ca, Sr, Ba, the combination of one or more elements among the Zn;
Ln is for being selected from Sc, Y, La, Lu, Yb, the combination of one or more elements among the Gd;
0.0001≤a≤0.2；0.8≤b≤1.2；0.4≤c≤1.5；0.001≤x≤0.3；y＝0。
4, long after glow luminous material as claimed in claim 1 is characterized in that:
Me is for being selected from Mg, Ca, Sr, Ba, the combination of one or more elements among the Zn;
Ln is for being selected from Sc, Y, La, Lu, Yb, Gd, Tm, Er, Ho, the combination of one or more elements among the Sm;
Re is for being selected from Si, Al, Sn, Ti, Zr, one or more element combinations among the Pb;
0.0001≤a≤0.2；0.8≤b≤1.2；0.4≤c≤1.5；0.001≤x≤0.3；0.001≤y≤0.6。
5, long after glow luminous material as claimed in claim 2, its main crystalline structure expression formula is: MeLn
2S
4
6, as claim 3 or 4 described long after glow luminous material, its main crystalline structure expression formula is: Ln
2O
2S.
7, the manufacture method of long after glow luminous material as claimed in claim 1 is characterized in that: by the mole proportioning of chemical expression requirement, use the simple substance or the compound of expressed element, through batching, behind the porphyrize mixing,, form through the one or many calcining in 1100-1400 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001184377A CN1150296C (en) | 2000-06-22 | 2000-06-22 | Light-accumulation long-afterglow luminous material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001184377A CN1150296C (en) | 2000-06-22 | 2000-06-22 | Light-accumulation long-afterglow luminous material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1330124A CN1330124A (en) | 2002-01-09 |
| CN1150296C true CN1150296C (en) | 2004-05-19 |
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ID=4587217
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352888C (en) * | 2006-02-27 | 2007-12-05 | 江苏博特新材料有限公司 | Fluorescent powder for white light diode and its production method and usage method |
| CN100386405C (en) * | 2006-02-28 | 2008-05-07 | 华南理工大学 | Red long afterglow luminescent material and its prepn |
| CN100427567C (en) * | 2006-08-30 | 2008-10-22 | 吉林大学 | Preparation method of multi-metal oxygen cluster organic/inorganic hybridization liquid crystal material |
| CN100540629C (en) * | 2007-11-12 | 2009-09-16 | 中国科学院长春光学精密机械与物理研究所 | Near ultraviolet or blue-light excited red fluorescence powder and preparation method thereof |
| CN103377599B (en) * | 2012-04-17 | 2015-09-09 | 梁清源 | A kind of long-persistence luminous fire symbol and preparation method thereof |
| CN115646551B (en) * | 2022-11-08 | 2023-12-08 | 喀什大学 | Preparation method and application of all-weather composite nano photocatalyst |
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2000
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