CN1670123A - Fast light-storage long-afterglow fluorescent powder and preparation method thereof - Google Patents
Fast light-storage long-afterglow fluorescent powder and preparation method thereof Download PDFInfo
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- CN1670123A CN1670123A CN 200410014319 CN200410014319A CN1670123A CN 1670123 A CN1670123 A CN 1670123A CN 200410014319 CN200410014319 CN 200410014319 CN 200410014319 A CN200410014319 A CN 200410014319A CN 1670123 A CN1670123 A CN 1670123A
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- 239000000843 powder Substances 0.000 title claims abstract description 21
- 238000003860 storage Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 239000012190 activator Substances 0.000 claims abstract description 6
- 230000005496 eutectics Effects 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 3
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 230000007704 transition Effects 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 230000002688 persistence Effects 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 230000003081 coactivator Effects 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 abstract 1
- 229910052721 tungsten Inorganic materials 0.000 abstract 1
- 230000005283 ground state Effects 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 3
- SFEPYDFMDUERPZ-UHFFFAOYSA-N aluminum;strontium;borate Chemical compound [Al+3].[Sr+2].[O-]B([O-])[O-] SFEPYDFMDUERPZ-UHFFFAOYSA-N 0.000 description 3
- 238000010893 electron trap Methods 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000006690 co-activation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000941 radioactive substance Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a fast light-storage long-afterglow fluorescent powder taking Eu as a main activator, which is characterized by being defined by the following general formula: 1－w－x－yBwDxEy)O·a(G1－2H2) 2O3In the formula, A represents at least one of alkaline earth metals Mg, Ca, Sr, Ba and trivalent metal Zn; b represents one of Si, Ge and Sn; d represents an activator Eu; e represents at least one of co-activators Dy, Nd, Pr, Ho, Er, Tm, Yb, La, Gd and Lu, transition elements Mn, Zr, Nb, Ti, Sb, Li, In, Ni and W; g represents matrix eutectic Al; h represents matrix eutectic B or Ga, wherein W is more than or equal to 0.0001 and less than or equal to 0.2, X is more than or equal to 0.0001 and less than or equal to 0.5, Y is more than or equal to 0.0001 and less than or equal to 0.3, Z is more than or equal to 0.0001 and less than or equal to 0.5, and a is more than or equal to 0.5 and less than or equal to 3.0.
Description
Technical field
The present invention relates to quick light storage long persistence luminescent powder and manufacture method thereof.
Background technology
Long persistence luminescent powder is a kind ofly to have the optical property of holding after the irradiation of the sun or other light sources, in the dark can send residual light for a long time, can repeatedly repeat to hold light and luminous again material.Long persistence luminescent powder in the past mostly is sulfide-based compound, for example ZnS:Cu, Co or CaS:Ce etc., though this class long persistence luminescent powder can absorb extraneous luminous energy, in the dark launch residual light then, have about 0.5 to 1 hour but inhale between the residual light time, and the weak chemical stability of sulfide-based compound has determined their not water-fast, easy aging, life-span weak points.The another kind of long persistence luminescent powder of exploitation in the past contains radioactive substance, can be luminous voluntarily in for a long time, but radioactive substance is the dangerous source of pollution of generally acknowledging, all can produce severe impairment to human body and environment, so forbidden in the world to have used.
It is the long persistence luminescent powder of matrix that nineteen nineties has worked out with the alkaline earths aluminate, it activates the alkaline earths aluminate substrate jointly by europium (Eu) and other elements and is luminous, has the luminosity height, fluorescent lifetime reached more than 24 hours, advantages such as and chemical stability is good, and weather resistance is good, and the life-span is long, so be widely used in luminescent ink, luminescent coating, noctilucence glass, on various emergent written instructions signs and the products such as ornament and low-light (level) light source.
But, the place that this alkaline earths aluminate long afterglow fluorescent material also comes with some shortcomings, the speed that for example absorbs extraneous luminous energy is unhappy, and it is slow promptly to hold light, under the irradiation of ultraviolet lamp, wants usually could fully hold light about 15 minutes, and state reaches capacity.And for example water tolerance though improve a lot than sulfide-based fluorescent material, is soaked in water for a long time, still has the partial hydrolysis phenomenon to take place.
The principle of luminosity of long persistence luminescent powder is after the out-shell electron when molecule or atom is subjected to outside energy (as heat, light or ray etc.) and excites, to jump to excited state from ground state, the electronics of excited state is unsteady state, after extraneous excitation energy disappears, electronics just turns back to stable ground state from unsettled excited state, and the form of unnecessary energy with light discharged, form luminous image.But if during the element that in crystal, mixes specific, not only can reduce the energy that is excited of unstable electronics, make its be easy to be excited (promptly being easy to hold light), can also form electron trap at luminescence center, electronics is caught by these electron traps in the way of returning ground state, and its unstable degree is only second to ground state, when the external world excite stop after, the captive electronics electron trap that jumps out is gradually got back to ground state, sends light at leisure.
Summary of the invention
The object of the present invention is to provide a kind of long persistence luminescent powder that reaches quick light storage by doping techniques.
Another object of the present invention is to provide quick light storage long-afterglow fluorescent powder, preparation method thereof.
Purpose of the present invention can reach by following measure:
According to the present invention, the new composition of quick light storage long persistence luminescent powder can be defined by following general expression:
(A
1-w-x-yB
wD
xE
y) Oa (G
1-2H
2)
2O
3A represents among alkaline-earth metal Mg, Ca, Sr, Ba and the divalent metal Zn at least a in the formula; B represents among Si, Ge, the Sn a kind of; D represents activator Eu; E represents coactivator Dy, Nd, Pr, Ho, Er, Tm, Yb, La, Gd, Lu, and is at least a among transition element Mn, Zr, Nb, Ti, Sb, Li, In, Ni, the W; G represents matrix eutectic Al; H represents matrix eutectic B or Ga, wherein
0.0001≤W≤0.2
0.0001≤X≤0.5
0.0001≤Y≤0.3
0.0001≤Z≤0.5
0.5≤a＜3.0
According to the present invention, with Al
2O
3Starting raw material as component Al source; With SrCO
3As the starting raw material in component Sr source, with SiO
2As the starting raw material in component Si source, with Eu
2O
3, Dy
2O
3, Gd
2O
3, H
3BO
3, NiCO
3Starting raw material as corresponding component Eu, Dy, Gd, B, Ni source, desired raw material is placed on the crucible of packing into behind the thorough mixing in the blender, be heated to 1000-1500 ℃ in the reducing atmosphere of activated carbon, be incubated and naturally cool to room temperature after 0.5-5 hour, product gets product after pulverizing.
Advantage of the present invention:
The defined component of the embodiment of the invention, crushing screening again behind batch mixing and sintering, the firing time of products obtained therefrom and brightness such as table 1.Table 1 expression manufactured according to the present invention by Eu, Dy co-activation mixed aluminium strontium borate long persistence luminescent powder firing time and the brightness contrast of the aluminium strontium borate long persistence luminescent powder of Gd, Si, Ni and the Gd that undopes, Si, Ni.Can find out that therefrom this is a kind of fast long persistence luminescent powder of auroral poles that holds.
Table 1, firing time and brightness contrast table
| Test portion | 0.5 the brightness after dividing | Brightness after 1 minute | Brightness after 10 minutes | Brightness after 30 minutes |
| The embodiment product | ????0.7 | ????1.0 | ????1.0 | ????1.0 |
| Common long persistence luminescent powder | ????0.3 | ????0.6 | ????0.8 | ????1.0 |
Description of drawings
Fig. 1 represents manufactured according to the present invention by the mixed emmission spectrum of aluminium strontium borate long persistence luminescent powder of Gd, Si, Ni of Eu, Dy co-activation.
Embodiment
Further specify the purpose that the present invention reaches below with reference to accompanying drawing and preparation example.
Embodiment:
Accurately take by weighing SrCO
3150g
Al
2O
3???????????????????120g
Eu
2O
3???????????????????3g
Dy
2O
3???????????????????4g
SiO
2?????????????????????0.0042g
Gd
2O
3???????????????????0.0014g
NiCO
3????????????????????0.00014g
H
3BO
3???????????????????12g
Be placed on the crucible of packing into behind the thorough mixing in the blender, be heated to 1350 ℃ in the reducing atmosphere of activated carbon, be incubated and naturally cool to room temperature after 2 hours, product promptly obtains the quick light storage long persistence luminescent powder after pulverizing.
Claims (2)
1, a kind of is the quick light storage long persistence luminescent powder of main activator with Eu, it is characterized in that by following general expression definition:
(A
1-w-x-yB
wD
xE
y) Oa (G
1-2H
2)
2O
3A represents among alkaline-earth metal Mg, Ca, Sr, Ba and the trivalent metal Zn at least a in the formula; B represents among Si, Ge, the Sn a kind of; D represents activator Eu; E represents coactivator Dy, Nd, Pr, Ho, Er, Tm, Yb, La, Gd, Lu, and is at least a among transition element Mn, Zr, Nb, Ti, Sb, Li, In, Ni, the W; G represents matrix eutectic Al; H represents matrix eutectic B or Ga, wherein
0.0001≤W≤0.2
0.0001≤X≤0.5
0.0001≤Y≤0.3
0.0001≤Z≤0.5
0.5≤a＜3.0。
2, a kind of quick light storage long-afterglow fluorescent powder, preparation method thereof is characterized in that with Al
2O
3Starting raw material as component Al; With SrCO
3As the starting raw material of component Sr, with SiO
2As the starting raw material of component Si, with Eu
2O
3, Dy
2O
3, Gd
2O
3, H
3BO
3, NiCO
3Starting raw material as corresponding component Eu, Dy, Gd, B, Ni, desired raw material is placed on the crucible of packing into behind the thorough mixing in the blender, be heated to 1000-1500 ℃ in the reducing atmosphere of activated carbon, be incubated and naturally cool to room temperature after 0.5-5 hour, product gets product after pulverizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410014319 CN1670123A (en) | 2004-03-15 | 2004-03-15 | Fast light-storage long-afterglow fluorescent powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410014319 CN1670123A (en) | 2004-03-15 | 2004-03-15 | Fast light-storage long-afterglow fluorescent powder and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1670123A true CN1670123A (en) | 2005-09-21 |
Family
ID=35041566
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410014319 Pending CN1670123A (en) | 2004-03-15 | 2004-03-15 | Fast light-storage long-afterglow fluorescent powder and preparation method thereof |
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| Country | Link |
|---|---|
| CN (1) | CN1670123A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191062A (en) * | 2010-03-12 | 2011-09-21 | 长春师范学院 | Red fluorescent powder for white light-emitting diode (LED) and preparation method thereof |
| CN103194228A (en) * | 2013-03-28 | 2013-07-10 | 华南理工大学 | Long-lasting phosphorescent material with optical excitation characteristic for biological imaging and preparation method and application thereof |
| CN107336556A (en) * | 2017-07-14 | 2017-11-10 | 李梦娟 | A kind of crystalloid printing opacity porcelain plate picture display structure and its preparation technology |
-
2004
- 2004-03-15 CN CN 200410014319 patent/CN1670123A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191062A (en) * | 2010-03-12 | 2011-09-21 | 长春师范学院 | Red fluorescent powder for white light-emitting diode (LED) and preparation method thereof |
| CN102191062B (en) * | 2010-03-12 | 2014-03-19 | 长春师范学院 | Red fluorescent powder for white light-emitting diode (LED) and preparation method thereof |
| CN103194228A (en) * | 2013-03-28 | 2013-07-10 | 华南理工大学 | Long-lasting phosphorescent material with optical excitation characteristic for biological imaging and preparation method and application thereof |
| CN103194228B (en) * | 2013-03-28 | 2015-06-03 | 华南理工大学 | Long-lasting phosphorescent material with optical excitation characteristic for biological imaging and preparation method and application thereof |
| CN107336556A (en) * | 2017-07-14 | 2017-11-10 | 李梦娟 | A kind of crystalloid printing opacity porcelain plate picture display structure and its preparation technology |
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|---|---|---|---|
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |