CN101429432A - Superfine grain size high light efficiency long afterglow fluorescent powder and its production method - Google Patents
Superfine grain size high light efficiency long afterglow fluorescent powder and its production method Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title description 14
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052788 barium Inorganic materials 0.000 claims abstract description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 43
- 230000002688 persistence Effects 0.000 claims description 33
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 16
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 230000001795 light effect Effects 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 4
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 150000002823 nitrates Chemical class 0.000 abstract 1
- -1 printing Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 238000005090 crystal field Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- 239000005084 Strontium aluminate Substances 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000006690 co-activation Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005524 hole trap Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
A kind of superfine particle size high light efficiency long afterglow phosphor powder, the chemical structural formula is: srm－pMepAl2O(3+m+q):Eux，Dyy，RzWherein Me is at least one of Ba and Mg; r is at least one of La and Gd; m is more than 1 and less than or equal to 1.3; p is more than or equal to 0.006 and less than 0.3; q ═ x + y + z; x is more than or equal to 0.005 and less than or equal to 0.05; y is more than or equal to 0.005 and less than or equal to 0.08; z is more than or equal to 0.0001 and less than or equal to 0.01. The preparation method comprises the following steps: 1) taking the chemical structural formula of a target product as a measuring basis, and taking oxides, nitrates or carbonates of Sr, Ba, Mg, Eu, Dy, La and Gd as raw materials; 2) adding a reaction auxiliary agent into the raw materials; 3) placing the mixed raw materials in a high-temperature reducing atmosphere furnace in N2/H2Carrying out high-temperature synthesis under the protection of mixed gas; 4) crushing the sintered fluorescent powder block to obtain the superfine grain size long afterglow fluorescent powder; 5) and (4) carrying out post-treatment on the crushed fluorescent powder to obtain a finished product. The invention has fine particle size and concentrated distribution, still has higher luminous brightness and longer afterglow time, and can well meet the application in the fields of luminous fiber, printing, coating and the like.
Description
Technical field
The present invention relates to a kind of fluorescent material and manufacture method thereof, mainly relate to high light efficiency long persistence luminescent powder of a kind of fine grain size and manufacture method thereof.
Background technology
About europkium-activated alkali earth metal aluminate long after glow luminous material more existing report and patent introductions, wherein utilize europkium-activated strontium aluminate to be widely used as long after glow luminous material.About europkium-activated strontium aluminate fluorescent material SrAl
2O
4: Eu promptly has report in US3294699 (1966), it discloses a kind of green long afterglow fluorescent material of launching main peak at 520nm.Disclosing chemical constitution formula among the Chinese patent CN1053g007 is m (Sr
1-xEu
x) OnAl
2O
3YB
2O
3Long persistence luminescent powder and manufacture method thereof, wherein each coefficient scope is 1≤m≤5,1≤n≤8,0.001≤x≤0.1,0.005≤y≤0.35, adopts the oxide compound, carbonate or the nitrate that contain aluminium, strontium and boron as raw material, obtains by high temperature solid-state method is synthetic.Chinese invention patent CN1126746A has proposed Eu, Ce, Tb, Dy activated alkali earth metal aluminate long persistence luminescent powder; Chinese invention patent CN1152018A has announced a kind of long Persistence and high brightness fluorescent materials and manufacture method thereof, and general expression is MNAl
2-xB
xO
4, wherein M represents alkaline-earth metal, is generally strontium, and N represents rare earth element, 0.1＜x＜1.
Although at present with europkium-activated yellowish green photoemissive strontium aluminate long afterglow fluorescent powder owing to have higher after-glow brightness and time of persistence, obtained widespread use in fields such as traffic, fire-fightings, but be difficult to the very tiny field of fluorescent material particle diameter requirement be obtained well to use in fiber, weaving etc. always, this mainly be since the particle diameter of long persistence luminescent powder powder must be reduced to a certain degree after (powder medium particle diameter d50≤8 μ m), can be applied in the fiber.But for long persistence luminescent powder, after diameter of particle is reduced to below the 10 μ m, after-glow brightness significantly descends, obviously shorten time of persistence, after particularly the fluorescent material powder adds organic resin as filler, also can further reduce the assimilated efficiency of exciting light to external world, cause it can't satisfy actual service requirements.The composition proportion and the manufacture method of this and fluorescent material all have important relation.Existing disclosed fluorescent material only considers from general application particle diameter angle that in the composition design on the other hand, the production of long persistence luminescent powder at present is difficult to making a breakthrough aspect the superfine high brightness type fluorescent material still based on traditional high temperature solid-state method.
This shows, develop possess fine grain size simultaneously, high after-glow brightness luminosity and the fluorescent material of steady persistence time, for the application characteristic of further lifting long persistence luminescent powder, expand its Application Areas and all have great importance.
Summary of the invention
The objective of the invention is to solve long persistence luminescent powder existing contradiction between after-glow brightness and time of persistence and diameter of particle, a kind of long-persistence phosphor with ultra-fine grain diameter and high light effect and manufacture method thereof are provided.
In order to obtain tiny diameter of particle and stronger after-glow brightness simultaneously, must start with from phosphor surface degree of crystallinity and fluorescent powder crystal field simultaneously, owing to the reduction along with the fluorescent material diameter of particle, specific surface area sharply increases, surface imperfection quantity also increases thereupon, causes luminous efficiency significantly to descend; On the other hand, the increase of surface imperfection quantity also can reduce the degree of depth of trap level, causes originally by Dy
3+The electronics that the hole trap energy level that forms is captured and stored is overflowed at faster speed, at room temperature constantly gets back to 4f
65d excited state is returned
8S
7/2Ground state shows as the shortening of time of persistence.
Based on above-mentioned theory, one aspect of the present invention is regulated crystal field by element doping and co-activation technology, obtains the darker trap level degree of depth; Further improve phosphor surface degree of crystallinity by manufacture method on the other hand.
The molecular formula of long-persistence phosphor with ultra-fine grain diameter and high light effect of the present invention is as follows:
(Sr
m-p?Me
p)·Al
2O
(3+m+q)：Eu
x，Dy
y，R
z
Wherein Me is Ba, at least a among the Mg; R is at least a among La, the Gd; 1＜m≤1.3; 0.006≤p＜0.3; Q=x+y+z; 0.005≤x≤0.05; 0.005≤y≤0.08; 0.0001≤z≤0.01.
Preparation method of the present invention may further comprise the steps:
1) with the chemical structural formula of target product: Sr
M-pMe
pAl
2O
(3+m+q): Eu
x, Dy
y, R
zBe payment foundation, oxide compound, nitrate or the carbonate of Sr, Ba, Mg, Eu, Dy, La, Gd of getting corresponding weight is as raw material;
2) add reaction promoter in above-mentioned fluorescent material synthesis material, addition accounts for 0.2～5% of raw material gross weight;
3) mixing raw material that adds reaction promoter is placed the high temperature reduction atmosphere furnace, at N
2/ H
2Mixed gas protectedly down be incubated 2～12h after being warming up to 1320～1525 ℃, be cooled to room temperature then and come out of the stove.
4) with after the fluorescence powder agglomates pulverizing of burning till, enter the jet mill grinding machine and pulverize, obtain the ultra-fine grain diameter long persistence luminescent powder, powder medium particle diameter d50 is 3～8 μ m, d10 〉=1 μ m, d90≤12 μ m.
5) getting the long persistence luminescent powder that crushes, to add the mass percent concentration that has prepared be 10～50% post-treatment solution, be mixed with solid content and be 10～50% phosphor suspension, pigment separate stir 5～48h under temperature is 15～45 ℃ after, be placed in the drying machine 100～120 ℃ through washing and dry by the fire to water ratio and be lower than 2%, promptly obtain ultrafine long afterglow fluorescent material finished product after sieve.
Material purity in the step 1) is 99.5～99.999%, the d of powder
50=2～8 μ m, d
90＜10 μ m, d
100.5 μ m.
Step 2) reaction promoter in is made of by mass percentage following substances: H
3BHO
340～80%, BaF
220～60.
Step 2) reaction promoter in also can be made of by mass percentage following substances: H
3BO
360～90%, NH
4F10～40%.
Temperature rise rate in the step 3) is 350～450 ℃/h, and rate of temperature fall is 100～150 ℃/h.
Wash with dehydrated alcohol in the step 5), the bake out temperature of drying machine is 100～120 ℃, and 200 mesh sieves are crossed in the oven dry back.
Post-treatment solution in the step 5) is an aluminum nitrate.
Post-treatment solution in the step 5) can be made of by mass percentage following substances: magnesium nitrate 20～50%, aluminum nitrate 50～80%.
Post-treatment solution in the step 5) also can be made of by mass percentage following substances: magnesium nitrate 15～50%, aluminum nitrate 35～70% and Yttrium trinitrate 10～40%.
Compare with prior art, the present invention has following advantage:
1) adopts micro-doping techniques, in fluorescent material matrix, mix rare earth La and Gd, reduce activator Eu simultaneously, the consumption of Dy and other coactivators, can guarantee under the prerequisite of luminosity at the beginning so on the one hand, by to the fluorescent material matrix trap level degree of depth, prolong the after-glow brightness and the time of persistence of fine grain size long persistence luminescent powder; On the other hand, also can effectively reduce the consumption of activator Eu, Dy and other coactivators, help reducing production costs.
2) because in the high temperature building-up process, certain scaling loss can take place in the carbonate or the nitrate raw material that contain elements such as kation S r, Ba, Mg in the raw material, causes synthetic fluorescent material to be difficult to obtain pure single-phase, causes the after-glow brightness of fluorescent material on the low side.In the present invention,, can effectively avoid the problems referred to above, be easy to obtain the pure single-phase of high-crystallinity by adding excessive metallic element.
3) adopt H
3BO
3With NH
4F or BaF
2Be combined into the binary reaction auxiliary agent, not only can guarantee after-glow brightness and time of persistence, but also the fluorescent powder grain that burns till is control effectively.The fluorescent material powder agglomates that adopts the inventive method to burn till is loose, and powder granule is tiny, helps alleviating the degree of injury of the surface crystallinity that causes in the follow-up crushing process.
4) adopt advanced jet mill grinding technology to substitute traditional ball grinding technique, realize distribute the again controlled production of fluorescent material of fine grain size, diameter of particle Tile Width d
75/ d
25Reduce to about 2.0 than 3.0 of the commercial powder in market.
5) adopt wet method powder surface modification technique, can effectively remove phosphor surface at the unformed layer that crushing process produces, significantly improve powder surface degree of crystallinity, promote the after-glow brightness of fluorescent material by the nitrate post-treatment solution.
Description of drawings
Fig. 1 long persistence luminescent powder after-glow brightness extinction curve in time.The A# sample is for pressing the fluorescent material that embodiment 1 makes; The B# sample is the equal particle diameter fluorescent material according to comparative example's preparation.As can be seen from this figure, although initially twilight sunset is a little less than comparative sample for the fluorescent material that the present invention makes, along with time lengthening (behind about 5min), after-glow brightness surpasses comparative sample on the contrary.When the time extended to 30min, the after-glow brightness of A# sample had promoted 38% than comparative sample.The characteristics of luminescence that shows ultra-fine grain diameter long persistence luminescent powder provided by the invention has obtained remarkable lifting.Concrete after-glow brightness data see Table 1.
Table 1 phosphor persistence brightness data relatively.
Fig. 2 has shown the grain size distribution curve of the present invention fluorescent material of making and the fluorescent material of making according to the comparative example respectively.Wherein the A# sample is the fluorescent material that embodiment 1 makes; The B# sample is comparative example's fluorescent material.As can be seen, the fluorescent material of manufacturing of the present invention has narrower size distribution characteristic than comparative sample, effectively promotes its application characteristic in coating, resin.
Specific embodiment
The comparative example
By chemical constitution formula is Sr
0.945Al
2O
4: Eu
0.02, Dy
0.035Take by weighing the SrCO of corresponding weight
330.87g, Al
2O
322.44g, Eu
2O
30.78g, Dy
2O
31.45g, H
3BO
31.15g.Mix and be placed in the high temperature reduction atmosphere furnace, at N
2/ H
2Mixed gas protectedly down be incubated 4h after rising to 1350 ℃, cool to room temperature with the furnace and come out of the stove.After the fluorescence powder agglomates broken pulverizer coarse crushing of employing jaw earlier of burning till, enter the broken pulverizer of roller again and pulverize, adopt the rotary type ball mill to pulverize at last, promptly obtain fine grain size long persistence luminescent powder finished product.
Embodiment 1
Chemical constitution formula with target product: Sr
0.93Mg
0.12Al
2O
4.112: Eu
0.022, Dy
0.035, Gd
0.005Be payment foundation, get the SrCO of corresponding weight
327.34g, Al
2O
320.2g, MgO 0.96g, Eu
2O
30.77g, Dy
2O
31.31g, Gd
2O
30.18g, H
3BO
31.27g,
1.78g.Mix and be placed in the high temperature reduction atmosphere furnace, at N
2/ H
2Mixed gas protectedly down be incubated 3h after rising to 1330 ℃ with the heat-up rate of 350 ℃/h, the cooling rate with 120 ℃/h is cooled to room temperature again, comes out of the stove.After the fluorescence powder agglomates pulverizing of burning till, enter the jet mill grinding machine and pulverize, obtain the ultra-fine grain diameter long persistence luminescent powder, powder medium particle diameter d50 is 3～8 μ m, d10 〉=1 μ m, d90≤12 μ m.
Getting the long persistence luminescent powder that crushes, to add the mass percent concentration that has prepared be in 15% aluminum nitrate solution, be mixed with solid content and be 20% phosphor suspension, pigment separate stir 10h under temperature is 25 ℃ after, absolute ethanol washing 1 time, place 120 ℃ in drying machine to dry by the fire to water ratio and be lower than 2%, promptly obtain ultrafine long afterglow fluorescent material finished product after 200 mesh sieves.
Chemical constitution formula with target product: Sr
0.94Mg
0.21Al
2O
4.192: Eu
0.012, Dy
0.025, La
0.0046Be payment foundation, get the SrCO of corresponding weight
327.64g, Al
2O
320.2g, MgO 1.68g, Eu
2O
30.42g, Dy
2O
30.93g, La
2O
30.15g, H
3BO
30.51g, NH
4F 0.18g.Mix and be placed in the high temperature reduction atmosphere furnace, at N
2/ H
2Mixed gas protectedly down be incubated 5h after rising to 1380 ℃ with the heat-up rate of 415 ℃/h, the cooling rate with 110 ℃/h is cooled to room temperature again, comes out of the stove.After the fluorescence powder agglomates pulverizing of burning till, enter the jet mill grinding machine and pulverize, obtain the ultra-fine grain diameter long persistence luminescent powder, powder medium particle diameter d50 is 3～8 μ m, d10 〉=1 μ m, d90≤12 μ m.
Getting the long persistence luminescent powder that crushes, to add the mass percent concentration that has prepared be (wherein the mass ratio of aluminum nitrate and magnesium nitrate is respectively 65% and 35%) in 30% post-treatment solution, be mixed with solid content and be 40% phosphor suspension, pigment separate stir 15h under temperature is 40 ℃ after, absolute ethanol washing 1 time, place 120 ℃ in drying machine to dry by the fire to water ratio and be lower than 2%, promptly obtain ultrafine long afterglow fluorescent material finished product after 200 mesh sieves.
Chemical constitution formula with target product: Sr
1.2Mg
0.08Al
2O
4.334: Eu
0.016, Dy
0.028, La
0.01Be payment foundation, get the SrCO of corresponding weight
333.92g, MgO 0.62g, Al
2O
319.42g, Eu
2O
30.54g, Dy
2O
31.00g, La
2O
30.31g, H
3BO
30.84g, NH
4F 0.25g.Mix and be placed in the high temperature reduction atmosphere furnace, at N
2/ H
2Mixed gas protectedly down be incubated 4.5h after rising to 1450 ℃ with the heat-up rate of 375 ℃/h, the cooling rate with 110 ℃/h is cooled to room temperature again, comes out of the stove.After the fluorescence powder agglomates pulverizing of burning till, enter the jet mill grinding machine and pulverize, obtain the ultra-fine grain diameter long persistence luminescent powder, powder medium particle diameter d50 is 3～8 μ m, d10 〉=1 μ m, d90≤12 μ m.
Getting the long persistence luminescent powder that crushes, to add the mass percent concentration that has prepared be (wherein the mass ratio of magnesium nitrate, aluminum nitrate and Yttrium trinitrate is respectively 18%:68%:14%) in 42% post-treatment solution, be mixed with solid content and be 35% phosphor suspension, pigment separate stir 20h under temperature is 35 ℃ after, absolute ethanol washing 1 time, place 120 ℃ in drying machine to dry by the fire to water ratio and be lower than 2%, promptly obtain ultrafine long afterglow fluorescent material finished product after 200 mesh sieves.
Embodiment 4
Chemical constitution formula with target product: Sr
0.89Mg
0.16Al
2O
4.16: Eu
0.035, Dy
0.068, Gd
0.002, La
0.0013Be payment foundation, get the SrCO of corresponding weight
329.07g, MgCO
33.0g, Al (NO
3)
394.67g, Eu
2O
31.37g, Dy
2O
32.82g, Gd
2O
30.05g, La
2O
30.08g, H
3BO
32.09g, NH
4F 1.21g.Mix and be placed in the high temperature reduction atmosphere furnace, at N
2/ H
2Mixed gas protectedly down be incubated 2.5h after rising to 1520 ℃ with the heat-up rate of 450 ℃/h, the cooling rate with 150 ℃/h is cooled to room temperature again, comes out of the stove.After the fluorescence powder agglomates pulverizing of burning till, enter the jet mill grinding machine and pulverize, obtain the ultra-fine grain diameter long persistence luminescent powder, powder medium particle diameter d50 is 3～8 μ m, d10 〉=1 μ m, d90≤12 μ m.
Getting the long persistence luminescent powder that crushes, to add the mass percent concentration that has prepared be (wherein the mass ratio of magnesium nitrate, aluminum nitrate and Yttrium trinitrate is respectively 35%:55%:10%) in 42% post-treatment solution, be mixed with solid content and be 25% phosphor suspension, pigment separate stir 35h under temperature is 20 ℃ after, absolute ethanol washing 1 time, place 110 ℃ in drying machine to dry by the fire to water ratio and be lower than 2%, promptly obtain ultrafine long afterglow fluorescent material finished product after 200 mesh sieves.
By embodiment 4 manufacturing chemistry structural formulas is Sr
0.89Mg
0.16Al
2O
4.16: Eu
0.035, Dy
0.068, Gd
0.002, La
0.0013Fluorescent material, enter the jet mill grinding machine and pulverize that to obtain medium particle diameter d50 be 3～8 μ m, d10 〉=1 μ m, the fine grain size fluorescent material of d90≤12 μ m, adding the mass percent concentration that has prepared again is (wherein the mass ratio of magnesium nitrate and aluminum nitrate is respectively 48%:52%) in 42% post-treatment solution, be mixed with solid content and be 50% phosphor suspension, pigment separate stir 40h under temperature is 15 ℃ after, absolute ethanol washing 1 time, place 110 ℃ in drying machine to dry by the fire to water ratio and be lower than 2%, promptly obtain ultrafine long afterglow fluorescent material finished product after 200 mesh sieves.
Claims (10)
1, a kind of long-persistence phosphor with ultra-fine grain diameter and high light effect, its chemical structural formula is: Sr
M-pMe
pAl
2O
(3+m+q): Eu
x, Dy
y, R
z, wherein Me is Ba, at least a among the Mg; R is at least a among La, the Gd; 1＜m≤1.3; 0.006≤p＜0.3; Q=x+y+z; 0.005≤x≤0.05; 0.005≤y≤0.08; 0.0001≤z≤0.01.
2, the preparation method of the described long-persistence phosphor with ultra-fine grain diameter and high light effect of claim 1 is characterized in that may further comprise the steps:
1) with the chemical structural formula of target product: Sr
M-pMe
pAl
2O
(3+m+q): Eu
x, Dy
y, R
zBe payment foundation, oxide compound, nitrate or the carbonate of Sr, Ba, Mg, Eu, Dy, La, Gd of getting corresponding weight is as raw material;
2) add reaction promoter in above-mentioned fluorescent material synthesis material, addition accounts for 0.2～5% of raw material gross weight;
3) mixing raw material that adds reaction promoter is placed the high temperature reduction atmosphere furnace, at N
2/ H
2Mixed gas protectedly down be incubated 2～12h after being warming up to 1320～1525 ℃, be cooled to room temperature, come out of the stove.
4) with after the fluorescence powder agglomates pulverizing of burning till, enter the jet mill grinding machine and pulverize, obtain the ultra-fine grain diameter long persistence luminescent powder, powder medium particle diameter d50 is 3～8 μ m, d10 〉=1 μ m, d90≤12 μ m.
5) getting the long persistence luminescent powder that crushes, to add the mass percent concentration that has prepared be 10～50% post-treatment solution, be mixed with solid content and be 10～50% phosphor suspension, pigment separate stir 5～48h under temperature is 15～45 ℃ after, be placed in the drying machine 100～120 ℃ through washing and dry by the fire to water ratio and be lower than 2%, promptly obtain ultrafine long afterglow fluorescent material finished product after sieve.
3,, it is characterized in that material purity is 99.5～99.999%, the d of powder according to the described preparation method of claim 2
50=2～8 μ m, d
90＜10 μ m, d
100.5 μ m.
4, according to the described preparation method of claim 2, its feature is in step 2) in reaction promoter form by mass percentage by following substances: H
3BO
340～80%, BaF
220～60.
5, according to the described preparation method of claim 2, it is characterized in that step 2) in reaction promoter form by mass percentage by following substances: H
3BO
360～90%, NH
4F10～40%.
6, according to the described preparation method of claim 2, it is characterized in that the temperature rise rate in the step 3) is 350～450 ℃/h, rate of temperature fall is 100～150 ℃/h.
7, according to the described preparation method of claim 2, it is characterized in that washing with dehydrated alcohol in the step 5), the bake out temperature of drying machine is 100～120 ℃, and 200 mesh sieves are crossed in the oven dry back.
8,, it is characterized in that the post-treatment solution in the step 5) is an aluminum nitrate according to the described preparation method of claim 2.
9, according to the described preparation method of claim 2, it is characterized in that the post-treatment solution in the step 5) is made of by mass percentage following substances: magnesium nitrate 20～50%, aluminum nitrate 50～80%.
10, according to the described preparation method of claim 2, it is characterized in that the post-treatment solution in the step 5) is made of by mass percentage following substances: magnesium nitrate 15～50%, aluminum nitrate 35～70% and Yttrium trinitrate 10～40%.
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