CN1445330A - Artificial synthesized luminescent powder with long afterglow and high light brightness as well as is preparing method - Google Patents
Artificial synthesized luminescent powder with long afterglow and high light brightness as well as is preparing method Download PDFInfo
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- CN1445330A CN1445330A CN 02107414 CN02107414A CN1445330A CN 1445330 A CN1445330 A CN 1445330A CN 02107414 CN02107414 CN 02107414 CN 02107414 A CN02107414 A CN 02107414A CN 1445330 A CN1445330 A CN 1445330A
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- 239000000843 powder Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims description 36
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 37
- 238000001238 wet grinding Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium 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
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 47
- 239000002994 raw material Substances 0.000 claims description 47
- 230000002688 persistence Effects 0.000 claims description 43
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 39
- 150000002910 rare earth metals Chemical class 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 21
- 239000004327 boric acid Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 20
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 7
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 abstract 1
- -1 alkaline earth metal carbonate Chemical class 0.000 description 20
- 238000002156 mixing Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000010189 synthetic method Methods 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 229910003668 SrAl Inorganic materials 0.000 description 4
- 238000009837 dry grinding Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000005084 Strontium aluminate Substances 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000941 radioactive substance Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001337 aliphatic alkines Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 230000008859 change 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
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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Abstract
An artificially synthetic long-persistance high-brightness luminescent powder has the chemical formula: MOn[(Al1-aBa)2-b/3O3-b(OH)b]:CRE, where M is chosen Mg, Ca, Sr and Ba or alkali-earth metals, RE is chosen from La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Eu, Ho, Er, Tm, Yb and Lu, n=0.05-10, a=0.0001-0.5, b=0.0001-2, and c=0.0001-0.6. It is prepared through wet grinding.
Description
Invention field
The present invention relates to steady persistence high brightness luminescent powder of synthetic and preparation method thereof.More particularly, the alkali earth metal aluminate that the present invention relates to boracic is a matrix, adds multiple rare earth (RE) element activator, and the oxygen part in the crystal lattices is by steady persistence high brightness luminescent powder of " OH " metathetical synthetic and preparation method thereof.
Background technology
Phosphor material is meant and is being subjected to sunlight, luminescent lamp and other source of artificial light, particularly ultraviolet ray swash with the time energy-absorbing, change the energy that absorbs into visible light, can continue luminous material after stopping exciting.Keep luminous material of long period after stopping exciting.
In the past, the luminescent coating that uses such as dial or safe label was to mix in paint, the printing ink etc. as the phosphor material of representative as the activated material and prepare to add copper (ZnS:Cu) in zinc sulphide.When this class sulfide is subjected to certain wavelength ultraviolet ray excited, absorb its energy, then, give off energy with the form of visible light, identical with the luminescence mechanism of above-mentioned phosphor material.But this class sulfide is extremely short time of persistence, and the chemical structure instability is not had a photostabilization etc.So aspect practical application, there are many problems.For example, when being used for Luminous Timekeeper, human eye is looked other time of persistence and is had only 20-30 minute; When being subjected to uviolizing, the photolysis phenomenon takes place, so that lose out luminescent properties, so can not wait the place to use outdoor.
In order to prolong the time of persistence of sulfide, adopted and added the method that radioactive substance invests spontaneous luminescence.But, owing to used radioactive substance, strict on material processing, and, make processing such as used utensil and draining and need high cost, now give it up.
Different with this sulfide phosphor material, proposed in alkali earth metal aluminate, to add the fluorescent material that rare earth elements europium is made the sixties.For example, disclosing with the divalent europium in No. 3294699, the United States Patent (USP) is the strontium aluminate luminous material (SrAl of activator
2O
4: Eu), the addition of this divalent europium is the 2-8 mole % of strontium aluminate.Its luminescence peak is 520nm to this fluorescent material when ultraviolet ray excited being subjected to.But this fluorescent material possesses twilight sunset hardly, and is different with phosphor material and long-decay phosphor material.
CN95109878.0 discloses a kind of preparation method of long persistence phosphor, and this method comprises that the mixed oxide with alpha-type aluminum oxide and γ type aluminum oxide is an alumina composition, mixes with other material composition, prepares through steps such as calcining, reduction.Owing to make alumina composition with the mixed oxide of alpha-type aluminum oxide and γ type aluminum oxide in the method, reduced the temperature of calcining or reduction step, make that process is easier carries out, saved energy consumption.In addition, because the boron nuclear power is more effectively replaced the aluminium atom in the crystal lattices, make sintered body have higher briliancy and longer twilight sunset.
CN96100981 has described highlighted long hair luminescent material of a kind of steady persistence and preparation method thereof.This luminescent material sintered body formula M .N.A
2-xB
xO
4Expression, wherein the part aluminium atom in the crystal lattices is by the boron atomic substitutions, and rare earth metal europium part has been obtained a kind of phosphor material of steady persistence by displacements such as other rare earth metal such as lanthanum, cerium, neodymiums.
Though prior art has been carried out some researchs to artificial synthetic luminous material feedstock, method and preparation process condition thereof, obtained certain progress, made quality luminescent material preferably.But these luminescent materials still can not be satisfactory at aspects such as briliancy, time of persistences.Particularly excite stop after, it is the big problem that present long-afterglow material exists that briliancy descends rapidly.So, but people are desirably in luminescent material in 30 minutes-1 hour sufficiently high apparent brightness and long as far as possible visual time of persistence are arranged, to satisfy in some Application Areas enhanced needs day by day.So, the inventor is at problems of the prior art, aspects such as the artificial luminescent material of involutory one-tenth is raw materials used, prescription and synthetic processing condition carry out deeply and carefully studying, found that, to be used to prepare the raw material of jewel, before mixing or after mixing, use one or more material solution to carry out wet grinding as abrasive solvents, making its particle diameter is the 50-10000 nanometer, be preferably the 100-10000 nanometer, more preferably 500-10000 nanometer, the luminescent material briliancy height of preparing, time of persistence is long, thereby has finished the present invention.
Summary of the invention
Therefore, the high briliancy luminescent material of the steady persistence with higher practical value that the purpose of this invention is to provide a kind of synthetic.
This another luminous purpose provides the preparation method of described luminescent material, particularly carries out the preparation method of the luminescent material of wet grinding as abrasive solvents with one or more material solution.
The high briliancy luminescent material of steady persistence of the present invention is generally particulate state or Powdered, it is characterized in that the alkali earth metal aluminate with boracic is a matrix, and more than one RE element is an activator, and chemical molecular formula is:
MOn[(Al
1-aB
a)
2-b/3O
3-b(OH)
b]: in the cRE formula:
M represents to be selected from least a or more than one alkaline-earth metal in magnesium, calcium, strontium or the barium;
RE represents to be selected from least a in lanthanum, cerium, praseodymium, neodymium, samarium, Gadolinium, , Dysprosium, europium, holmium, erbium, thulium, ytterbium or the lutetium or more than one rare earth element;
0.5≤n≤10.0; Preferred 1.0≤n≤10.0; More preferably 1.5≤n≤5.0;
0.0001≤a≤0.5; Preferred 0.001≤a≤0.4; More preferably 0.001≤a≤0.1;
0.0001≤b≤2.0; Preferred 0.001≤b≤1.0; More preferably 0.001≤b≤2.0;
0.0001≤c≤0.6; Preferred 0.001≤c≤0.4; More preferably 0.001≤c≤0.1;
Sauerstoffatom in the crystalline structure of the sintered body that above chemical molecular formula is represented to small part is replaced by " OH ", it is to carry out wet grinding by the material solution with one or more, makes in the raw material each composition be ground to particle diameter and prepares for the 50-10000 nanometer.
A feature again of steady persistence high brightness luminescent powder of the present invention is that RE is preferably from europium, dysprosium, neodymium or its combination.
Long Persistence and high brightness fluorescent materials of the present invention carries out differential thermal analysis with the general differential thermal analyzer in laboratory in 50-1400 ℃, and the result as shown in Figure 1.Find out when about 680 ℃ of temperature, one clearly " heat absorption paddy " is arranged from Fig. 1 is clear, prove has " OH " existence in the crystal lattices of long Persistence and high brightness fluorescent materials of the present invention.This may be hydrogen and oxygen generation " OH " in calcination process, enters crystal lattices and replaced the cause of part Sauerstoffatom in the crystal lattices under molten state.
Fig. 2 shows the X-diffracting spectrum of luminescent material of the present invention.
Table 1 luminescent material powder X-ray diffraction of the present invention is analyzed
Test condition: CuK
αTarget; Voltage 50KV; Electric current 60mA.
Table 1
| Numbering | ????2θ | ????d() | ????I/I 0 |
| ????1 | ????7.040 | ????12.546 | ????11 |
| ????2 | ????14.420 | ????6.138 | ????8 |
| ????3 | ????19.580 | ????4.530 | ????7 |
| ????4 | ????19.860 | ????4.467 | ????45 |
| ????5 | ????20.020 | ????4.432 | ????22 |
| ????6 | ????21.440 | ????4.141 | ????7 |
| ????7 | ????22.040 | ????4.030 | ????17 |
| ????8 | ????22.640 | ????3.924 | ????17 |
| ????9 | ????22.980 | ????3.867 | ????11 |
| ????10 | ????25.380 | ????3.507 | ????15 |
| ????11 | ????27.740 | ????3.213 | ????9 |
| ????12 | ????28.320 | ????3.149 | ????100 |
| ????13 | ????29.220 | ????3.054 | ????80 |
| ????14 | ????29.860 | ????2.990 | ????68 |
| ????15 | ????30.160 | ????2.961 | ????9 |
| ????16 | ????31.360 | ????2.850 | ????30 |
| ????17 | ????33.960 | ????2.638 | ????9 |
| ????18 | ????34.200 | ????2.620 | ????11 |
| ????19 | ????34.760 | ????2.579 | ????35 |
| ????20 | ????35.060 | ????2.557 | ????65 |
| ????21 | ????35.820 | ????2.505 | ????10 |
| ????22 | ????36.220 | ????2.478 | ????18 |
| ????23 | ????36.720 | ????2.446 | ????17 |
| ????24 | ????37.040 | ????2.425 | ????14 |
| ????25 | ????37.280 | ????2.410 | ????10 |
| ????26 | ????37.820 | ????2.377 | ????12 |
| ????27 | ????38.500 | ????2.336 | ????10 |
| ????28 | ????40.460 | ????2.228 | ????20 |
| ????29 | ????40.740 | ????2.213 | ????16 |
| ????30 | ????41.060 | ????2.196 | ????21 |
| ????31 | ????41.840 | ????2.157 | ????15 |
| ????32 | ????42.860 | ????2.108 | ????22 |
| ????33 | ????45.020 | ????2.012 | ????13 |
| ????34 | ????46.400 | ????1.955 | ????20 |
| ????35 | ????47.120 | ????1.927 | ????21 |
| ????36 | ????47.780 | ????1.902 | ????10 |
| ????37 | ????48.720 | ????1.868 | ????11 |
| ????38 | ????49.00 | ????1.858 | ????8 |
| ????39 | ????55.680 | ????1.649 | ????9 |
| ????40 | ????56.380 | ????1.631 | ????9 |
| ????41 | ????57.500 | ????1.601 | ????14 |
| ????42 | ????58.000 | ????1.589 | ????9 |
| ????43 | ????58.440 | ????1.578 | ????9 |
| ????44 | ????58.740 | ????1.571 | ????8 |
| ????45 | ????59.080 | ????1.562 | ????11 |
| ????46 | ????59.960 | ????1.542 | ????10 |
| ????47 | ????60.220 | ????1.535 | ????14 |
| ????48 | ????62.600 | ????1.483 | ????18 |
| ????49 | ????63.180 | ????1.470 | ????12 |
| ????50 | ????65.060 | ????1.432 | ????8 |
X ray diffracting data is through the ICDD database retrieval, finds that on all four thing is mutually on crystalline structure and chemical ingredients with luminescent material of the present invention.Though, many compound such as the SrAl that contain strontium, aluminium, boron, oxygen, OH in the JCPDS card
3O
5(OH) (JCPDS card number (down together) 30-1277), SrAl
2O
4(34-0379), SrAl
12O
19(26-1208), Sr
3B
2O
6(31-1343) with luminescent material powder X ray diffracting spectrum of the present invention in characteristic peak similarity is arranged.But luminescent material of the present invention is not a mixture, is by chemical molecular formula MOn[(A
L1-aB
a)
2-b/3O
3-b(OH)
b]: the one matter of cRE representative, have one matter as 50 unique crystal structures that peak value characterized of table 1, it and any existing material are inequality.
The preparation method of long Persistence and high brightness fluorescent materials of the present invention is characterized in that comprising:
(1) take by weighing raw material by proportioning, being ground into particle diameter is the 50-10000 nanometer, is preferably the 100-10000 nanometer, more preferably the 500-10000 nanometer;
(2) raw material that (1) is ground is inserted in the crucible, and this crucible is put into atmosphere furnace, under reducing atmosphere, in 600-1200 ℃, preferred 900-1100 ℃ temperature lower calcination 2-5 hour;
(3) sintered body is taken out from atmosphere furnace be cooled to room temperature;
(4) cooled sintered body is crushed and screened.
The synthetic method of steady persistence high brightness luminescent powder of the present invention is characterized in that described alkaline-earth metal raw material is the salt that the oxide compound of alkaline-earth metal maybe can produce alkaline earth metal oxide.
Another feature of the synthetic method of steady persistence high brightness luminescent powder of the present invention is that alkaline earth metal oxide is selected from least a in calcium oxide, magnesium oxide, strontium oxide or the barium oxide or more than one combination, preferred calcium oxide or strontium oxide or its combination.
Another feature of the synthetic method of steady persistence high brightness luminescent powder of the present invention is that RE element raw material is selected from one or more the combination in oxide compound, acetate, oxalate or the carbonate of RE element.
Another feature of the synthetic method of steady persistence high brightness luminescent powder of the present invention is that the RE oxide compound is selected from Eu
2O
3, Dy
2O
3Or Nd
2O
3In at least a or more than one combination.
Another feature of the synthetic method of steady persistence high brightness luminescent powder of the present invention is that raw alumina is selected from α-Al
2O
3And γ-Al
2O
3Mixture.
Another feature of the preparation method of steady persistence high brightness luminescent powder of the present invention is that reduction reaction is to carry out under hydrogen atmosphere, or carries out in the reducing atmosphere that reaction produced that takes place in calcination process, preferably carries out in hydrogen atmosphere.
Another feature of the preparation method of steady persistence high brightness luminescent powder of the present invention is that calcining temperature is 800-1200 ℃, preferably carries out under 900-1100 ℃, more preferably carries out under 950-1100 ℃.
Another feature of the preparation method of steady persistence high brightness luminescent powder of the present invention is that available " doing " method of the grinding of raw material or " wetting " method are ground.The grinding of raw material can be carried out after several raw materials mix, or after each former abrasive lapping reaches the particle diameter of defined, mixes again.Preferably grind with wet method.Be abrasive solvents can water, aqueous ethanolic solution, one or more the aqueous solution etc. of raw material make abrasive solvents, preferred water or aqueous solution of raw material are made solvent.If make abrasive solvents with aqueous solution of raw material, then available alumina sol, the alkaline-earth metal aqueous solution, the rare earth metal aqueous solution or boric acid aqueous solution are made abrasive solvents, and the aqueous solution or the boric acid aqueous solution of preferred alumina sol, water, aqueous ethanolic solution, rare earth metal are made abrasive solvents; More preferably the mixed aqueous solution of mixed aqueous solution, alumina sol and the boric acid aqueous solution of the aqueous solution of the mixed aqueous solution of the mixed aqueous solution of the alumina sol and the rare earth metal aqueous solution, alumina sol and the alkaline-earth metal aqueous solution, rare earth metal and boric acid aqueous solution is made abrasive solvents.If carry out wet grinding, then can reach wonderful effect by method of the present invention.
By the performance comparison of the performance of the luminescent material (powder) of the inventive method preparation and traditional luminescent powder (CP-05) as table 2.
The contrast of table 2 colour solid
| ????CP-05 | Luminescent powder of the present invention | |
| ????L | ????94.1-92.0 | ????92.0-93.5 |
| ????a | ????-5.5--6.0 | ????-5.5--6.0 |
| ????b | ????+17.0-+19.0 | ????+21.0-+19.0 |
Contrast by the briliancy of the briliancy of the luminescent material of the inventive method preparation and traditional luminescent powder is as shown in table 3
Table 3CP-05 and luminescent powder briliancy synopsis of the present invention
| Elapsed time | Briliancy (mcd/m 2) | |
| ????CP-05 | Luminescent powder of the present invention | |
| 10 seconds | ????8499 | ????7724 |
| 30 seconds | ????3592 | ????3894 |
| 1 minute | ????2185 | ????2556 |
| 5 minutes | ????621 | ????865 |
| 10 minutes | ????349 | ????508 |
| 20 minutes | ????186 | ????275 |
| 30 minutes | ????121 | ????194 |
| 40 minutes | ????96 | ????150 |
| 50 minutes | ????75 | ????121 |
| 1 hour | ????64 | ????106 |
| 2 hours | ????33 | ????57 |
| 3 hours | ????21 | ????37 |
| 4 hours | ????16 | ????29 |
| 5 hours | ????13 | ????22 |
| 6 hours | ????10 | ????19 |
| 7 hours | ????8 | ????17 |
| 8 hours | ????7 | ????15 |
| 9 hours | ????6 | ????14 |
| 10 hours | ????5 | ????14 |
| 11 hours | ????5 | ????13 |
| 12 hours | ????4 | ????12 |
| 13 hours | ????2 | ????12 |
| 14 hours | ????1 | ????11 |
Initial briliancy by the luminescent powder of the inventive method preparation is 7400mcd/m
2More than, visual time of persistence is more than 80 hours.
Embodiment
Below, be raw material with the chemical, the preparation method of long-afterglow luminescent powder of the present invention is described.
The chemical in alkaline earth metal source, RE element source, boron source and aluminium element source in the present invention, raw material is not particularly limited, as long as can be provided.
Alkaline earth metal source can be an alkaline earth metal oxide, alkaline earth metal hydroxides, alkaline earth metal carbonate, alkine earth metal nitrate, alkaline earth metal borate, alkali earth metal phosphate, alkaline earth metal chromate, the alkaline-earth metal molybdate, titanates of alkali-earth metals, alkaline-earth metal acetate or alkaline-earth metal oxalate and composition thereof etc., the preferred bases soil metal oxide, alkaline earth metal hydroxides, alkaline earth metal carbonate, alkaline earth metal borate, titanates of alkali-earth metals, alkaline-earth metal acetate or alkaline-earth metal oxalate and composition thereof etc., more preferably alkaline earth metal borate, titanates of alkali-earth metals, alkaline-earth metal acetate or alkaline-earth metal oxalate and composition thereof etc.
The RE element source can be used single RE element, also can use RE element mixture (mishmetal), as RE oxide compound, RE oxyhydroxide, RE muriate, RE nitrate, RE acetate and RE oxalate etc. and composition thereof etc., preferably mix RE oxide compound, single RE oxyhydroxide, mixing RE nitrate, single RE oxalate, mix RE oxalate and composition thereof etc.
Boron oxide compound, boric acid and basic metal or alkaline earth salt etc. can be used in the boron source.
The aluminum oxide of various crystalline phases can be used in the aluminium source, as α-Al
2O
3, β-Al
2O
3, γ-Al
2O
3, η-Al
2O
3Or θ-Al
2O
3Deng; Aluminium hydroxide and composition thereof etc., preferred α-Al
2O
3, γ-Al
2O
3, η-Al
2O
3And composition thereof etc., more preferably α-Al
2O
3, γ-Al
2O
3And composition thereof.
The preparation method of luminescent powder of the present invention comprises the steps:
(1) take by weighing raw material by proportioning, with traditional device and above-mentioned method, being ground into particle diameter is the 50-10000 nanometer, is preferably the 100-10000 nanometer, more preferably the 500-10000 nanometer;
(2) raw material that (1) is ground is inserted in the crucible, and this crucible is put into atmosphere furnace, under reducing atmosphere, in 600-1200 ℃, under the preferred 800-1200 ℃ of temperature, more preferably 900-1100 ℃ temperature lower calcination 2-5 hour;
(3) sintered body is taken out from atmosphere furnace be cooled to room temperature;
(3) cooled sintered body is ground into powder material.
In preparation method of the present invention, available " doing " method of the grinding of raw material or " wetting " method are ground.The grinding of raw material can be carried out after several raw materials mix, or after each former abrasive lapping reaches the particle diameter of defined, mixes again.Preferably grind with wet method.Be abrasive solvents can water, aqueous ethanolic solution, one or more the aqueous solution etc. of raw material make abrasive solvents, preferred water or aqueous solution of raw material are made solvent.If make abrasive solvents with aqueous solution of raw material, then available alumina sol, the alkaline-earth metal aqueous solution, the rare earth metal aqueous solution or boric acid aqueous solution are made abrasive solvents, and the aqueous solution or the boric acid aqueous solution of preferred alumina sol, water, aqueous ethanolic solution, rare earth metal are made abrasive solvents; More preferably the mixed aqueous solution of mixed aqueous solution, alumina sol and the boric acid aqueous solution of the aqueous solution of the mixed aqueous solution of the mixed aqueous solution of the alumina sol and the rare earth metal aqueous solution, alumina sol and the alkaline-earth metal aqueous solution, rare earth metal and boric acid aqueous solution is made abrasive solvents.
Below, further describe the present invention with embodiment.These embodiment are used to illustrate purpose of the present invention, rather than limit the invention.Scope of the present invention proposes in the appended claims.
Take by weighing the SrCO that pulverized respectively by prescription
3720g, CaCO
320 grams, Al
2O
3620g, Eu
2O
310g, Dy
2O
38.0g, B
2O
314g (boric acid 24.5 grams) mixes it.Then, carry out dry grinding, it directly is 100 nanometers to make its grain, and the mixing raw material after grinding is inserted in the crucible, under hydrogen atmosphere,, is cooled to room temperature and takes out crucible after 2 hours 1200 ℃ of calcinings, makes luminescent powder A through pulverizing.
Embodiment 2
Take by weighing the SrCO that pulverized respectively by prescription
3720g, CaCO
320 grams, Al
2O
3620g, Eu
2O
310g, Nd
2O
38.0g, B
2O
332g (boric acid 56.8 grams) mixes it.Then, be that abrasive solvents is carried out wet grinding with water, it directly is 100 nanometers to make its grain, and the mixing raw material after grinding is inserted in the crucible, under hydrogen atmosphere,, is cooled to room temperature and takes out crucible after 2 hours 1000 ℃ of calcinings, makes luminescent powder B through pulverizing.
Embodiment 3
Take by weighing the SrCO that pulverized respectively by prescription
3720g, MgCO
310 grams, Al
2O
3620g, Eu
2O
310g, Dy
2O
38.0g, B
2O
35g (boric acid 8.9 grams) mixes it.Then, be that abrasive solvents is carried out wet grinding with the alumina hydrosol, making its particle diameter is 1000 nanometers, mixing raw material after grinding is inserted in the crucible, under hydrogen atmosphere, 1200 ℃ of calcinings after 3 hours, be cooled to room temperature and take out crucible, make luminescent powder C through pulverizing.
Embodiment 4
Take by weighing the SrCO that pulverized respectively by prescription
3720g, CaCO
330 grams, Al
2O
3620g, Eu
2O
310g, Nd
2O
38.0g, B
2O
340g (boric acid 71.0 grams) mixes it.Then, carry out wet grinding with boric acid aqueous solution as abrasive solvents, making its particle diameter is 250 nanometers, and the mixing raw material after grinding is inserted in the crucible, under hydrogen atmosphere,, is cooled to room temperature and takes out crucible after 4 hours 900 ℃ of calcinings, makes luminescent powder D through pulverizing.
Embodiment 5
Take by weighing the SrCO that pulverized respectively by prescription
3720g, CaCO
340 grams, Al
2O
3620g, Eu
2O
310g, Dy
2O
38.0g, B
2O
322.5g (boric acid 45 grams) mix it.Then, the mixed solution of alumina sol and boric acid aqueous solution carries out wet grinding as abrasive solvents, and making its particle diameter is 250 nanometers, mixing raw material after grinding is inserted in the crucible, under hydrogen atmosphere, 1100 ℃ of calcinings after 3 hours, be cooled to room temperature and take out crucible, make luminescent powder E through pulverizing.
Except that the grinding of mixing raw material is to carry out in earth solution and 1000 ℃ of calcinings 3 hours, other carries out preparation luminescent powder F by the method identical with embodiment 2.
Embodiment 7
Except that the grinding of mixing raw material is to carry out in boric acid aqueous solution and 850 ℃ of calcinings 3 hours, other carries out preparation luminescent powder G by the method identical with embodiment 3.
The phosphorescent characteristics test of luminescent powder of the present invention is carried out as follows.
At first, the lucifuge that sample carried out 24 hours is stored, and then, goes up luminescent lamp (about 1000 lumens) with the table of 27W, in shining at a distance of 60 centimeters, after irradiation 30 minutes, stops irradiation, uses TOPCON, the residual brilliant degree of BM-B brightness photometer measure sample.
Table 4: the remaining briliancy of embodiment luminescent powder A-G luminescent powder
| Stop irradiation time | The remaining briliancy mcd/m of luminescent powder A | The remaining briliancy mcd/m of luminescent powder B | The remaining briliancy mcd/m of luminescent powder C | The remaining briliancy mcd/m of luminescent powder D | The remaining briliancy mcd/m of luminescent powder E 2 | The remaining briliancy mcd/m of luminescent powder F | The remaining briliancy mcd/m of luminescent powder G |
| 10 (seconds) | ????7742 | ????7025 | ????7592 | ????8012 | ????7294 | ????7412 | ????8046 |
| ????30 | ????3914 | ????3841 | ????3901 | ????3854 | ????3867 | ????3891 | ????3859 |
| 1 (branch) | ????2556 | ????2521 | ????2543 | ????2632 | ????2532 | ????2536 | ????2610 |
| ????5 | ????871 | ????843 | ????867 | ????893 | ????856 | ????861 | ????885 |
| ????10 | ????508 | ????487 | ????501 | ????511 | ????497 | ????499 | ????501 |
| ????20 | ????284 | ????267 | ????272 | ????293 | ????269 | ????270 | ????285 |
| ????30 | ????200 | ????184 | ????197 | ????204 | ????191 | ????193 | ????199 |
| ????40 | ????154 | ????143 | ????151 | ????156 | ????148 | ????149 | ????150 |
| ????50 | ????126 | ????112 | ????122 | ????131 | ????117 | ????120 | ????116 |
| 1 (hour) | ????106 | ????94 | ????101 | ????107 | ????96 | ????99 | ????100 |
| ????2 | ????57 | ????45 | ????52 | ????59 | ????49 | ????49 | ????46 |
| ????3 | ????37 | ????27 | ????32 | ????38 | ????30 | ????31 | ????33 |
| ????4 | ????29 | ????21 | ????27 | ????31 | ????25 | ????26 | ????24 |
| ????5 | ????22 | ????15 | ????19 | ????24 | ????17 | ????17 | ????16 |
| ????6 | ????19 | ????14 | ????17 | ????21 | ????15 | ????16 | ????14 |
| ????7 | ????17 | ????12 | ????16 | ????18 | ????13 | ????13 | ????12 |
| ????8 | ????15 | ????10 | ????14 | ????17 | ????12 | ????12 | ????11 |
As can be known, steady persistence high brightness luminescent powder of the present invention is after stopping irradiation, and is initial from table
From the table as can be known, steady persistence high brightness luminescent powder of the present invention stop the irradiation after, initial brightness height, time of persistence is longer.Particularly, be the time that long-afterglow luminescent powder has practical value most within an hour exciting after stopping.High nearly one times of the briliancy of identical time, high like this brightness can make people identify in the dark to luminescent powder of the present invention, thereby reaches the purpose that finds the outlet of taking refuge than the luminescent powder of prior art.This is because this luminescent powder sintered body cause of the twinkler characteristics of luminescence of jljl phase not.Also be that promptly the partial oxygen atom in the luminescent powder crystal lattices has been produced " hole " by " OH " displacement owing to have " OH " in the luminescent powder crystal lattices; The specific surface area of nanoparticle raw materials is big, active high, and reacting to each other in calcination process between the raw material is more abundant; Owing to adopt wet grinding, use alumina sol etc. as abrasive solvents, make to grind and carry out more fully, raw material mix more uniform synthesis result, the initial brightness and the persistence of having improved luminescent powder, produced unexpected effect.
Moreover because raw material is a nanometer grade powder, specific surface is big, and is active high, therefore reduced calcining temperature, shortened calcination time, thereby reduced energy consumption, saved cost.But the initial briliancy of luminescent powder has but improved, and lasting time of persistence is longer.
Fully aware of, those skilled in the art can carry out some modifications and improvement to the technical scheme of luminescent powder of the present invention and preparation method thereof, as dry grinding and wet grinding combination being carried out, that is to say, part material carries out dry grinding, and another part raw material carries out wet grinding; Or mixing raw material carries out dry grinding earlier, carries out wet grinding etc. then.But only otherwise deviate from spirit of the present invention, all within the scope of the invention.This scope proposes in appended claims.
Claims (23)
1. the long Persistence and high brightness fluorescent materials of a synthetic is characterized in that the alkali earth metal aluminate with boracic is a matrix, and more than one RE element is an activator, and chemical molecular formula is:
MOn[(Al
1-aB
a)
2-b/3O
3-b(OH)
b]: in the cRE formula:
M represents to be selected from least a or more than one alkaline-earth metal in magnesium, calcium, strontium or the barium;
RE represents to be selected from least a in lanthanum, cerium, praseodymium, neodymium, samarium, Gadolinium, , Dysprosium, europium, holmium, erbium, thulium, ytterbium or the lutetium or more than one rare earth element;
0.5≤n≤10.0
0.0001≤a≤0.5；
0.0001≤b≤2.0；
0.0001≤c≤0.6
Sauerstoffatom in the crystalline structure of the sintered body that above chemical molecular formula is represented to small part is replaced by " OH ", it is to carry out wet grinding by the material solution with one or more, makes in the raw material each composition be ground to particle diameter and prepares for the 50-10000 nanometer.
2. by the described steady persistence high brightness luminescent of claim 1 powder, it is characterized in that 1.0≤n≤10.0.
3. by the described steady persistence high brightness luminescent of claim 1 powder, it is characterized in that 1.5≤n≤5.0;
4. by the described steady persistence high brightness luminescent of claim 1 powder, it is characterized in that preferred 0.001≤a≤0.4.
5. by the described steady persistence high brightness luminescent of claim 1 powder, it is characterized in that 0.001≤a≤0.1.
6. by the described steady persistence high brightness luminescent of claim 1 powder, it is characterized in that 0.001≤b≤1.0.
7. by the described steady persistence high brightness luminescent of claim 1 powder, it is characterized in that 0.001≤b≤2.0.
8. by the described steady persistence high brightness luminescent of claim 1 powder, it is characterized in that 0.001≤c≤0.4.
9. by the described steady persistence high brightness luminescent of claim 1 powder, it is characterized in that 0.001≤c≤0.1.
10. by the described synthetic steady persistence of claim 1 high brightness luminescent powder, it is characterized in that RE is selected from europium, dysprosium, neodymium or its combination.
11. the preparation method of the described synthetic steady persistence of claim 1-10 high brightness luminescent powder is characterized in that comprising:
(1) take by weighing raw material by proportioning, being ground into particle diameter is the 50-10000 nanometer;
(2) raw material that (1) is ground is inserted in the crucible, and this crucible is put into the pressure electric furnace, under reducing atmosphere, in 600-1200 ℃ of temperature lower calcination 2-5 hour;
(3) sintered body is taken out from electric furnace be cooled to room temperature;
(4) cooled sintered body is ground to form powder.
12. by the described method of claim 11, it is characterized in that described alkaline-earth metal raw material is the salt that the oxide compound of alkaline-earth metal maybe can produce alkaline earth metal oxide.
13. by the described method of claim 12, it is characterized in that alkaline earth metal oxide is selected from least a in calcium oxide, magnesium oxide, strontium oxide or the barium oxide or more than one combination.
14. by the described method of claim 11, it is characterized in that RE element raw material is selected from one or more the combination in oxide compound, acetate, oxalate or the carbonate of RE element.
15., it is characterized in that the RE oxide compound is selected from Eu by the described method of claim 14
2O
3, Dy
2O
3Or Nd
2O
3In at least a or more than one combination.
16., it is characterized in that raw alumina is selected from α-Al by the described method of claim 11
2O
3And γ-Al
2O
3Mixture.
17. each the described method by claim 11-16 is characterized in that reduction reaction is to carry out under hydrogen atmosphere.
18. each the described method by claim 11-16 is characterized in that reducing atmosphere is the reducing atmosphere that reaction produced that takes place in calcination process.
19., it is characterized in that calcining temperature is 800-1100 ℃ by the described method of claim 11.
20. by the described method of claim 11, the grinding that it is characterized in that raw material is to carry out after several raw materials mix.
21. by the described method of claim 11, the grinding that it is characterized in that raw material is after each former abrasive lapping reaches the granularity of defined, mixes again.
22. by the described method of claim 11, the grinding that it is characterized in that raw material is to be undertaken by wet method, but the group that used abrasive solvents selects free water, aqueous ethanolic solution, a kind of more than one aqueous solution of raw material to form.
23. by the described method of claim 22, it is characterized in that aqueous solution of raw material is selected from one or more in the group of being made up of mixed aqueous solution, alumina sol and the boric acid aqueous solution of the aqueous solution of mixed aqueous solution, alumina sol and the alkaline-earth metal aqueous solution of alumina sol, the alkaline-earth metal aqueous solution, the rare earth metal aqueous solution, boric acid aqueous solution, alumina sol and the rare earth metal aqueous solution, rare earth metal and boric acid aqueous solution or the alkaline-earth metal aqueous solution and boric acid aqueous solution.
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| CN100457852C (en) * | 2005-06-16 | 2009-02-04 | 中国科学院合肥物质科学研究院 | Nanotube, nano bar-shape aluminate long afterglow materials and method for preparing same |
| CN115678408A (en) * | 2022-11-21 | 2023-02-03 | 河北环宸科技有限公司 | High-brightness fluorescent paint for rough surface |
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| CN100457852C (en) * | 2005-06-16 | 2009-02-04 | 中国科学院合肥物质科学研究院 | Nanotube, nano bar-shape aluminate long afterglow materials and method for preparing same |
| CN115678408A (en) * | 2022-11-21 | 2023-02-03 | 河北环宸科技有限公司 | High-brightness fluorescent paint for rough surface |
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