CN1062581C - Long persistence luminescent silicate material and its producing method - Google Patents
Long persistence luminescent silicate material and its producing method Download PDFInfo
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- CN1062581C CN1062581C CN98105078A CN98105078A CN1062581C CN 1062581 C CN1062581 C CN 1062581C CN 98105078 A CN98105078 A CN 98105078A CN 98105078 A CN98105078 A CN 98105078A CN 1062581 C CN1062581 C CN 1062581C
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- 239000000463 material Substances 0.000 title claims abstract description 251
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 8
- 230000002688 persistence Effects 0.000 title abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 25
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 21
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 15
- 229910052788 barium Inorganic materials 0.000 claims abstract description 15
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 10
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 9
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 70
- 229910017639 MgSi Inorganic materials 0.000 claims description 62
- 238000001228 spectrum Methods 0.000 claims description 40
- 239000002994 raw material Substances 0.000 claims description 27
- 239000011777 magnesium Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 241000233855 Orchidaceae Species 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- -1 vitriol Chemical compound 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 3
- OGWLTJRQYVEDMR-UHFFFAOYSA-F tetramagnesium;tetracarbonate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O OGWLTJRQYVEDMR-UHFFFAOYSA-F 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000010671 solid-state reaction Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 32
- 229910052787 antimony Inorganic materials 0.000 abstract description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 description 69
- 238000012360 testing method Methods 0.000 description 55
- 238000000695 excitation spectrum Methods 0.000 description 29
- 238000002441 X-ray diffraction Methods 0.000 description 26
- 229910052693 Europium Inorganic materials 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 8
- 238000005286 illumination Methods 0.000 description 8
- 229920002994 synthetic fiber Polymers 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 229910019440 Mg(OH) Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000000295 emission spectrum Methods 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 101150027751 Casr gene Proteins 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 4
- 239000012190 activator Substances 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- PLXMOAALOJOTIY-FPTXNFDTSA-N Aesculin Natural products OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)[C@H]1Oc2cc3C=CC(=O)Oc3cc2O PLXMOAALOJOTIY-FPTXNFDTSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910017625 MgSiO Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003081 coactivator Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229940009493 gel-one Drugs 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003904 radioactive pollution Methods 0.000 description 1
- 238000005395 radioluminescence Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a luminescent silicate material with long persistence, which has the main chemical composition expression of aMO. bM'O. cSiO2. dR: Eux. Lny, wherein M is one element or more elements selected from Sr, Ca, Ba and Zn; M' is one element or more elements selected from Mg, Cd and Be; R is one component or more components selected from B2O3 and P2O5; Ln is one element or more elements selected from Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Mn, Bi, Sn and Sb; a, b, c, d, x and y are molar coefficients, wherein a is from 0.6 to 6, b is from 0 to 5, c is from 1 to 9, d is from 0 to 0.7, x is from 0.00001 to 0.2 and y is from 0 to 0.3. After absorbing light with a short wavelength, the material has luminescent effect with long persistence.
Description
The present invention is a long after glow luminous material, particularly be long persistence luminescent silicate material and manufacture method thereof.
Traditional ZnS series long after glow luminous material is since the invention of 19th century, through constantly improving, several typical products have been formed, as: ZnS:Cu (green emitting), (CaSr) S:Bi (blue look luminous), (ZnCd) S:Cu (yellow orange is luminous), and be applied to some commercial field, but the shortcoming of this class material is a poor stability, easily decomposes in air, and variable ash is to black under solar radiation, luminous time of persistence is short, generally in 0.5-2 hour, and luminosity is on the low side, does not satisfy practical requirement.In order to improve the luminosity of material, prolong time of persistence, people have successively added Co, Ra, H in this class material
3In radioelement, made the radioluminescence long-afterglow material, though make material sustainable luminous and once be applied to fields such as instrument, clock and watch, because radioactive pollution and costing an arm and a leg, use range is subjected to very big restriction.
The early 1990s, invented the long after glow luminous material of aluminates system, shown in Chinese patent publication number CN1053807A and Chinese patent ZL92110744.7, its luminosity, steady persistence performance, stability all significantly are better than above-mentioned sulfide series product, have begun to be applied at aspects such as daily necessities, weak illumination Pointing sign board, clock and watch.But this class material remains in poor water resistance, purity of raw materials, form is required high, and production cost is higher, and shortcoming such as illuminant colour is single, can not satisfy the requirement to long after glow luminous material to a certain extent again well.
Nineteen sixty-eight T.L.Barry once delivered Me
3MgSi
2O
8: Eu
Z+(Me=Ca, Sr, Ba) and Me
2SiO
4: Eu
2+The luminescent spectrum of (Me=Sr, Ba) and excitation spectrum result of study (j.Electrochem.Soc.V115 No.7,733-738, nineteen sixty-eight; V115 No.11,1181-1184, nineteen sixty-eight); T.L.Barry has delivered BaMg again subsequently
2Si
2O
7: Eu
Z+The result of study (J.Electrochem.Soc.V117 NO.3,381-385,1970) of luminous and excitation spectrum; Nineteen sixty-eight Blasse, G. etc. have delivered Fluorescence of Eu
2+Activated silicates (Philips Res.Rep. (1968), 23 (2), 189-200).But do not see the report of silicate material so far with strong steady persistence performance.
At above the deficiencies in the prior art, the invention provides that a kind of color is various, spectral range is wide, water tolerance and excellent in stability, the silicate series long after glow luminous material that afterglow intensity height and time are long.
The present invention is after the aluminates system long after glow luminous material, the long after glow luminous material of another novel system, Here it is with silicate is that matrix, rare earth ion and other ion are activator, and the compound that adds a certain amount of boron or the phosphorus long after glow luminous material of facilitating the steady persistence performance to improve, in silicate systems, realized the long-persistence luminous characteristics of polychrome such as blue, green, Huang.
The main chemical constitution of long after glow luminous material of the present invention can be used formula (1) expression:
AMObM ' OcSiO
2DR:Eux, Lny (1) wherein M are selected from one or more elements in strontium (Sr), calcium (Ca), barium (Ba), the zinc (Zn); M ' is selected from one or more elements in magnesium (Mg), cadmium (Cd), the beryllium (Be); R is selected from B
2O
3, P
2O
5In a kind of or two kinds of compositions; Ln is selected from one or more elements in neodymium (Nd), dysprosium (Dy), holmium (Ho), thulium (Tm), lanthanum (La), praseodymium (Pr), terbium (Tb), cerium (Ce), manganese (Mn), bismuth (Bi), tin (Sn), the antimony (Sb), a, b, c, d, x, y are mole coefficient, 0.6≤a≤6 wherein, 0≤b≤5,1≤c≤9,0≤d≤0.7,0.00001≤x≤0.2,0≤y≤0.3; This material excites down in the following short wavelength light of 500nm, sends the emmission spectrum of 420～650nm, and peak value is 450～580nm, and it is long-persistence luminous to present colors such as orchid, blue green, green, greenish-yellow, Huang.
M is selected from a kind of or two kinds of elements among Sr, the Ca in a kind of long after glow luminous material of preferred version according to the present invention, its formula of (1); M ' is Mg; Ln is selected from one or more elements among Nd, Dy, Ho, Bi, the Sn, and wherein: 0.6≤a≤4,0.6≤b≤4,1≤c≤5,0＜d≤0.4, R is selected from B
2O
3, P
2O
5In a kind of or two kinds of compositions.
A kind of long after glow luminous material according to the present invention, wherein the main compound of material is: M
2MgSi
2O
7Or M
3MgSi
2O
8, wherein M is Sr
1-zCa
z, 0≤z≤1.
A kind of long after glow luminous material according to the present invention, wherein the main chemical expression formula of material is: M
2MgSi
2O
7: Eu, Ln or M
3MgSi
2O
8: Eu, Ln, wherein M is Sr
1-zCa
z, 0≤z≤1.
When making long after glow luminous material of the present invention, employing contains the compound of element in the expression (1), generally select for use in the raw material, the compound of M, M ', Ln, Eu is carbonate, vitriol, nitrate, phosphoric acid salt, borate, acetate, oxalate, Citrate trianion or its oxide compound of using their representative elements respectively, oxyhydroxide, halogenide etc., and the compound of Si is to use SiO
2, silicic acid, silica gel or silicate, R is the compound of boron, phosphorus, raw materials used in element mole proportioning be:
M:0.6～6 R:0～0.7 is with B
2O
3, P
2O
5Meter
M′：0～5 Eu：0.00001～0.2
Si:1～9 Ln:0～0.3 is wherein: M represents the compound of one or more elements among Sr, Ca, Ba, the Zn;
M ' represents the compound of one or more elements among Mg, Cd, the Be;
R represents the compound of a kind of or two kinds of elements among B, the P;
Ln represents among Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Mn, Bi, Sn, the Sb
The compound of one or more elements;
Si represents the compound of Si;
Eu represents the compound of Eu.
Its manufacturing process adopts high-temperature solid phase reaction method to make, above-mentioned raw materials is taken by weighing by the mole proportioning, porphyrize also mixes, can be used for the method for mixing during mixing, also available solubilizing agent (as ethanol, acetone etc.) mixes the back oven dry, or adopts chemical reaction melten gel one gel method, make mixture, pack in the vessels crucible, put into High Temperature Furnaces Heating Apparatus, under reducing atmosphere (as hydrogen (H
2), ammonia (NH
3), nitrogen and hydrogen (N
2+ H
2), carbon granules (C grain)), in 1100-1400 ℃, according to body of heater capacity and weight of material, sintering 2 to 50 hours, general a small amount of material is 2-5 hour.For improving the quality of material, can in raw material, add a small amount of other compound, as NH
4Cl, NH
4F, CaF
2, SrF
2, Li
2CO
3, CaSO
4, SrSO
4, SrHPO
4, CaHPO
4Deng.Behind the sintering,,, sieve into particle diameter materials at different levels according to service requirements through cooling off, pulverize, sieve operation.
It is the disk that sample is placed diameter 50mm, dark 5mm that the present invention carries out luminous afterglow measurement to sample, keep more than the 10h in the darkroom, taking-up places under the standard D65 light source 10001x illumination, uses its time dependent luminous intensity of glorious degrees instrumentation behind the irradiation 10min.Comparative sample to prior art in the time of test excites under identical conditions, is 100 with comparative sample, asks for the relative afterglow intensity of sample.Blue colour excess brightness comparative sample is (CaSr) S:Bi; Yellow twilight sunset comparative sample is (ZnCd) S:Cu; Green, blue comparative sample green, greenish-yellow twilight sunset is ZnS:Cu.The crystalline structure of material and compound are formed employing x-ray diffraction mode and are recorded, and survey its x-ray diffraction numerical value, and contrast with the card value, determine its main compound.The emmission spectrum of material and excitation spectrum adopt the fluorescence spectrophotometer test.
Research work show in a large number, in chemical constitution expression (1), and the element difference in M, M ', the long-persistence luminous color difference of material, the main compound difference of material; A, b, the numerical value change of c has certain influence to luminous intensity, compound structure and the glow color of material; The numerical value change of different elemental compositions among R and the Ln and coefficient d, x, y has tangible influence to luminous intensity, and the main compound structure is not seen tangible influence.
Glow color and M, M ' that table 1 has provided material reach a, b relative section test-results.
Table 1 test conditions is to select c=2.5 in the expression, d=0.1, R=B for use
2O
3, x=0.005, y=0.04 Ln=Nd, reducing atmosphere is selected N for use
2(90%)+H
2(10%), synthesis temperature 1250-1320 ℃, 4 hours time.
The test of table 1 glow color
When representing Sr or Sr, M is principal element wherein, Ca, Ba, Zn are minor element, on behalf of Mg or Mg, M ' be principal element wherein, and when Cd, Be were minor element, the synthetic material presented Lan Se-Lan green long afterglow glow color after the following short wavelength light irradiation of 450nm.Experiment shows the different numerical value of a, b, c, luminous intensity and structure to material have certain influence, when 0.6≤a≤4,0.6≤b≤4,1≤c≤5, material present stronger Lan Se-Lan green emitting, when 1.5≤a≤2.4,0.6≤b≤2,1.5≤c≤2.5 o'clock are Sr from the main compound of X one optical diffraction data analysis material
2MgSi
2O
7, as shown in Figure 2; When exceeding above-mentioned coefficient scope, also compound S r can appear in the material
2MgSi
2O
7, but other compound composition is more; When 2.7≤a≤3.3,0.8≤b≤1.2,1.7≤c≤2.3 o'clock.The main compound of material is Sr
3MgSi
2O
8, as shown in figure 14.
Be principal element wherein when M represents Ca or Ca, Sr, Ba, Zn are minor element, and on behalf of Mg or Mg, M ' be principal element wherein, and when Cd, Be were minor element, the synthetic material presented green-yellow longpersistent glow color after the following short wavelength light irradiation of 500nm.Same experiment shows the different numerical value of a, b, c, and the luminous intensity and the structure of material had certain influence.When 0.6≤a≤4,0.6≤b≤4,1≤c≤5, material present stronger green-Yellow luminous, when 1.5≤a≤2.4,0.6≤b≤2,1.5≤c≤2.5 o'clock, be Ca from the main compound of x-ray diffraction data analysis material
2MgSi
2O
7, as shown in Figure 6; When exceeding above-mentioned coefficient scope, also Compound C a can appear in the material
2MgSi
2O
7, but other compound composition is more; When 2.7≤a≤3.3,0.8≤b≤1.2,1.7≤c≤2.3 o'clock, the main compound of material is Ca
3MgSi
2O
8, as shown in figure 16.
When M represents Sr or/and Ca for representing convenience, adopts Sr
1-zCa
zFormula is represented, wherein 0≤z≤1, or Sr
1-zCa
zBe principal element wherein, Mg, Ba, Zn, Cd, when Be is minor element, it is its principal element that M ' represents Mg or Mg, when Sr, Ca were minor element, the synthetic material changed with the z value, present Lan-Lan green-green-greenish-yellow-yellow longpersistent glow color changes.When z=0 is blue look, z=1 is green-yellow, 0＜z＜0.5 be mainly blue green-green color, green-greenish-yellow color that 0.5＜z＜1 is mainly, near z=0.5 or be green when.Same a, b, the different numerical value of c have certain influence to the luminous intensity and the structure of material, when 0.6≤a≤4,0.6 it is luminous that≤b≤4,1≤c≤5, material present stronger blue green-green-green-yellow, when 1.5≤a≤2.4,0.6≤b≤2,1.5≤c≤2.5, the main compound of material is from its diffraction spectrogram of x-ray diffraction data analysis and above-mentioned Sr
2MgSi
2O
7And Ca
2MgSi
2O
7Spectrogram is very close, in conjunction with element proportioning in the expression, therefore is inferred as (Sr
1-zCa
z)
2MgSi
2O
7Compound, as shown in Figure 9; When exceeding above-mentioned coefficient scope, also (Sr can appear in the material
1-zCa
z)
2MgSi
2O
7Compound, but other compound composition is more.
With reference to the expression of the relevant material of luminescence, when the crystalline structure of material still be can not determine, represent that with the main component of this material promptly the chemical constitution expression is represented; After the main chemical combination of material and crystalline structure are determined, represent with the chemical expression formula.
Compound and crystalline structure according to above-mentioned materials.The main chemical expression formula of this class material of the present invention: M
2MgSi
2O
7Eu
x, Ln
yOr M
3MgSi
2O
8Eu
x, Ln
y, wherein M is Sr
1-zCa
z, 0≤z≤1.
When M represents Ba, 4≤a≤6, b=0,6≤c≤9, it is long-persistence luminous that material presents light green, determines that from the x-ray diffraction data main compound is Ba
5Si
8O
21The main chemical expression formula of this class material of the present invention: Ba
5Si
8O
21: Eu
x, Ln
y
When M represents Zn, 1≤a≤3, b=0,0.7≤c≤1.5, it is long-persistence luminous that material presents light green, determines that from the x-ray diffraction analytical data main compound is Zn
2SiO
4The main chemical expression formula of this class material of the present invention: Zn
2SiO
4: Eu
x, Ln
y
When M represents Sr
1-zCa
z, 0≤2≤1, M ' represents Mg, and wherein 0～40% of M, M ' mole can be replaced by Ba, Zn, Cd, Be, and material has the luminescent properties of steady persistence, and especially when Ba, Cd accounted for the 5-20% mole, material had good luminous property.
In the chemical constitution expression, there is not R or/and the Ln element when being zero (be d or/and y), the synthetic material also can send twilight sunset, and the combination that has has stronger afterglow.But R has been arranged in the material or/and Ln, its twilight sunset luminous intensity has had significant enhancing, and the different of its mole coefficient d and y have certain influence to afterglow intensity certainly.The adding of various element among the Ln, the element difference, the luminous intensity difference, mixing of two above complex elements is more better than the adding illumination effect of single-element.
Work as y=0, the chemical constitution expression of material is aMObM ' OcSiO
2DR:Eux, europium (Eu) is an activator, from the spectroscopic analysis of material, the emmission spectrum of this material is divalent europium (Eu
2+) characteristic emission spectrum, promptly europium is a dominant activator, along with x numerical value difference, its long-persistence luminous intensity presents different variations, the preferred range of x is: 0.00001≤x≤0.2.
When y＞0, increase the Ln composition in the material, experiment shows, a kind of or several existence of Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Mn, Bi, Sn, Sb in the Ln composition are to the long-persistence luminous intensity generation reinforced effects in various degree of material, especially Nd, Dy, Ho, Bi, Sn effect are remarkable, experiment shows that when 0＜y≤0.3 material is all had tangible enhancement, shown in table 2～10 tests, by the luminescence theory, can be as the coactivator effect.
Work as d=0, the chemical constitution expression of material is aMObM ' OcSiO
2: Eux, Lny, this material present certain long-persistence luminous effect, and along with the change of x, y value, the long-persistence luminous intensity of material also is certain variation.
When d＞0, the adding of R composition when making the relative d=0 of the long-persistence luminous intensity of material, is significantly improved, and the raw material of d composition can be the compound of boron (B) or phosphorus (P), as boron trioxide (B
2O
3), boric acid (H
3BO
3), Vanadium Pentoxide in FLAKES (P
2O
5), phosphoric acid (H
3PO
4), Secondary ammonium phosphate ((NH
4)
2HPO
4), primary ammonium phosphate (NH
4H
2PO
4) etc., the adding of these compositions has improved the long-persistence luminous intensity of material; Reduced the synthesis temperature of material, improved the synthetic quality of material, the synthetic materials powder is loose, the yield rate height.
The R composition sees Table 2 to the luminous influence of material.
Blue green material is selected in table 2 test for use, gets M=Sr
0.75Ca
0.25, M '=Mg, R=B
2O
3Or/and P
2O
5, Ln=Dy, a=1.5, b=1.5, c=2.5, x=0.01, y=0.08, reducing atmosphere are NH
3Gas, synthesis temperature are 1280 ℃.
Table 2 R, Ln composition effect test
The R add-on is as shown in table 3 to the luminous influence of material.
Lan Se and green material are selected in table 3 test for use, wherein test 1～8 blue look material and get M=Sr, M '=Mg, a=2, b=1, c=2, x=0.004, R=B
2O
3
Test 9～14 is green material, wherein M=Sr
0.5Ca
0.5, M '=Mg, a=2, b=1, c=2.3, R=P
2O
5, Ln=Dy, x=0.004, y=0.01.
Table 3 R becomes component (d) influence test
Experiment shows that 0＜d≤0.7 pair material luminous intensity has certain influence, and add-on is good with 0＜d≤0.4.The existence of R composition, x-ray diffraction data analysis from material, the known crystalline structure compound composition of previous materials is not produced big influence, main compound is the silicate composition, but material is carried out the ultimate analysis test, confirm to show that boron (B), phosphorus (P) element among the R are present in the material, promptly contain boron, phosphorus composition in the material, by chemical constitution, be labeled as B
2O
3And P
2O
5
Narrate material of the present invention below in conjunction with part test: (one) blue look long after glow luminous material
Work as M=Sr, M '=Mg, R=B
2O
3, a=2, b=1, c=2, d=0.1, the chemical constitution expression of material is: 2SrOMgO2SiO
20.1 B
2O
3: Eux, Lny, element and the y value of change x value, Ln, its test-results is as shown in table 4
Table 4
Continuous table 4
Last table 4 test materials is behind sunlight, fluorescent lamp or ultra violet lamp, and it is luminous to present blue colour excess brightness; Under the 365nm ultraviolet excitation, present 420-550nm broadband emission spectrum, near the peak value 469nm; Monitoring 469nm place, its excitation spectrum is the following wideband spectrum of 450nm, illustrates that this material has stronger receptivity to short wavelength light; Determine its main compound Sr through the x-ray diffraction spectrogram
2MgSi
2O
7Because the composition difference that adds, the spectrographic peak value can produce certain displacement.Fig. 1 (a) and (b) and Fig. 2 are respectively emmission spectrum, excitation spectrum and the x-ray diffraction spectrograms of test 1-4 material, and its emmission spectrum peak value is 469nm; Fig. 3 (a) and (b) are emmission spectrum, excitation spectrums of test 3-4 material, and its emmission spectrum peak value is 470nm.
1. as if y=0 in the chemical constitution expression, promptly do not have the Ln ion and exist, the add-on of Eu has certain influence to the twilight sunset effect, sees Table to test in 4 shown in 1-1～7.Same comparative sample (CaSr) S:Bi compares, and this material presents certain long-persistence luminous effect.Further experiment shows, when the molar weight of Eu * less than 0.00001 with greater than 0.2 the time, its illumination effect is relatively poor, therefore given 0.00001≤x≤0.2.
2. if x=0.004, Ln=Nd, the twilight sunset effect of the variation correspondence of add-on y sees Table and tests 2-1～6 in 4, and add-on y is advisable with 0.0001≤y≤0.3, afterglow intensity is apparently higher than test 1-1～7 as can be seen, and the adding of this explanation Nd has increased the luminescent properties of material.The luminous twilight sunset of test 2-4 material changed in time carry out the curve plotting of double-log persistence characteristic, this curve is straight line substantially, the minimum visual luminosity 0.32mcd/m of intelligent's eye
2Time is more than 20h.
3. if x=0.004, Ln=Dy, the variation of add-on y sees Table the twilight sunset effect and tests 3-1～7 in 1, and add-on is advisable with 0.0001≤y≤0.3, and afterglow intensity is apparently higher than test 1-1～7 as can be seen, and the adding of this explanation Dy has increased the luminescent properties of material.The luminous twilight sunset of test 3-4 material changed in time carry out the curve plotting of double-log persistence characteristic, this curve is straight line substantially, sees shown in Figure 4ly, and the time of the minimum visual luminosity of intelligent's eye is more than 35h.
4. as if x=0.004, Ln is respectively Ho, Tm, La, Pr, Tb, Ce, Mn, Bi, Sb, Sn and dual element Nd, Dy; Nd, Sn; Dy, Bi, the twilight sunset effect of its add-on y correspondence sees Table 4 test 4～16 respectively.
The above result luminous twilight sunset effect of this class material as can be seen all obviously is better than contrast material.Particularly add Nd, Dy, Ho, Bi, its effect of Sn is more remarkable.According to the crystalline structure and the main compound of above-mentioned materials, the chemical expression formula of this orchid color system material is Sr
2MgSi
2O
7: Eu, Ln.
Two, yellow longpersistent luminescent material
Work as M=Ca, M '=Mg, R=B
2O
3, a=2, b=1, c=2, d=0.15, the chemical constitution expression of material is: 2CaOMgO2SiO
20.15B
2O
3: Eux, Lny, element and the y value of change x value, Ln, its test-results is as shown in table 5.Table 5
Last table 5 test materials presents yellow afterglow behind sunlight, fluorescent lamp or ultra violet lamp; Under the 365nm ultraviolet excitation, present 420～650nm broadband emission spectrum, near the peak value 535nm; Monitoring 535nm place, its excitation spectrum is the following wideband spectrum of 500nm, illustrates that this material has stronger receptivity to short wavelength light; Determine that through the x-ray diffraction spectrogram main compound is Ca
2MgSi
2O
7Because the composition difference that adds, its spectrographic peak value can produce certain displacement.Fig. 5 (a) and (b) and Fig. 6 are respectively test 2-3 material emmission spectrum, excitation spectrum and x-ray diffraction spectrogram, its emmission spectrum peak value 535nm.
1. as if y=0 in the chemical constitution expression, the add-on of Eu has certain influence to the twilight sunset effect, sees Table to test in 5 shown in 1-1～7.
2. if x=0.004, Ln=Dy, the variation of add-on y sees Table shown in 2-1 in 5～4 the twilight sunset effect, the adding of Dy has strengthened the luminescent properties of material as can be seen, experiment shows that the Dy add-on is good with 0.0001≤y≤0.2, and Fig. 7 is the time dependent double-log rational curve of luminous twilight sunset of test 2-3 material.
3. during as if x=0.004, Ln is respectively Nd, Ho, Tm, Ce, Sn, Bi and dual element Dy, Nd; Dy, Bi, add-on and twilight sunset effect see Table respectively to be tested in 5 shown in 3～10, and its luminous twilight sunset effect all obviously is better than contrast material.
According to the crystalline structure and the main compound of above-mentioned materials, the chemical expression formula of this corpora flava based material is Ca
2MgSi
2O
7: Eu, Ln.Three, green long afterglow luminescent material
Work as M=Sr
0.5Ca
0.5, M '=Mg, R=B
2O
3, a=2, b=1, c=2, d=0.05, the chemical constitution expression of material is 2 (Sr
0.5Ca
0.5) OMgO2SiO
20.05B
2O
3: Eux, Lny, change x value, Ln element and y value, its test-results is as shown in table 6.
Table 6
Last table 6 test materials presents green afterglow behind sunlight, fluorescent lamp or ultra violet lamp; Under the 365nm ultraviolet excitation, present 430～600nm broadband emission spectrum, near the peak value 500nm; Monitoring 500nm place, its excitation spectrum is the wideband spectrum below 460nm, this illustrates that this material has stronger receptivity to short wavelength light; Through the x-ray diffraction data analysis, its diffraction spectrogram and Sr
2MgSi
2O
7And Ca
2MgSi
2O
7Spectrogram is very close, in conjunction with Sr, Ca mole proportioning in the expression, infers that its main compound is (Sr
0.5Ca
0.5)
2MgSi
2O
7, as shown in Figure 9.Because add the composition difference, its spectrum peak can produce certain displacement.Fig. 8 (a) and (b) and Fig. 9 are respectively emmission spectrum, excitation spectrum and the x-ray diffraction spectrograms of test 2-5 material, and its emmission spectrum peak value is 500nm.
1. as if y=0 in the chemical constitution expression, the add-on of Eu sees Table the twilight sunset effect and tests in 6 shown in 1-1～6.
2. if x=0.005, Ln=Dy, the variation of add-on y to the twilight sunset effect see Table test in 6 2-1～
3. if during x=0.005, Ln=Nd, the variation of add-on y sees Table test 3-1～3 in 6 to the twilight sunset effect, and afterglow intensity also is very high as can be seen, and time of persistence is also very long.
4. as if x=0.005, Ln is respectively Ho, Tm, Ce, Sn, Tb, Pr, Bi, and influence sees Table 6 test 4-10 to its add-on to afterglow intensity.
5. if x=0.005, Ln=Dy and Bi, it adds simultaneously has bigger enhancing to luminous afterglow intensity, sees Table to test 11 in 6.
According to the crystalline structure and the main compound of above-mentioned materials, the chemical expression formula of this green body based material is: (Sr
0.5Ca
0.5)
2MgSi
2O
7: Eu, Ln.Four, blue green-green-yellow long after glow luminous material
Work as M=Sr
1-zCa
z, M '=Mg, R=B
2O
3, a=2, b=1, c=2, d=0.1, the chemical constitution expression of material is: 2 (Sr
1-zCa
z) OMgO2SiO
20.1B
2O
3: Eu
x, Lny, 0≤z≤1, along with the z value is different, the luminous twilight sunset color difference of its material is when z=0 then is blue look; Z=1 then is yellow; Z=0.5 then is green.Along with the variation of z value from 0 to 1, promptly change the ratio of Sr and Ca, the glow color of material then presents the blue green xanchromatic variation of arriving of arriving.
1. table 7 is listed in 2 (Sr
1-zCa
z) OMgO2SiO
20.1B
2O
3: Eu
0.004, Dy
0.02In, the ratio of test Sr and Ca changes the influence to the emmission spectrum peak value, and along with the variation of z value from 0～1, emission spectra peak causes glow color to present orchid, green, green, greenish-yellow, the yellow variation of orchid from 496nm to 535nm, is shown in Table 7 as can be seen.Table 7
2. at z=0.25, select chemical constitution expression 2 (Sr
0.75Ca
0.25) OMgO2SiO
20.1B
2O
3: Eu0.00
4, Ln
0.02Test, as testing in the table 8 shown in 1～6, it is luminous that its material is blue green long afterglow, the Ln ionic adds, its luminous intensity is significantly strengthened, compared very big difference as test 2 in the table 8 with comparative sample, presented very strong blue green afterglow, its emmission spectrum, excitation spectrum are seen shown in Figure 11 (a) and (b).
3. at z=0.75, select chemical expression formula 2 (Sr
0.25Ca
0.75) OMgO2SiO
20.1B
2O
3: Eu
0.004, Ln
0.02Test, shown in test 7-12 in the table 8, it is long-persistence luminous that its material is yellow-green colour, the Ln ionic adds, its luminous intensity is significantly strengthened, compared significant difference as test 8 in the table 8 with comparative sample, its emmission spectrum, excitation spectrum are seen shown in Figure 12 (a) and (b).
Table 8
Five, other is luminous
1. in the chemical constitution expression, work as M=Sr
1-zCa
z, 0≤z≤1 wherein, M '=Mg, R=B
2O
3, a=3, b=1, c=2, d=0.1, i.e. 3MOMgO2SiO
20.1B
2O
3: Eux, Lny, this material present orchid-yellow-green colour afterglow.
M=Sr is selected in test 1 in the table 9, and it is luminous that Ln=Dy, Nd, this material are blue colour excess brightness.Figure 13 (a) and (b) and Figure 14 are respectively 3SrOMgO2SiO
20.1B
2O
3: Eu
0.004, Dy
0.02The emmission spectrum of material, excitation spectrum and x-ray diffraction spectrogram, its emmission spectrum peak value is 462nm, main compound is Sr
3MgSi
2O
8, less important compound is Sr
2MgSiO
7The chemical expression formula of material: Sr
3MgSi
2O
8: Eu, Ln.
M=Ca is selected in test 2 in the table 9, Ln=Dy, Nd, and this material presents the light green afterglow.Figure 15 (a) is respectively 3CaOMgO2SiO with Figure 16 (b)
2: Eu
0.004, Dy
0.02The emmission spectrum of material, excitation spectrum and x-ray diffraction spectrogram, its emmission spectrum peak value 475nm, main compound is Ca
3MgSi
2O
8, less important compound is Ca
2MgSi
2O
7
Equally, work as M=Sr
0.5Ca
0.5, Ln=Dy, Nd, this material are blue green afterglow, and its luminous twilight sunset effect sees Table to be tested in 9 shown in the 3-1,2.
Table 9
2. in the chemical constitution expression, when M represents Sr
1-zCa
z, 0≤z≤1 wherein, M ' represents Mg, and the middle element of M and M ' can be replaced by the Ba of 0-40% mole, Zn, Cd, Be, and material can present orchid, green, yellow isochrome afterglow.
M presents the green twilight sunset of Lan-Lan based on the material of Sr, and shown in test 1-1～4 in the table 10, its twilight sunset illumination effect is a comparative sample with (CaSr) S:Bi; M presents green-yellow twilight sunset based on the material of Ca, and shown in test 2-1～4 in the table 10, its twilight sunset illumination effect is a comparative sample with (ZnCd) S:Cu; M presents green twilight sunset based on the material of Sr and Ca, and shown in test 3-1～2 in the table 10, its twilight sunset illumination effect is comparative sample with ZnS:Cu.From showing to find out that luminous intensity significantly is better than comparative sample.Table 10
3. work as M=Ba, a=5, b=0, c=8, R=B
2O
3, d=0.1, material expression are 5BaO8SiO
20.1B
2O
3: Eux, Lny, select x=0.01, Ln=Dy, y=0.02, it is luminous that the test synthetic materials is light green, and its main compound is Ba
5Si
8O
21Its emmission spectrum, excitation spectrum are shown in Figure 17 (a) and (b), and table 11 is the relative effect of its twilight sunset.With Ca, Sr, Zn, Cd, Be replacement part Ba long-persistence luminous effect is arranged also.Table 11
4. work as M=Zn, R=B
2O
3, a=2, b=0, c=1, d=0.1, Ln=Dy and Mn, x=0.01, y=0.02, the test synthetic materials is the light green afterglow, and its main compound is Zn
2SiO
4: Eu, Dy, Mn, its twilight sunset illumination effect is shown in Table 12.With Ca, Sr, Ba, Cd, Be replacement part Zn long-persistence luminous effect is arranged also.Table 12
In material synthetic, when making same compound, use and contain in the raw material of Mg element, higher more than 50% with magnesium basic carbonate than the material luminous intensity that magnesium oxide makes.
The present invention finds that also other compound composition that adds its weight 0-15% in the raw material of material participates in solid state reaction, helps to improve the long-persistence luminous intensity of product, improves the synthetic quality of product, and does not influence the main crystalline structure of material.The effect that adds some compounds in greenish-yellow material is as shown in table 13.
Greenish-yellow material is selected in table 13 test for use, gets M=Sr
0.3Ca
0.7, M '=Mg, R=B
2O
3, Ln=Dy, a=2.5, b=1.2, c=2.5, d=0.1, x=0.02, y=0.1.
The adding influence test of other compound of table 13
In other combination in the chemical constitution expression, can find that equally also the adding of these compounds influences the twilight sunset effect more or less.
Material of the present invention has excellent water tolerance energy and stability, under identical conditions, the aluminate long afterglow materials and the silicate long-afterglow material of the present invention of prior art are put into water respectively, find that the aluminate material promptly begins hydrolysis after three days, to decompose fully after one week, the forfeiture luminescent properties, and silicate material is not seen decomposition after 3 months under similarity condition, still as seen luminous.
Product of the present invention can be widely used in the various long-persistence luminous goods of indoor and outdoor, sign and decoration as night or dark condition, this material can combine with media such as coating, plastics, rubber, printing ink, in fields such as building, traffic, fitting-up, fire-fighting emergent, daily necessities, clock and watch, fishing gear, toys, has better purposes.
The present invention compared with prior art has three big characteristics:
(1) having invented is the novel system long after glow luminous material of main matrix composition with silicate, has higher chemical stability and water resistance, and has realized that blue, blue green, green, greenish-yellow, yellow multiple color is long-persistence luminous.
(2) in this system material, found the remarkable enhancement that different kinds of ions is luminous to europium ion, improved the luminescent properties of material.
(3) interpolation of boron and phosphoric compound has further improved the luminescent properties of material.
Caption: Fig. 1 represents Sr
2MgSi
2O
7: the emmission spectrum of Eu material (a) and excitation spectrum (b) Fig. 2 represent Sr
2MgSi
2O
7: x-ray diffraction pattern Fig. 3 of Eu material represents Sr
2MgSi
2O
7: the emmission spectrum of EuDy material (a) and excitation spectrum (b) Fig. 4 represent Sr
2MgSi
2O
7The persistence characteristic graphic representation 5 expression Ca of EuDy material
2MgSi
2O
7: the emmission spectrum of EuDy material (a) and excitation spectrum (b) Fig. 6 represent Ca
2MgSi
2O
7: x-ray diffraction pattern Fig. 7 of EuDy material represents Ca
2MgSi
2O
7: the persistence characteristic graphic representation 8 expression (Sr of EuDy material
0.5Ca
0.5)
2MgSi
2O
7: the emmission spectrum of EuDy material (a)
And excitation spectrum (b) Fig. 9 represents (Sr
0.5Ca
0.5)
2MgSi
2O
7: x-ray diffraction pattern Figure 10 of EuDy material represents (Sr
0.5Ca
0.5)
2MgSi
2O
7: persistence characteristic curve Figure 11 of EuDy material represents (Sr
0.75Ca
0.25)
2MgSi
2O
7: the emmission spectrum of EuDy material (a)
And excitation spectrum (b) Figure 12 represents (Sr
0.25Ca
0.75)
2MgSi
2O
7: the emmission spectrum of EuDy material (a)
And excitation spectrum (b) Figure 13 represents Sr
3MgSi
2O
8: the emmission spectrum of EuDy material (a) and excitation spectrum (b) Figure 14 represent Sr
3MgSi
2O
8: x-ray diffraction pattern Figure 15 of EuDy material represents Ca
3MgSi
2O
8: the emmission spectrum of EuDy material (a) and excitation spectrum (b) Figure 16 represent Ca
3MgSi
2O
8: x-ray diffraction pattern Figure 17 of EuDy material represents Ba
5Si
8O
21: emmission spectrum of EuDy material (a) and excitation spectrum (b)
Embodiment example 1.2SrOMgO2SiO
20.1B
2O
3: Eu
0.004Synthetic and the analytical results proportioning raw materials of material
| Element | Mole number | Raw material | Quantity |
| Sr Mg Si E Eu | 1.996 1 2 0.2 0.004 | SrCO 34MgCO 3·Mg(OH) 2·5H 2O SiO 2E 2O 3Eu 2O 3 | 294.6 restrain 97.1 grams, 120 grams, 6.96 grams, 0.704 gram |
Behind its porphyrize mixing, the alumina crucible of packing into is inserted in the High Temperature Furnaces Heating Apparatus, feeds ammonia (NH
3), in 1350 ℃ of sintering 3 hours, cooling was pulverized burned material again, and 100 eye mesh screens sieve, and make example materials.
This example materials outward appearance is canescence, and behind solar light irradiation, it is luminous in the dark to present blue colour excess brightness; Material carries out luminous afterglow intensity to be measured, shown in experiment 1-4 in the table 4; Example materials is carried out spectrum and structured testing, is respectively emmission spectrum, excitation spectrum and the x-ray diffraction spectrogram of example materials as Fig. 1 (a) and (b) and Fig. 2, and the main crystalline structure of this material is the structure of melilith, and its compound is Sr
2MgSi
2O
7According to its main compound, determine the chemical expression formula Sr of material
2MgSi
2O
7: Eu.Example 2.2SrOMgO2SiO
20.1B
2O
3: Eu
0.004Dy
0.04Synthetic and the analysis knot of material
The fruit proportioning raw materials
| Element | Mole number | Raw material | Quantity |
| Sr Mg Si B Eu Dy | 1.96 0.996 2 0.2 0.004 0.04 | SrCO 34MgCO 3·Mg(OH) 2·5H 2O SiO 2H 3BO 3Eu 2O 3Dy 2O 3 | 289.3 restrain 96.7 grams, 120 grams, 12.56 grams, 0.704 gram, 7.46 grams |
After the porphyrize mixing was dried in ethanolic soln with it, the alumina crucible of packing into placed High Temperature Furnaces Heating Apparatus, feeds ammonia (NH
3), in 1350 ℃ of sintering 3 hours, cooling, burned material is pulverized, and 100 eye mesh screens sieve, and make example materials.
This example materials outward appearance is canescence, and behind the sight light irradiation, it is luminous in the dark to present very strong blue colour excess brightness; The luminous twilight sunset relative intensity of material is shown in test 3-4 in the table 4, and its intensity level is apparently higher than example 1; The time of persistence of material is long, as shown in Figure 4; Fig. 3 (a) and (b) are emmission spectrum, the excitation spectrum of material; The main compound of material is Sr
2MgSi
2O
7, identical with example 1, the chemical expression formula Sr of therefore definite material
2MgSi
2O
7: Eu, Dy.Example 3.SrO3MgO2SiO
20.05P
2O
5: Eu
0.004Nd
0.01The synthesis material proportioning of material
| Element | Mole number | Raw material | Quantity |
| Sr Mg Si P Eu Nd | 0.993 2.993 2 0.1 0.004 0.01 | SrCO 34MgCO 3·Mg(OH) 2·5H 2O SiO 2(NH 4) 2HPO 4Eu 2O 3Nd 2O 3 | 146.6 restrain 290.6 grams, 120 grams, 13.2 grams, 0.704 gram, 1.68 grams |
After the porphyrize mixing was dried in acetone soln with it, the alumina crucible of packing into placed High Temperature Furnaces Heating Apparatus, feeds hydrogen (H
2), in 1350 ℃ of sintering 3 hours, cooling, burned material is pulverized, and 100 eye mesh screens sieve, and make example materials.
This example materials is behind ultra violet lamp, and it is luminous to be stronger blue colour excess brightness, and through the x-ray diffraction analysis, its main compound composition is Sr
2MgSi
2O
7And Mg
2SiO
4Therefore material adopts chemical constitution expression SrO3MgO2SiO
20.05P
2O
5: Eu, Nd.Example 4.2CaOMgO2SiO
20.15B
2O
3: Eu
0.004Dy
0.05Synthetic and the analytical results proportioning raw materials of material
| Element | Mole number | Raw material | Quantity |
| Ca Mg Si B Eu Dy | 1.946 1 2 0.3 0.004 0.05 | CaCO 34MgCO 3·Mg(OH) 2·5H 2O SiO 2H 3BO 3Eu 2O 3Dy 2O 3 | 194.6 restrain 97.1 grams, 120 grams, 18.84 grams, 0.764 gram, 9.325 grams |
Behind its porphyrize mixing, the alumina crucible of packing into places High Temperature Furnaces Heating Apparatus, feeds hydrogen and nitrogen (H
230%+N
270%), in 1320 ℃ of sintering 5 hours, cooling, burned material is pulverized, and 100 eye mesh screens sieve, and make example materials.
This example materials outward appearance is light yellow, after the fluorescent lamp irradiation, in the dark presents very strong yellow afterglow; The luminous twilight sunset relative intensity value of material shown in test 2-3 in the table 5, the test 1-4 of its intensity in the table 5, its emmission spectrum, excitation spectrum are shown in Fig. 5 (a) and (b); The time of persistence of material is long, and Fig. 7 is the persistence characteristic curve of material; The main compound of material is Ca
2MgSi
2O
7, as shown in Figure 6, therefore determine the chemical expression formula Ca of material
2MgSi
2O
7: Eu, Dy.Example 5.1.5CaO3MgO2SiO
20.15B
2O
3: Eu
0.004Ho
0.08The synthesis material proportioning of material
This example materials synthesis preparation method is with example 1.
| Element | Mole number | Raw material | Quantity |
| Ca Mg Si B Eu Ho | 1.5 3 2 0.15 0.004 0.08 | CaCO 34MgCO 3·Mg(OH) 2·5H 2O H 2SiO 3B 2O 3Eu 2O 3Ho 2O 3 | 150 grams, 291.3 grams, 156 grams, 10.44 grams, 0.704 gram, 15.1 grams |
This material is light yellow afterglow behind ultra violet lamp; Through the x-ray diffraction analysis, its compound composition is Ca
2MgSi
2O
7, CaMgSiO
4And Ca
3Si
2O
7The chemical constitution expression 1.5Ca03MgO2SiO of material
20.15B
2O
3: Eu, Ho.Example 6.2 (Sr
0.5Ca
0.5) OMgO2SiO
20.05B
2O
3: Eu
0.005Dy
0.08Proportioning raw materials
| Element | Mole number | Raw material | Quantity |
| Sr Ca Mg Si | 1 1 1 2 0.1 0.005 0.08 | SrCO 3CaCO 34MgCO 3·Mg(OH) 2·5H 2O SiO 2H 3BO 3Eu 2O 3Dy 2O 3 | 147.6 restrain 100 grams, 97.1 grams, 120 grams, 6.28 grams, 0.88 gram, 14.92 grams |
Behind its porphyrize mixing, the alumina crucible of packing into places High Temperature Furnaces Heating Apparatus, feeds ammonia (NH
3), in 1330 ℃ of sintering 3 hours, cooling, burned material is pulverized, and 100 eye mesh screens sieve, and make example materials.
This example materials is light green, after the fluorescent lamp irradiation, presents very strong green afterglow; Its luminous twilight sunset relative intensity is as shown in table 6, its emmission spectrum, excitation spectrum and x-ray diffraction light; Its luminous twilight sunset relative intensity is as shown in table 6, its emmission spectrum, excitation spectrum and x-ray diffraction pattern such as Fig. 8 (a) and (b) and shown in Figure 9; The time of persistence of material is long.Figure 10 is the persistence characteristic curve of material.The materials chemistry expression is (Sr
0.5Ca
0.5)
2MgSi
2O
7: Eu, Dy.Example 7.2 (Sr
0.25Ca
0.75) OMgO2.3SiO
20.05P
2O
5: Eu
0.01Nd
0.02The synthesis material proportioning of material
This example materials synthesis preparation method is with example 1.
| Element | Mole number | Raw material | Quantity |
| Sr Ca Mg Si P Eu Nd | 0.5 1.5 1 2.3 0.1 0.01 0.02 | Sr(NO 3) 2Ga(NO 3) 2·4H 2O Mg(NO 3) 2·6H 2O silica gel NH 4H 2PO 4Eu 2O 3Nd 2O 3 | 105.8 restrain 354 grams, 256.4 grams, 138 grams, 11.5 grams, 1.76 grams, 3.36 grams |
This material presents the green-yellow afterglow after the fluorescent lamp irradiation; Fig. 9 is very similar in the x-ray diffraction spectrogram of material and the example 6, therefore infers that its compound is (Sr
0.25Ca
0.75)
2MgSi
2O
7, its chemical expression formula (Sr
0.25Ca
0.75)
2MgSi
2O
7: Eu, Nd.Example 8.3SrOMgO2SiO
2: Eu
0.01Ho
0.08The synthesis material proportioning of material
This example materials synthesis preparation method is with example 1.This example materials is behind solar light irradiation, and it is luminous to be blue colour excess brightness, the main compound composition Sr of material
3MgSi
2O
8, less important compound S r
2Mg
2SiO
7, the chemical expression formula Sr of material
3MgSi
2O
8: Eu, Ho.Replace magnesium oxide with equimolar magnesium basic carbonate, the afterglow intensity of its synthetic materials is high by 75%.Example 9.2 (Sr
0.6Ca
0.4) O (Mg
0.8Cd
0.2) 02.5SiO
40.1B
2O
3: Eu
0.01Dy
0.02Bi
0.01The synthesis material proportioning of material
| Element | Mole number | Raw material | Quantity |
| Sr Mg Si Eu Ho | 3 1 2 0.01 0.08 | Sr(NO 3) 2MgO H 2SiO 3Eu 2O 3Ho 2O 3 | 634.8 restrain 40.3 grams, 156 grams, 1.76 grams, 15.1 grams |
In above mixing raw material, add the NH of its weight 5%
4Cl, behind porphyrize and the mixing, sintering process such as example 1, the material of preparing behind solar light irradiation, presents very strong blue green afterglow.Example 10.5BaO8SiO
20.1B
2O
3: Eu
0.01Dy
0.02The synthesis material proportioning of material
| Element | Mole number | Raw material | Quantity |
| Ba Si B Eu Dy | 5 8 0.2 0.01 0.02 | BaCO 3SiO 3B 2O 3Eu 2O 3Dy 2O 3 | 985 grams, 480 grams, 6.96 grams, 1.76 grams, 3.73 grams |
The synthesis preparation method of this example materials behind solar light irradiation, in the dark presents the light green afterglow with example 1, and the compound of material is Ba
5Si
eO
21, its chemical expression formula is Ba
5Si
8O
21: Eu, Dy.
Claims (14)
1. long after glow luminous material, it is characterized by main chemical constitution expression is aMObM ' OcSi0
2DR:Eu
x, Ln
y, wherein M is one or more elements that are selected among Sr, Ca, Ba, the Zn; M ' is selected from one or more elements among Mg, Cd, the Be; R is selected from B
2O
3, P
2O
5In a kind of or two kinds of compositions; Ln is selected from one or more elements among Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Mn, Bi, Sn, the Sb; A, b, c, d, x, y are mole coefficient, wherein 0.6≤a≤6,0≤b≤5,1≤c≤9,0≤d≤0.7,0.00001≤x≤0.2,0≤y≤0.3; Wherein y and d can not be 0 simultaneously, and when Ln is Bi, Mn or Sn d ≠ 0; This material excites down in the following short wavelength light of 500nm, presents the emmission spectrum of 420-650nm, and peak value is from 450-580nm, can present orchid, blue green, green, greenish-yellow, yellow color is long-persistence luminous.
2. long after glow luminous material as claimed in claim 1, it is characterized by main chemical constitution expression is aMObM ' OcSiO
2DR:Eu
x, wherein M is selected from one or more elements among Sr, Ca, Ba, the Zn; M ' is selected from one or more elements among Mg, Cd, the Be; R is selected from B
2O
3, P
2O
5In a kind of or two kinds of compositions; 0.6≤a≤6,0≤b≤5,1≤c≤9,0＜d≤0.7,0.00001≤x≤0.2.
3. long after glow luminous material as claimed in claim 1 is characterized by M in the chemical constitution expression and is selected from a kind of or two kinds of elements among Sr, the Ca; M ' is Mg; Ln is selected from one or more elements among Nd, Dy, the Ho; R is selected from B
2O
3, P
2O
5In a kind of or two kinds of compositions; 0.6≤a≤4,0.6≤b≤4,1.0≤c≤5,0≤d≤0.4.
4. long after glow luminous material as claimed in claim 1 is characterized by main chemical structure expression and is: M
2MgSi
2O
7: Eu
x, Ln
yOr M
3MgSi
2O
8: Eu
x, Ln
y, wherein M is Sr
1-zCa
z, 0≤z≤1; Ln is selected from one or more elements among Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, the Sb; 0.00001≤x≤0.2,0＜y≤0.3.
5. long after glow luminous material as claimed in claim 4 is characterized by Ln and is selected from one or more elements among Nd, Dy, the Ho.
6. as claim 4 or 5 described long after glow luminous material, it is characterized by the material main compound is M
2MgSi
2O
7Or M
3MgSi
2O
8, wherein M is Sr
1-zCa
z, 0≤z≤1.
7. long after glow luminous material as claimed in claim 1, it is characterized by main chemical structure expression is Ba
5Si
8O
21: Eu
x, Dy
y, 0.00001≤x≤0.2,0＜y≤0.3 wherein.
8. long after glow luminous material as claimed in claim 1, it is characterized by the main chemical structure expression of material is Zn
2SiO
4: Eu
x, Ln
y, wherein Ln=Dy, Mn, 0.00001≤x≤0.2,0＜y≤0.3.
9. long after glow luminous material as claimed in claim 2 is characterized by M in its chemical constitution expression and is selected from a kind of or two kinds of elements among Sr, the Ca; M ' is Mg; R is selected from B
2O
3, P
2O
5In a kind of or two kinds of compositions; 0.6≤a≤4.0,0.6≤b≤4.0,1≤c≤5,0＜d≤0.4.
10. as claim 3 or 9 described long after glow luminous material, the 0-40% mole that it is characterized by M, the middle element of M ' can be replaced by Ba, Zn, Cd, Be.
11. the preparation method of long after glow luminous material as claimed in claim 1, it is characterized by raw materials used in element mole proportioning be: M:0.6～6.0 R:O～0.7M ': 0～5.0 Eu:0.00001～0.2Si:1～9 Ln:0～0.3 wherein: M represents one or more element compounds among Sr, Ca, Ba, the Zn;
M ' represents one or more element compounds among Mg, Cd, the Be;
R represents the compound of a kind of or two kinds of elements among B, the P, with B
2O
3, P
2O
5Meter;
Ln represents the compound of one or more elements among Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Mn, Bi, Sn, the Sb;
Wherein representing mole coefficient y and the d of Ln and R can not be 0 simultaneously, and when Ln is Bi, Mn or Sn, d ≠ 0;
M, M ', Ln, Eu are one or more in carbonate, vitriol, nitrate, phosphoric acid salt, borate, acetate, oxalate, Citrate trianion or its oxide compound of using these representative elements respectively, oxyhydroxide, the halogenide, and the compound of Si is to use SiO
2, silicic acid, silica gel or silicate one or more, R is to use the compound of boron, phosphorus, it is measured with B
2O
3, P
2O
5Meter; Make and to carry out according to the following steps: with above-mentioned raw materials in molar ratio example take by weighing, porphyrize also mixes, and under reducing atmosphere,, forms through cooling off, pulverize, sieving after 2～50 hours in 1100-1400 ℃ of sintering.
12. the preparation method of long after glow luminous material as claimed in claim 11 is characterized by described reducing atmosphere and is selected under hydrogen, ammonia, nitrogen and hydrogen or the carbon granules existence.
13. the preparation method of long after glow luminous material as claimed in claim 11 is characterized by the NH that can add the 0-15% of raw material weight in mixing raw material
4Cl, NH
4F, Li
2CO
3, CaF, SrF
2, CaSO
4, SrSO
4, SrHPO
4Or CaHPO
4Participate in solid state reaction.
14. the manufacture method of long after glow luminous material as claimed in claim 11, to it is characterized by M ' be the Mg element, uses raw material to be magnesium basic carbonate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98105078A CN1062581C (en) | 1997-03-26 | 1998-03-20 | Long persistence luminescent silicate material and its producing method |
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|---|---|---|---|
| CN97103524.5 | 1997-03-26 | ||
| CN97103524 | 1997-03-26 | ||
| CN97123325.X | 1997-12-03 | ||
| CN98105078A CN1062581C (en) | 1997-03-26 | 1998-03-20 | Long persistence luminescent silicate material and its producing method |
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| CN1062581C true CN1062581C (en) | 2001-02-28 |
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Cited By (1)
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|---|---|---|---|---|
| CN1315982C (en) * | 2001-12-19 | 2007-05-16 | 住友化学工业株式会社 | Method for preparing silicate inorganic luminescent material |
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| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 116025 No. 32, high energy street, Dalian hi tech Zone, Dalian, Liaoning Patentee after: Dalian Luming Light Emitting Sci-Tech Co., Ltd. Address before: 116025 Liaoning Province, Dalian City High-tech Park Qixianling high-energy Street No. 1 Patentee before: Dalian Luming Light Emitting Sci-Tech Co., Ltd. |
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| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20010228 |