CN1194292A - Long persistence luminescent silicate material and its producing method - Google Patents
Long persistence luminescent silicate material and its producing method Download PDFInfo
- Publication number
- CN1194292A CN1194292A CN 98105078 CN98105078A CN1194292A CN 1194292 A CN1194292 A CN 1194292A CN 98105078 CN98105078 CN 98105078 CN 98105078 A CN98105078 A CN 98105078A CN 1194292 A CN1194292 A CN 1194292A
- Authority
- CN
- China
- Prior art keywords
- mgo
- 2sio
- long
- compound
- mgsi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 14
- 238000000034 method Methods 0.000 title claims description 11
- 230000002688 persistence Effects 0.000 title abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 28
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 20
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 17
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- 229910052788 barium Inorganic materials 0.000 claims abstract description 14
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 9
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 9
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 73
- 229910017639 MgSi Inorganic materials 0.000 claims description 64
- 238000001228 spectrum Methods 0.000 claims description 41
- 239000011777 magnesium Substances 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 29
- 241000233855 Orchidaceae Species 0.000 claims description 16
- 229910052693 Europium Inorganic materials 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 239000012190 activator Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000003746 solid phase reaction Methods 0.000 claims description 4
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 3
- 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
- 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
- 125000005587 carbonate group Chemical group 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
- 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 group O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 304
- 239000011575 calcium Substances 0.000 description 162
- 239000000395 magnesium oxide Substances 0.000 description 153
- 238000012360 testing method Methods 0.000 description 67
- 238000000695 excitation spectrum Methods 0.000 description 29
- 238000002441 X-ray diffraction Methods 0.000 description 27
- 239000011701 zinc Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000011572 manganese Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 8
- 238000005286 illumination Methods 0.000 description 8
- 229920002994 synthetic fiber Polymers 0.000 description 8
- 229910019440 Mg(OH) Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 101150027751 Casr gene Proteins 0.000 description 6
- 238000001816 cooling Methods 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
- 150000004645 aluminates Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- -1 rare earth ion Chemical class 0.000 description 4
- 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
- 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
- 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
- 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
- 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
- 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
- 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
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The silicate material has the chemical composition expression of aMO.bM'O.cSiO2.dR:Rux.Lny, where M is one or more of Sr, Ca, Ba, Zn; M' is one or more of Mg, Cd, Be; R is B2O3 and/or P2O5; Ln is one or more of Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Mn, Bi, Sn and Sb; and a, b, c, d, x and y are molar coefficients, a is 0.6-6, b 0-5, c 1-9, d 0-0.7, x 0.00001-0.2 and y 0-0.3. After absorbing short wavelength light, the said material has luminescent effect of long-term 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
2+(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
2+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 be selected from strontium (Sr), calcium (Ca),, one or more elements in the barium (Ba), 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
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 use dry mix during mixing, also available solubilizing agent (as ethanol, acetone etc.) mixes the back oven dry, or adopts chemical reaction melten gel-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 1000lx 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
| Test | The element coefficient | M：Sr????Ca????Ba????Zn a： | M′：Mg??Cd??Be b： | Glow color |
| ?????1 ?????2 ?????3 ?????4 ?????5 ?????6 ?????7 ?????8 ?????9 ????10 ????11 ????12 ????13 ????14 ????15 ????16 ????17 ????18 ????19 ????20 ????21 ????22 ????23 ????24 ????25 ????26 ????27 ????28 ????29 ????30 ????31 ????32 | ?????????????3???????0 ?????????????0???????3 ?????????????2???????0 ?????????????0???????2 ?????????????0.5?????1.5 ?????????????1.0?????1.0 ?????????????1.5?????0.5 ?????????????1???????0 ?????????????0???????1 ?????????????0.2?????0.8 ?????????????0.5?????0.5 ?????????????0.7?????0.3 ?????????????1???????0 ?????????????0???????1 ?????????????0.25????0.75 ?????????????0.5?????0.5 ?????????????0.75????0.25 ?????????????1???????1.8????0.2 ?????????????1.4?????1.4????????0.2 ?????????????2.0?????1 ?????????????1.4?????0.35 ?????????????1.2?????0.3 ?????????????1.0?????0.25 ?????????????0.875???0.875 ?????????????0.75????0.75 ?????????????0.625???0.625 ?????????????0.525???1.225 ?????????????0.45????1.05 ?????????????0.375???0.875 ?????????????0.263???1.487 ?????????????0.225???1.275 ?????????????0.187???1.063 | ?????1 ? ???1 ?????1 ?????1 ?????1 ?????1 ?????1 ?????2 ?????2 ?????1.9??0.1 ?????2 ?????1.9???????0.1 ?????3 ?????3 ?????3.0 ?????3.0 ?????3 ?????1 ?????1 ?????1 ?????1.25 ?????1.5 ?????1.75 ?????1.25 ?????1.5 ?????1.75 ?????1.25 ?????1.5 ?????1.75 ?????1.25 ?????1.5 ?????1.75 | The green orchid of the blue look green blue look yellow greenish-yellow green blue green blue look yellow greenish-yellow green blue green blue look yellow greenish-yellow green orchid of the green blue blue green orchid of greenish-yellow green is green green greenish-yellow greenish-yellow pale yellow pale yellow | |
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 blue look-blue 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-ray 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 orchid-orchid green-green-greenish-yellow-yellow longpersistent glow color variation.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.
According to the compound and the crystalline structure of above-mentioned materials, the main chemical expression formula of this class material of the present invention: M
2MgSi
2O
7: Eu, Ln or M
3MgSi
2O
8: Eu, Ln, 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, Ln.
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, Ln.
When M represents Sr
1-zCa
z, 0≤z≤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
| Sequence number | The chemical constitution expression | Luminous twilight sunset relative intensity 10 ' 60 ' |
| ??1 ??2 ??3 ??4 ??5 ??6 ??7 ??8 | 1.5(Sr 0.75Ca 0.25)O·1.5MgO·2.5SiO 2∶Eu 0.011.5(Sr 0.75Ca 0.25)O·1.5MgO·2.5SiO 2·0.1B 2O 3∶Eu 0.011.5(Sr 0.75Ca 0.25)O·1.5MgO·2.5SiO 2·0.05P 2O 5∶Eu 0.011.5(Sr 0.75Ca 0.25)O·1.5MgO·2.5SiO 2·0.1B 2O 3·0.05P 2O 5∶Eu 0.011.5(Sr 0.75Ca 0.25)O·1.5MgO·2.5SiO 2∶Eu 0.01Dy 0.081.5(Sr 0.75Ca 0.25)O·1.5MgO·2.5SiO 2·0.1B 2O 3∶Eu 0.01Dy 0.081.5(Sr 0.75Ca 0.25)O·1.5MgO·2.5SiO 2·0.05P 2O 5∶Eu 0.01Dy 0.081.5(Sr 0.75Ca 0.25)O·1.5MgO·2.5SiO 2·0.1B 2O 3·0.05P 2O 5∶Eu 0.01Dy 0.08 | ?40.1??????102 ?114???????176 ?94.6??????137 ?121???????182 ?772???????1540 ?2541??????4808 ?1724??????3946 ?2638??????4972 |
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
| Test | The chemical constitution expression | R composition (raw material) | ?d | Luminous twilight sunset relative intensity 10 ' 60 ' | Synthesis temperature (℃) |
| ??1 ??2 ??3 ??4 ??5 ??6 ??7 ??8 ??9 ??10 ??11 ??12 ??13 ??14 | ??2SrO·MgO·2SiO 2∶Eu 0.004??2SrO·MgO·2SiO 2·0.01B 2O 3∶Eu 0.004??2SrO·MgO·2SiO 2·0.05B 2O 3∶Eu 0.004??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004??2SrO·MgO·2SiO 2·0.2B 2O 3∶Eu 0.004??2SrO·MgO·2SiO 2·0.3B 2O 3∶Eu 0.004??2SrO·MgO·2SiO 2·0.5B 2O 3∶Eu 0.004??2SrO·MgO·2SiO 2·0.7B 2O 3∶Eu 0.004??2(Sr 0.5·Ca 0.5)O·MgO·2.3SiO 2∶Eu 0.004Dy 0.01??2(Sr 0.5·Ca 0.5)O·MgO·2.3SiO 2·0.05P 2O 5∶Eu 0.004Dy 0.01??2(Sr 0.5·Ca 0.5)O·MgO·2.3SiO 2·0.1P 2O 5∶Eu 0.004Dy 0.01??2(Sr 0.5·Ca 0.5)O·MgO·2.3SiO 2·0.2P 2O 5∶Eu 0.004Dy 0.01??2(Sr 0.5·Ca 0.5)O·MgO·2.3SiO 2·0.3P 2O 5∶Eu 0.004Dy 0.01??2(Sr 0.5·Ca 0.5)O·MgO·2.3SiO 2·0.5P 2O 5∶Eu 0.004Dy 0.01 | ?O 2H 3BO 32H 3BO 32H 3BO 32H 3BO 32H 3BO 32H 3BO 32H 3BO 3??O 2NH 4H 2PO 42NH 4H 2PO 42NH 4H 2PO 42NH 4H 2PO 42NH 4H 2PO 4 | ?0 ?0.01 ?0.05 ?0.1 ?0.2 ?0.3 ?0.5 ?0.7 ?0 ?0.05 ?0.1 ?0.2 ?0.3 ?0.5 | ??37.4???????100 ??78.7???????115.4 ?134.8???????169.2 ?132.4???????158.5 ?109.2???????127 ??94.5???????102 ??73.4????????96.4 ??42.1????????74.2 ?482.4??????1263.2 ?613????????1804 1034????????2542 ?807????????2326 ?721????????1742 ?501????????1271 | 1350 1340 1330 1320 1310 1280 1230 1150 1350 1340 1320 1310 1250 1200 |
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
20.1B
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
| Test | The chemical constitution expression | Twilight sunset relative intensity 10 ' 60 ' |
| ???1-1 ???1-2 ???1-3 ???1-4 ???1-5 ???1-6 ???1-7 | 2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.00012SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.00042SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.0012SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.0042SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.012SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.12SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.2 | ???67???????114 ???81???????122 ??124???????143 ??136???????178 ??130???????167 ???91???????121 ???80???????102 |
| ???2-1 ???2-2 ???2-3 ???2-4 ???2-5 ???2-6 | 2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Nd 0.0012SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Nd 0.0052SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Nd 0.012SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Nd 0.042SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Nd 0.12SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Nd 0.3 | ??621???????734 ??884???????896 ?1130??????1175 ?1527??????1847 ??862???????859 ??645???????692 |
| ???3-1 ???3-2 ???3-3 ???3-4 ???3-5 ???3-6 ???3-7 | 2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.00052SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.0042SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.012SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.042SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.082SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.152SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.3 | ??592???????913 ??927??????1754 ?1108??????2100 ?1658??????3947 ?1421??????3136 ?1215??????2306 ??823??????1214 |
| ???4-1 ???4-2 ???4-3 ???4-4 | 2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Ho 0.00042SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Ho 0.0012SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Ho 0.052SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Ho 0.1 | ??827??????1512 ?1014??????1894 ?1472??????2246 ?1034??????1675 |
| ???5-1 ???5-2 ???5-3 | 2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Tm 0.0012SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Tm 0.052SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Tm 0.1 | ??289???????310 ??378???????420 ??384???????456 |
Continuous table 4
| Test | The chemical constitution expression | Twilight sunset relative intensity 10 ' 60 ' |
| ???6-1 ???6-2 ???6-3 | ??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004La 0.001??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004La 0.005??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004La 0.02 | ?204????189 ?235????267 ?269????317 |
| ???7-1 ???7-2 ???7-3 | ??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Pr 0.001??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Pr 0.004??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Pr 0.02 | ?275????292 ?254????264 ?250????253 |
| ???8-1 ???8-2 ???8-3 | ??2SrO·mgO·2SiO 2·0.1B 2O 3∶Eu 0.004Tb 0.001??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Tb 0.004??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Tb 0.02 | ?224????267 ?284????368 ?230????276 |
| ???9-1 ???9-2 ???9-3 | ??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Ce 0.0017??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Ce 0.007??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Ce 0.027 | ?278????367 ?238????262 ?224????237 |
| ??10-1 ??10-2 ??10-3 | ??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Mn 0.001??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Mn 0.005??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Mn 0.02 | ?264????290 ?273????287 ?232????264 |
| ??11-1 ??11-2 ??11-3 | ??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Bi 0.001??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Bi 0.005??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Bi 0.02 | ?254????347 ?314????472 ?421????564 |
| ??12-1 ??12-2 ??12-3 | ??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Sb 0.0016??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Sb 0.006??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Sb 0.025 | ?195????227 ?184????215 ?147????169 |
| ??13-1 ??13-2 ??13-3 | ??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Sn 0.001??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Sn 0.005??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Sn 0.02 | ?124????138 ?278????367 ?167????236 |
| ??14-1 | ??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Nd 0.02Dy 0.01 | 1831???3150 |
| ??15-1 | ??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Nd 0.02Sn 0.01 | 1672???2804 |
| ??16-1 | ??2SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.02Bi 0.01 | 1837???4356 |
| Comparative sample | ??????????????ZnS∶Cu | ?100????100 |
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 x 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
| Test | The chemical constitution expression | Twilight sunset relative intensity 10 ' 60 ' |
| ???????1-1 ???????1-2 ???????1-3 ???????1-4 ???????1-5 ???????1-6 ???????1-7 | ?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.0001?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.0004?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.001?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.01?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.1?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.2 | ?127???????217 ?201???????404 ?238???????417 ?223???????389 ?152???????345 ??56???????127 ??45????????87 |
| ???????2-1 ???????2-2 ???????2-3 ???????2-4 | ?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Dy 0.0005?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Dy 0.01?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Dy 0.05?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Dy 0.15 | ?387??????1071 ?832??????1324 ?914??????1451 ?597???????921 |
| ???????3-1 ???????3-2 | ?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Nd 0.002?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Nd 0.01 | ?512???????714 ?490???????837 |
| ???????4-1 ???????4-2 | ?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Ho 0.01?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Ho 0.05 | ?482???????694 ?531???????728 |
| ???????5-1 ???????5-2 | ?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Tm 0.01?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Tm 0.05 | ?417???????623 ?465???????704 |
| ???????6-1 ???????6-2 | ?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Ce 0.0015?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Ce 0.06 | ?317???????572 ?354???????643 |
| ???????7-1 ???????7-2 | ?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Sn 0.001?2CaO·MgO·ZSiO 2·0.15B 2O 3∶Eu 0.004Sn 0.004 | ?397???????845 ?492???????897 |
| ???????8-1 ???????8-2 | ?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Bi 0.001?2CaO·MgO·ZSiO 2·0.15B 2O 3∶Eu 0.004Bi 0.004 | ?426???????823 ?549???????864 |
| ???????9-1 | ?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004Dy 0.02?????????????????????????????Nd 0.01 | ?965??????1534 |
| ???????10-1 | ?2CaO·MgO·2SiO 2·0.15B 2O 3∶Eu 0.004?Dy 0.02?????????????????????????????Bi 0.01 | ?873??????1424 |
| Comparative sample | ?(ZnCd)S∶Cu | ?100???????100 |
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=O 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
| Test | The chemical constitution expression | Twilight sunset relative intensity 10 ' 60 ' |
| 1-1 1-2 1-3 1-4 1-5 1-6 | 2(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.00052(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.0012(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.0042(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.012(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.022(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.1 | ?89.5?????????226.3 105.3?????????247.4 ?89.5?????????323 ?52.6?????????215 ?42.1?????????110.5 ?21???????????57.9 |
| 2-1 2-2 2-3 2-4 2-5 | 2(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Dy 0.00052(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Dy 0.0042(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Dy 0.0082(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Dy 0.042(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Dy 0.08 | ?562??????????1515 1237??????????3333 1206??????????3158 1246??????????3421 1219??????????3591 |
| 3-1 3-2 3-3 | 2(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Nd 0.00642(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Nd 0.0082(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Nd 0.16 | 1127??????????2815 1212??????????3032 1146??????????3012 |
| 4-1 4-2 | 2(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Ho 0.012(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Ho 0.05 | ?472??????????1324 ?534??????????1427 |
| 5-1 5-2 | 2(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Tm 0.012(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Tm 0.05 | ?567??????????1624 ?621??????????1735 |
| 6-1 6-2 6-3 | 2(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Ce 0.00152(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Ce 0.0062(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Ce 0.02 | ?116??????????184 ??95??????????174 ?116??????????216 |
| 7-1 7-2 7-3 | 2(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Sn 0.0012(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Sn 0.0052(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Sn 0.02 | ?118??????????267 ?234??????????349 ?121??????????254 |
| 8-1 8-2 8-3 | 2(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Tb 0.00132(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Tb 0.00532(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Tb 0.021 | ??89.5????????231.6 ??94.7????????242 ??31.6????????368 |
| 9-1 9-2 9-3 | 2(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Pr 0.00152(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Pr 0.0062(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Pr 0.023 | ??52.6????????136.8 ??73.7????????194.7 ??89.5????????226.3 |
| 10-1 10-2 10-3 | 2(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Bi 0.0012(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Bi 0.0052(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Bi 0.02 | ?154??????????317 ?282??????????431 ?297??????????442 |
| 11-1 | 2(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.05B 2O 3∶Eu 0.005Dy 0.02??????????????????????????????????????Bi 0.01 | 2042??????????4127 |
| Comparative sample | ???? | 100???????????100 |
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: Eux, 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
| ??? | 0 | 0.1 | ?0.2 | ?0.3 | ?0.4 | ?0.5 | ?0.6 | ?0.7 | ?0.8 | ?0.9 | 1 |
| ???Sr | Sr | Sr 0.9 | Sr 0.8 | Sr 0.7 | Sr 0.6 | Sr 0.5 | Sr 0.4 | Sr 0.3 | Sr 0.2 | Sr 0.1 | 0 |
| ??? | 0 | Ca 0.1 | Ca 0.2 | Ca 0.3 | Ca 0.4 | Ca 0.5 | Ca 0.6 | Ca 0.7 | Ca 0.8 | Ca 0.9 | Ca |
| Emmission spectrum peak value (nm) | 469 | 473 | 482 | 485 | 496 | 500 | 505 | 509 | 517 | 532 | 535 |
2. at z=0.25, select chemical constitution expression 2 (Sr
0.75Ca
0.25) OMgO2SiO
20.1B
2O
3: Eu
0.004, 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
| Test | The chemical constitution expression | Twilight sunset relative intensity 10 ' 60 ' | Glow color |
| ??1 ??2 ??3 ??4 ??5 ??6 ??7 ??8 ??9 ??10 ??11 ??12 | 2(Sr 0.75Ca 0.25)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.012(Sr 0.75Ca 0.25)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.01Dy 0.022(Sr 0.75Ca 0.25)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.01Nd 0.022(Sr 0.75Ca 0.25)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.01Ho 0.022(Sr 0.75Ca 0.25)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.01Sn 0.022(Sr 0.75Ca 0.25)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.01Bi 0.022(Sr 0.25Ca 0.75)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.012(Sr 0.25Ca 0.75)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.01Dy 0.022(Sr 0.25Ca 0.75)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.01Nd 0.022(Sr 0.25Ca 0.75)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.01Ho 0.022(Sr 0.25Ca 0.75)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.01Sn 0.022(Sr 0.25Ca 0.75)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.01Bi 0.02 | ?121??????162 1758?????3874 1121?????1671 1023?????1642 ?267??????342 ?323??????407 ?171??????303 ?617?????1247 ?517??????928 ?361??????808 ?231??????431 ?272??????489 | The green orchid of the blue green orchid of the green orchid of the green orchid of green orchid is greenish-yellow greenish-yellow |
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
| Test | The chemical constitution expression | Twilight sunset relative intensity 10 ' 60 ' | Glow color |
| ?????1-1 ?????1-2 | 3SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Nd 0.023SrO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.02 | 211?????????489 300?????????579 | Blue look luminous blue look luminous |
| ?????2-1 ?????2-2 | 3CaO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Nd 0.023CaO·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.02 | 31.4????????56.1 67.1????????146 | The luminous pale green of pale green is luminous |
| ?????3-1 ?????3-2 | 3(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.023(Sr 0.5Ca 0.5)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Nd 0.02 | 173?????????345 91??????????183 | Blue green luminous orchid is green luminous |
| Comparative sample | ????(CaSr)S∶Bi ???? | 100?????????100 100?????????100 |
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 orchid-blue green twilight sunset 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 a comparative sample with ZnS: Cu.From showing to find out that luminous intensity significantly is better than comparative sample.Table 10
| Test | The chemical constitution expression | Twilight sunset relative intensity 10 ' 60 ' |
| ?????1-1 ?????1-2 ?????1-3 ?????1-4 | 2(Sr 0.9Zn 0.1)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.022SrO·(Mg 0.9Zn 0.1)O·2SiO 2·0.1B 2D 3∶Eu 0.004Nd 0.022SrO·(Mg 0.9Ba 0.1)O·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.022(Sr 0.9Cd 0.1)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.02 | ??976?????1793 ?1170?????2104 ??836?????1706 ?1031?????1842 |
| ?????2-1 ?????2-2 ?????2-3 ?????2-4 | 2(Ca 0.9Zn 0.1)·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.022CaO·(Mg 0.9Zn 0.1)·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.022(Ca 0.95Ba 0.05)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Nd 0.022CaO·(Mg 0.9Be 0.1)·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.02 | ??635??????784 ??703??????802 ??507??????769 ??603??????726 |
| ?????3-1 ?????3-2 | 2(Sr 0.495Ca 0.495Zn 0.05)O·MgO·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.022(Sr 0.5Ca 0.5)O·(Mg 0.9Ba 0.1)O·2SiO 2·0.1B 2O 3∶Eu 0.004Dy 0.02 | ?1083?????2835 ?1017?????2786 |
| Comparative sample | (CaSr) S: Bi (orchid) is S: Cu (Huang) ZnS: Cu (green) (ZnCd) | ??100??????100 ??100??????100 ??100??????100 |
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
| Test | Expression | Twilight sunset relative intensity 10 ' 60 ' |
| 1-1 | Ba 5Si 8O 21∶Eu、Dy | ???87.4???????174 |
| Comparative sample | ZnS∶Cu | ???100????????100 |
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
| Test | Expression | Twilight sunset relative intensity 10 ' 60 ' |
| 1-1 | ?Zn 2SiO 4∶Eu、Dy、Mn | ????32.6??????95.8 |
| Comparative sample | ?ZnS∶Cu | ????100???????100 |
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
| Test | The chemical constitution expression | Add composition | Add-on (mol) | Luminous twilight sunset relative intensity 10 ' 60 ' |
| ??????1 ??????2 ??????3 ??????4 ??????5 ??????6 ??????7 ??????8 ??????9 ?????10 | 2.5(Sr 0.3Ca 0.7O)·1.2MgO·2.5SiO 2·0.1B 2O 3∶Eu 0.02Dy 0.12.5(Sr 0.3Ca 0.7O)·1.2MgO·2.5SiO 2·0.1B 2O 3∶Eu 0.02Dy 0.12.5(Sr 0.3Ca 0.7O)·1.2MgO·2.5SiO 2·0.1B 2O 3∶Eu 0.02Dy 0.12.5(Sr 0.3Ca 0.7O)·1.2MgO·2.5SiO 2·0.1B 2O 3∶Eu 0.02Dy 0.12.5(Sr 0.3Ca 0.7O)·1.2MgO·2.5SiO 2·0.1B 2O 3∶Eu 0.02Dy 0.12.5(Sr 0.3Ca 0.7O)·1.2MgO·2.5SiO 2·0.1B 2O 3∶Eu 0.02Dy 0.12.5(Sr 0.3Ca 0.7O)·1.2MgO·2.5SiO 2·0.1B 2O 3∶Eu 0.02Dy 0.12.5(Sr 0.3Ca 0.7O)·1.2MgO·2.5SiO 2·0.1B 2O 3∶Eu 0.02Dy 0.12.5(Sr 0.3Ca 0.7O)·1.2MgO·2.5SiO 2·0.1B 2O 3∶Eu 0.02Dy 0.12.5(Sr 0.3Ca 0.7O)·1.2MgO·2.5SiO 2·0.1B 2O 3∶Eu 0.02Dy 0.1 | ??O NH 4Cl NH 4F 2Li 2CO 3SrF 2CaF 2CaSO 4SrSO 4SrHPO 4CaHPO 4 | ?0 0.1 0.1 0.05 0.1 0.1 0.1 0.1 0.1 0.1 | ?643????????1374 ?684????????1427 ?672????????1395 ?693????????1432 ?675????????1398 ?663????????1388 ?670????????1391 ?675????????1382 ?682????????1407 ?667????????1379 |
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: emmission spectrum of Eu material (a) and excitation spectrum (b)
Fig. 2 represents Sr
2MgSi
2O
7: the x-ray diffraction pattern of Eu material
Fig. 3 represents Sr
2MgSi
2O
7: emmission spectrum of EuDy material (a) and excitation spectrum (b)
Fig. 4 represents Sr
2MgSi
2O
7: the persistence characteristic curve of EuDy material
Fig. 5 represents Ca
2MgSi
2O
7: emmission spectrum of EuDy material (a) and excitation spectrum (b)
Fig. 6 represents Ca
2MgSi
2O
7: the x-ray diffraction pattern of EuDy material
Fig. 7 represents Ca
2MgSi
2O
7: the persistence characteristic curve of EuDy material
Fig. 8 represents (Sr
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: the x-ray diffraction pattern of EuDy material
Figure 10 represents (Sr
0.5Ca
0.5)
2MgSi
2O
7: the persistence characteristic curve of EuDy material
Figure 11 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: emmission spectrum of EuDy material (a) and excitation spectrum (b)
Figure 14 represents Sr
3MgSi
2O
8: the x-ray diffraction pattern of EuDy material
Figure 15 represents Ca
3MgSi
2O
8: emmission spectrum of EuDy material (a) and excitation spectrum (b)
Figure 16 represents Ca
3MgSi
2O
8: the x-ray diffraction pattern of EuDy material
Figure 17 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 ?B ?Eu | ???1.996 ???1 ???2 ???0.2 ???0.004 | ?SrCO 34MgCO 3·Mg(OH) 2·5H 2O ?SiO 2?B 2O 3?Eu 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 3?4MgCO 3·Mg(OH) 2·5H 2O ?SiO 2?H 3BO 3?Eu 2O 3?Dy 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 after the fluorescent lamp 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 3?4MgCO 3·Mg(OH) 2·5H 2O ?SiO 2?(NH 4) 2HPO 4?Eu 2O 3?Nd 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 3?4MgCO 3·Mg(OH) 2·5H 2O ?SiO 2?H 3BO 3?Eu 2O 3?Dy 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 3?4MgCO 3·Mg(OH) 2·5H 2O ?H 2SiO 3?B 2O 3?Eu 2O 3?Ho 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 1.5CaO3MgO2SiO 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 ??B ??Eu ??Dy | ???1 ???1 ???1 ???1 ???0.1 ???0.005 ???0.08 | ?SrCO 3?CaCO 3?4MgCO 3·Mg(OH) 2·5H 2O ?SiO 2?H 3BO 3?Eu 2O 3?Dy 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, and 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, and 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) 2??Ca(NO 3) 2·4H 2O ??Mg(NO 3) 2·6H 2O silica gel NH 4H 2PO 4??Eu 2O 3??Nd 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.
| Element | Mole number | Raw material | Quantity |
| ?Sr ?Mg ?Si ?Eu ?Ho | ????3 ????1 ????2 ????0.01 ????0.08 | ?Sr(NO 3) 2?MgO ?H 2SiO 3?Eu 2O 3?Ho 2O 3 | 634.8 restrain 40.3 grams, 156 grams, 1.76 grams, 15.1 grams |
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) O2.5SiO
40.1B
2O
3: Eu
0.01Dy
0.02Bi
0.01The synthesis material proportioning of material
| Element | Mole number | Raw material | Quantity |
| Sr Ca Mg Cd Si ?B Eu Dy Bi | ????1.3 ????0.8 ????0.8 ????0.2 ????2.5 ????0.2 ????0.01 ????0.02 ????0.01 | ??SrCO 3??CaCO 3??4MgCO 3·Mg(OH) 2·5H 2O ??CdO ??SiO 2??B 2O 3??Eu 2O 3??Dy 2O 3??Bi 2O 3 | 177.1 restrain 80 grams, 77.7 grams, 25.7 grams, 150 grams, 6.96 grams, 1.76 grams, 3.73 grams, 2.33 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 3?SiO 3?B 2O 3?Eu 2O 3?Dy 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
8O
21, its chemical expression formula is Ba
5Si
8O
21: Eu, Dy.
Claims (12)
1. a long after glow luminous material is characterized by and mainly contains silicate and activator ion, and its main chemical constitution expression is: aMObM ' OcSiO
2DR: Eux, Lny, 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; 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; 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, 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 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, Ho, Bi, the Sn, 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.
3. long after glow luminous material as claimed in claim 2,0～40% mole that it is characterized by M, the middle element of M ' can be replaced by Ba, Zn, Cd, Be.
4. long after glow luminous material as claimed in claim 1 or 2 is characterized by the material main compound and is: M
2MgSi
2O
7Or M
3MgSi
2O
8, wherein M is Sr
1-zCa
z, 0≤z≤1.
5. long after glow luminous material as claimed in claim 1 or 2 is characterized by main chemical expression formula and is: M
2MgSi
2O
7: Eu, Ln or M
3MgSi
2O
8: Eu, Ln, wherein M is Sr
1-zCa
z, 0≤z≤1.
6. long after glow luminous material as claimed in claim 1 or 2, the main chemical expression formula that it is characterized by 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, Ln is selected from one or more elements among Nd, Dy, Ho, Sn, the Bi.
7. long after glow luminous material as claimed in claim 1, the main chemical expression formula that it is characterized by material is: Ba
5Si
8O
21: Eu, Dy.
8. long after glow luminous material as claimed in claim 1, the main chemical expression formula that it is characterized by material is: Zn
2SiO
4: Eu, Dy, Mn.
9. the manufacture 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 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
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 one
The compound of kind or multiple element;
Si represents the compound of Si;
Eu represents the compound of Eu;
The compound of M, M ', Ln, Eu is carbonate, vitriol, nitrate, phosphoric acid salt, borate, acetate, oxalate, Citrate trianion or its oxide compound, oxyhydroxide, a halogenide of using their representative elements respectively, and the compound of Si is to use SiO
2, silicic acid, silica gel or silicate, R is the compound of boron, phosphorus; Manufacturing process is a high-temperature solid phase reaction method, and above-mentioned raw materials is taken by weighing by the mole proportioning, and porphyrize also mixes, under reducing atmosphere, in 1100-1400 ℃ of sintering 2～50h, after cool off, pulverize, sieving forms.
10. the manufacture method of long after glow luminous material as claimed in claim 9, it is characterized by described reducing atmosphere is that hydrogen, ammonia, nitrogen and hydrogen or carbon granules exist down.
11. the manufacture method of long after glow luminous material as claimed in claim 9 is characterized by can add the NH that accounts for raw material weight 0～15% in mixing raw material
4Cl, NH
4F, Li
2CO
3, SrF
2, CaF
2, CaSO
4, SrSO
4, SrHPO
4Or CaHPO
4Participate in solid state reaction.
12. the manufacture method of long after glow luminous material as claimed in claim 9, it is characterized by M ' is the Mg element, uses raw material to be magnesium basic carbonate.
Priority Applications (1)
| 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 |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103524 | 1997-03-26 | ||
| CN97103524.5 | 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1194292A true CN1194292A (en) | 1998-09-30 |
| CN1062581C CN1062581C (en) | 2001-02-28 |
Family
ID=25744255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98105078A Expired - Lifetime CN1062581C (en) | 1997-03-26 | 1998-03-20 | Long persistence luminescent silicate material and its producing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1062581C (en) |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6953536B2 (en) | 2003-02-25 | 2005-10-11 | University Of Georgia Research Foundation, Inc. | Long persistent phosphors and persistent energy transfer technique |
| CN1325603C (en) * | 2003-11-27 | 2007-07-11 | 上海交通大学 | Long-time afterglow luminescent silicate material and its producing method |
| CN100368507C (en) * | 2005-08-10 | 2008-02-13 | 广州有色金属研究院 | A highly expanded long-lasting luminescent material |
| CN100415849C (en) * | 2007-02-06 | 2008-09-03 | 江苏苏博特新材料股份有限公司 | Rare earth red phosphor and manufacturing method thereof |
| CN100513516C (en) * | 2004-07-14 | 2009-07-15 | 株式会社东芝 | Nitrogen-containing fluorescent substance, method for producing same, and light-emitting device |
| US7608200B2 (en) | 2004-01-16 | 2009-10-27 | Mitsubishi Chemical Corporation | Phosphor and including the same, light emitting apparatus, illuminating apparatus and image display |
| CN101792928A (en) * | 2010-03-30 | 2010-08-04 | 山东大学 | High temperature piezocrystal of melilite structure and preparation method and application thereof |
| CN101077973B (en) * | 2006-05-26 | 2010-09-29 | 大连路明发光科技股份有限公司 | Silicate fluorescent material, method for producing same, and light-emitting device using same |
| US7828993B2 (en) | 2002-12-20 | 2010-11-09 | Tovoda Gosei Co.. Ltd. | Phosphor and optical device using same |
| CN101126023B (en) * | 2006-08-15 | 2011-06-15 | 大连路明发光科技股份有限公司 | Multi-emission peak silicate matrix luminescent material, manufacturing method thereof, and luminescent device using same |
| CN102537739A (en) * | 2012-01-08 | 2012-07-04 | 浙江新天天光电科技有限公司 | Yellow LED light source component |
| CN102618278A (en) * | 2012-03-05 | 2012-08-01 | 昆明理工大学 | Bismuth ion-activated aluminosilicate long afterglow phosphor material and preparation method thereof |
| CN102660773A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Non-linear optical crystal boric acid cadmium yttrium oxide |
| CN102686702A (en) * | 2009-09-29 | 2012-09-19 | 韩国化学研究院 | (Halo)silicate-based phosphor and method for preparing same |
| CN102719245A (en) * | 2012-06-25 | 2012-10-10 | 重庆文理学院 | Secondary excitation type orange-red fluorescent powder and preparation method thereof |
| CN101935204B (en) * | 2009-10-23 | 2013-02-27 | 郑子山 | A kind of ultra-long afterglow blue light-storing ceramic material and its preparation method |
| CN103377599A (en) * | 2012-04-17 | 2013-10-30 | 梁清源 | Long afterglow light-emitting fire fighting symbol and preparation method thereof |
| CN104845476A (en) * | 2015-05-27 | 2015-08-19 | 浙江大学自贡创新中心 | Long-persistence texture paint and preparing method thereof |
| CN105038794A (en) * | 2015-06-12 | 2015-11-11 | 佛山市启正电气有限公司 | Photoconversion material for enhancing energy efficiency of solar cells and preparation method thereof |
| CN105086781A (en) * | 2015-07-30 | 2015-11-25 | 洛阳仲平实业有限公司 | Rare earth borate steady persistence polyester powder coating |
| CN105586034A (en) * | 2015-12-23 | 2016-05-18 | 上海大学 | Single-matrix near ultraviolet excited light color adjustable fluorescent powder and preparation method thereof |
| CN108424768A (en) * | 2018-05-02 | 2018-08-21 | 安徽沛隆智能机械科技有限公司 | A kind of environment-friendly type persistence luminous agent applied to plastic toy |
| CN111377722A (en) * | 2018-12-27 | 2020-07-07 | 中国科学院上海硅酸盐研究所 | A kind of microwave dielectric ceramic material, microwave dielectric ceramic antenna and preparation method thereof |
| CN112280554A (en) * | 2020-11-20 | 2021-01-29 | 广东电网有限责任公司电力科学研究院 | Energy storage type environment-friendly luminescent material and preparation method thereof |
| CN115932932A (en) * | 2022-11-03 | 2023-04-07 | 宁波虔东科浩光电科技有限公司 | Signal processing method of scintillator detection array and imaging device |
| CN117185664A (en) * | 2023-06-29 | 2023-12-08 | 河北光兴半导体技术有限公司 | Long afterglow microcrystalline glass and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6884367B2 (en) * | 2001-12-19 | 2005-04-26 | Sumitomo Chemical Company Limited | Method for producing silicate phosphor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61174291A (en) * | 1985-01-29 | 1986-08-05 | Sony Corp | Phosphor emitting blue light |
-
1998
- 1998-03-20 CN CN98105078A patent/CN1062581C/en not_active Expired - Lifetime
Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1729267B (en) * | 2002-12-20 | 2012-12-19 | 丰田合成株式会社 | Luminous bodies and optical devices using them |
| US7828993B2 (en) | 2002-12-20 | 2010-11-09 | Tovoda Gosei Co.. Ltd. | Phosphor and optical device using same |
| US6953536B2 (en) | 2003-02-25 | 2005-10-11 | University Of Georgia Research Foundation, Inc. | Long persistent phosphors and persistent energy transfer technique |
| CN1325603C (en) * | 2003-11-27 | 2007-07-11 | 上海交通大学 | Long-time afterglow luminescent silicate material and its producing method |
| US7608200B2 (en) | 2004-01-16 | 2009-10-27 | Mitsubishi Chemical Corporation | Phosphor and including the same, light emitting apparatus, illuminating apparatus and image display |
| CN100513516C (en) * | 2004-07-14 | 2009-07-15 | 株式会社东芝 | Nitrogen-containing fluorescent substance, method for producing same, and light-emitting device |
| CN101353576B (en) * | 2004-07-14 | 2011-12-07 | 株式会社东芝 | Fluorescent substance containing nitrogen, method for manufacturing the same, and light-emitting device |
| CN100368507C (en) * | 2005-08-10 | 2008-02-13 | 广州有色金属研究院 | A highly expanded long-lasting luminescent material |
| CN101077973B (en) * | 2006-05-26 | 2010-09-29 | 大连路明发光科技股份有限公司 | Silicate fluorescent material, method for producing same, and light-emitting device using same |
| CN101126023B (en) * | 2006-08-15 | 2011-06-15 | 大连路明发光科技股份有限公司 | Multi-emission peak silicate matrix luminescent material, manufacturing method thereof, and luminescent device using same |
| CN100415849C (en) * | 2007-02-06 | 2008-09-03 | 江苏苏博特新材料股份有限公司 | Rare earth red phosphor and manufacturing method thereof |
| CN102686702A (en) * | 2009-09-29 | 2012-09-19 | 韩国化学研究院 | (Halo)silicate-based phosphor and method for preparing same |
| CN102686702B (en) * | 2009-09-29 | 2014-12-03 | 韩国化学研究院 | (Halo)silicate-based phosphor and method for preparing same |
| CN101935204B (en) * | 2009-10-23 | 2013-02-27 | 郑子山 | A kind of ultra-long afterglow blue light-storing ceramic material and its preparation method |
| CN101792928A (en) * | 2010-03-30 | 2010-08-04 | 山东大学 | High temperature piezocrystal of melilite structure and preparation method and application thereof |
| CN102537739A (en) * | 2012-01-08 | 2012-07-04 | 浙江新天天光电科技有限公司 | Yellow LED light source component |
| CN102537739B (en) * | 2012-01-08 | 2013-10-30 | 浙江新天天光电科技有限公司 | Yellow LED light source component |
| CN102618278A (en) * | 2012-03-05 | 2012-08-01 | 昆明理工大学 | Bismuth ion-activated aluminosilicate long afterglow phosphor material and preparation method thereof |
| CN103377599A (en) * | 2012-04-17 | 2013-10-30 | 梁清源 | Long afterglow light-emitting fire fighting symbol and preparation method thereof |
| CN103377599B (en) * | 2012-04-17 | 2015-09-09 | 梁清源 | A kind of long-persistence luminous fire symbol and preparation method thereof |
| CN102660773A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Non-linear optical crystal boric acid cadmium yttrium oxide |
| CN102719245A (en) * | 2012-06-25 | 2012-10-10 | 重庆文理学院 | Secondary excitation type orange-red fluorescent powder and preparation method thereof |
| CN102719245B (en) * | 2012-06-25 | 2015-04-08 | 重庆文理学院 | Secondary excitation type orange-red fluorescent powder and preparation method thereof |
| CN104845476A (en) * | 2015-05-27 | 2015-08-19 | 浙江大学自贡创新中心 | Long-persistence texture paint and preparing method thereof |
| CN105038794A (en) * | 2015-06-12 | 2015-11-11 | 佛山市启正电气有限公司 | Photoconversion material for enhancing energy efficiency of solar cells and preparation method thereof |
| CN105086781A (en) * | 2015-07-30 | 2015-11-25 | 洛阳仲平实业有限公司 | Rare earth borate steady persistence polyester powder coating |
| CN105586034A (en) * | 2015-12-23 | 2016-05-18 | 上海大学 | Single-matrix near ultraviolet excited light color adjustable fluorescent powder and preparation method thereof |
| CN105586034B (en) * | 2015-12-23 | 2017-11-10 | 上海大学 | Near ultraviolet excitated photochromic adjustable fluorescent material of single-matrix and preparation method thereof |
| CN108424768A (en) * | 2018-05-02 | 2018-08-21 | 安徽沛隆智能机械科技有限公司 | A kind of environment-friendly type persistence luminous agent applied to plastic toy |
| CN111377722A (en) * | 2018-12-27 | 2020-07-07 | 中国科学院上海硅酸盐研究所 | A kind of microwave dielectric ceramic material, microwave dielectric ceramic antenna and preparation method thereof |
| CN112280554A (en) * | 2020-11-20 | 2021-01-29 | 广东电网有限责任公司电力科学研究院 | Energy storage type environment-friendly luminescent material and preparation method thereof |
| CN112280554B (en) * | 2020-11-20 | 2022-04-29 | 广东电网有限责任公司电力科学研究院 | Energy storage type environment-friendly luminescent material and preparation method thereof |
| CN115932932A (en) * | 2022-11-03 | 2023-04-07 | 宁波虔东科浩光电科技有限公司 | Signal processing method of scintillator detection array and imaging device |
| CN117185664A (en) * | 2023-06-29 | 2023-12-08 | 河北光兴半导体技术有限公司 | Long afterglow microcrystalline glass and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1062581C (en) | 2001-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1062581C (en) | Long persistence luminescent silicate material and its producing method | |
| EP2036967B1 (en) | Silicate-containing luminescent material,its making method and the light-emitting device using the same | |
| KR101439567B1 (en) | Silicate base luminescent materials having multiple emission peaks, processes for preparing the same and light emitting devices using the same | |
| KR100477347B1 (en) | Silicate phosphor with a long afterglow and manufacturing method thereof | |
| CN102660269B (en) | Illumination system comprising a radiation source and a luminescent material | |
| JPH08170076A (en) | Long afterglow phosphor | |
| JP6793549B2 (en) | Oxynitride fluorescent powder and its preparation method, oxynitride illuminant and light emitting device | |
| CN101134895A (en) | Wide-spectrum excitation fluorescent material, synthesis method thereof and light-emitting device using wide-spectrum excitation fluorescent material | |
| CN112126433B (en) | Aluminosilicate fluorescent material capable of emitting green light | |
| CN101443433A (en) | Illumination system comprising a radiation source and a luminescent material | |
| CN113355092B (en) | A kind of single-matrix double-emitting phosphor and its preparation method and application | |
| CN112094645A (en) | A blue light fluorescent material doped with Eu2+, its preparation method and white light LED light-emitting device | |
| CN102108297B (en) | Red fluorescent powder, preparation method thereof and luminescent device prepared therefrom | |
| CN101126023B (en) | Multi-emission peak silicate matrix luminescent material, manufacturing method thereof, and luminescent device using same | |
| CN100560688C (en) | Long afterglow luminescent material and its producing method | |
| CN108822842B (en) | Red strontium magnesium phosphate fluorescent material and preparation method and application thereof | |
| JPH0141673B2 (en) | ||
| CN102399554A (en) | Nitride red light emitting material, light emitting member including the same, and light emitting device | |
| CN108841383B (en) | Blue sodium rubidium magnesium phosphate fluorescent material with high luminous efficiency and preparation method and application thereof | |
| CN107142106A (en) | A kind of blue fluorescent powder for white-light LED and preparation method thereof | |
| CN1260321C (en) | Luminscent-powder in use for LED of white light, preparing method and electric light source produced | |
| CN102382655B (en) | Phosphorus-containing LED fluorescent powder, preparation method and prepared light-emitting device thereof | |
| CN110003910B (en) | A Eu3+ activated bismuth fluorotelluride red phosphor and its preparation method and application | |
| KR20100112445A (en) | Phosphors and white light emitting devices including same | |
| CN116120922A (en) | A kind of Eu2+ doped silicate fluorescent material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: XIAO ZHIQIANG Effective date: 20030530 Owner name: LUMING TECHNOLOGY GROUP CO., LTD., DALIAN CITY Free format text: FORMER OWNER: XIAO ZHIGUO |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20030530 Address after: Liaoning province Dalian City High-tech Park Qixianling Torch Road No. 10 Dalian luminglight science and Technology Co Ltd Patentee after: Dalian Luming Science & Technology Group Co., Ltd. Address before: Qixianling Torch Road Ganjingzi District of Dalian City, Liaoning Province, No. 10 Dalian Lu Ming Source Co. Ltd. Co-patentee before: Xiao Zhiqiang Patentee before: Xiao Zhiguo |
|
| ASS | Succession or assignment of patent right |
Owner name: MINGFA OPTICAL SCIENCE CO., LTD., DALIAN ROAD Free format text: FORMER OWNER: LUMING TECHNOLOGY GROUP CO., LTD., DALIAN CITY Effective date: 20090619 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20090619 Address after: Liaoning province Dalian City High-tech Park Qixianling high-energy Street No. 1 Patentee after: Dalian Luming Light Emitting Sci-Tech Co., Ltd. Address before: Liaoning province Dalian City High-tech Park Qixianling Torch Road No. 10 Dalian luminglight science and Technology Co Ltd Patentee before: Dalian Luming Science & Technology Group Co., Ltd. |
|
| 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. |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20010228 |