CN100463950C - Manganese ion activated green long afterglow luminescent material and its preparation method - Google Patents
Manganese ion activated green long afterglow luminescent material and its preparation method Download PDFInfo
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- CN100463950C CN100463950C CNB2005100167956A CN200510016795A CN100463950C CN 100463950 C CN100463950 C CN 100463950C CN B2005100167956 A CNB2005100167956 A CN B2005100167956A CN 200510016795 A CN200510016795 A CN 200510016795A CN 100463950 C CN100463950 C CN 100463950C
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Abstract
The invention discloses a inverse spinel structure magnesium stannate green long persistence phosphor to prepare Mg2SnO4 as substrate and Mn2+ as activating ion activate by bivalent manganese ion, which comprises the following steps: adopting MgO and SnO2 as substrate; blending Mn2+ ion; adding Mn(CH3COO)2 .4H2O; setting the quantity of doping agent at 0.005-1 percent mole; weighing MgO and SnO2 according to 2:1 molar proportion; putting 0.005-1 percent mole activator in the pot; setting igniting temperature at 950-1250 deg.c for 1-3 h; setting active carbon as reducer; fetching the reactor out of furnace; cooling in the air to produce almost white product; luminating the product through 254 nm ultraviolet lamp to see green long persistence phosphor; displaying the best effect when the doping quantity of Mn2+ is at 0.2-0.3 percent and color coordination of x is 0.0875 and y is 0.6083.
Description
Technical field
The present invention relates to a kind of long after glow luminous material magnesium stannate and preparation method thereof, more particularly, relate to a kind of divalent transition metal ion Mn
2+Activated high brightness green emitted long after glow luminous material and preparation method.
Background technology
The long-persistence luminous electron capture material that belongs to, it and optical stimulated luminescence material and thermoluminescence material do not have absolute boundary, and long after glow luminous material is a kind of special thermoluminescence material in a sense, that is thermoluminescence material at room temperature.According to long-persistence luminous general principle,, just can be observed long-persistence luminous as long as in matrix, cause the defective or the trap that at room temperature can discharge stored energy of the finite concentration and the degree of depth by thermal perturbation.Yet, the tempo of long after glow luminous material is quite slow, the long-persistence luminous time length is extended to tens hours from tens minutes experienced the almost time in 100 years, chief reason is the complicacy of defective in the material and lacks direct laboratory facilities (Appl.Phys.Lett.2002,80 (9), 1535).
Research major part for long after glow luminous material all concentrates on the alkali earth metal aluminate aspect at present, as: SrAl
2O
4: Eu
2+, Dy
3+, CaAl
2O
4: Eu
2+, Nd
3+And Sr
4Al
14O
25: Dy, Eu etc.Research to other color long after glow luminous material is less relatively, makes progress also slow relatively.
Summary of the invention
In order to solve the shortcoming of above-mentioned background technology, the objective of the invention is to seek and prepare the long after glow luminous material system that chemical stability is good, after-glow brightness is high, persistence is long, glow color is various, be the key breakthrough point of current steady persistence research field, the invention provides a kind of transient metal Mn
2+Ion-activated green high-brightness long persistence luminescent material.The purpose of this invention is to provide a kind of novel inverse spinel structure Mn
2+Ion-activated Mg
2SnO
4Green long shot long after glow luminous material.
Another object of the present invention is to provide a kind of preparation method of above-mentioned long after glow luminous material.
For achieving the above object, long after glow luminous material provided by the invention consists of: Mg
2SnO
4: Mn
2+, wherein, inverse spinel structure magnesium stannate Mg
2SnO
4Be matrix, Mn
2+Be active ions.
The present invention prepare above-mentioned green long afterglow luminescent material raw material be analytical pure or high-purity magnesium oxide (MgO) and tindioxide (SnO
2), the doping active ions are Mn
2+, thorough mixing is placed in the corundum crucible, adds a cover calcination; Cooling can obtain the near-white powdered product.
Described magnesium oxide (MgO) and tindioxide (SnO
2) be analytical pure or high-purity, take by weighing by 2:1 mole proportioning; The doping content of described active ions is 0.005-1%; Described calcination temperature is 950-1150 ℃, reaction times 1-3 hour; High temperature is come out of the stove after the described calcination, cools off in air.
Activator is with manganous oxalate (Mn (CH
3COO)
24H
2O) form adds.Activated carbon is a reductive agent, obtains a kind of efficient green long after glow luminous material by high temperature solid-state method.
At above-mentioned long after glow luminous material Mg
2SnO
4: Mn
2+In, Mn
2+Ion is as activator, Mn
2+Green emitted come from Mn
2+Ionic d transition of electron.Because SnO
4 4-Negatively charged ion has optics inertia structure, can be used to make up the matrix of luminescent material.Mg
2SnO
4It is a kind of stable cube inverse spinel structure.Mg
2SnO
4Have 96 positively charged ion cases, Mg
2+Ion has occupied 24 cases wherein; Wherein in 64 tetrahedron cases, there are 8 by the Mg of part
2+Ion occupies, and has 16 by remaining Mg in 32 octahedra cases
2+Ion and Sn
4+Ion occupies.Except a large amount of not occupied the case, positively charged ion distorts at Mg
2SnO
4Produce a large amount of defectives in the crystalline structure simultaneously, the trap that part defective wherein can be used as electronics or hole is used to store outside energy, such as being in Sn
4+The Mg of case
2+Ion can be used as hole trap, on the contrary, is in Mg
2+The Sn of case
4+Ion can be used as electron trap, and the oxygen room also can be used as the electron trap as F colour center class.Therefore, can expect Mg
2SnO
4Be a kind of good long-persistence luminous matrix.Long after glow luminous material of the present invention has very low optimum doping concentration, is because Mg
2SnO
4Occupy Mn in the matrix respectively at tetrahedron case and octahedra case
2+Due to the interaction between the ion.
At above-mentioned long after glow luminous material Mg
2SnO
4: Mn
2+In, need not to add the energy capture agent, by single Mn
2+Ion swashs agent just can produce good steady persistence emission.
Mg
2SnO
4: Mn
2+The concrete preparation method of long after glow luminous material: take by weighing MgO and SnO by the 2:1 mol ratio
2Raw material takes by weighing activator Mn (CH by the 0.005-1% molar fraction
3COO)
24H
2O, in agate mortar, adopt wet method to grind well, pack in the corundum crucible, compacting covers mouth of pot completely with the corundum sheet, put it into then in the bigger alumina crucible, and around corundum crucible, put into proper amount of active carbon, and bigger mouth of pot is covered completely with the corundum sheet, place in the High Temperature Furnaces Heating Apparatus, be heated to 950-1150 ℃, constant temperature 1-3 hour.High temperature is come out of the stove, and is cooled to room temperature and gets the near-white powder.XRD identifies that product is single-phase, mixes crystalline structure is not produced obvious influence.Phosphorescence spectrum is measured, and emission peak is positioned at 500nm, and the phosphorescence decay is index law.After UV-irradiation, long after glow luminous material presents strong green long afterglow emission.This long after glow luminous material has high brightness green long afterglow emission characteristic after the 254nm UV-irradiation, when can be used for the public place power failure, and the caution of the demonstration of crowd evacuation fire exit, the sign of fire passage and some other specific occasions etc.Prepared its excitation wavelength of green long afterglow luminescent material of the present invention is positioned at about 254nm, can utilize it to make the steady persistence fluorescent tube in a large number.
Long after glow luminous material utilizes natural sun power and other luminous energy to be converted to visible light naturally, because its good storage light-characteristics of luminescence, aspect industrial and agricultural production, military affairs, fire-fighting and people's life many, all be widely used, as building materials decoration, communications and transportation, military installations, fire-fighting emergent and daily necessities etc., and can make serial noctilucence products such as luminous paint, luminous printing ink, light-emitting film, luminescent fibre, luminescent ceramic, luminescent plastics.
Embodiment:
Embodiment 1
Take by weighing spectroscopically pure magnesium oxide (MgO) 8.0609g, analytical pure tindioxide (SnO
2) 15.0709g, manganous oxalate (Mn (CH
3COO)
24H
2O) 0.049g, after wet method fully grinds well in agate mortar, pack in the corundum crucible, compacting covers mouth of pot completely with dull and stereotyped crucible cover, put it into then in the bigger alumina crucible, and around corundum crucible, put into proper amount of active carbon, and bigger mouth of pot is covered completely with the corundum sheet, place in the High Temperature Furnaces Heating Apparatus, be heated to 950 ℃, constant temperature 3 hours.High temperature is come out of the stove, and is cooled to room temperature and gets the near-white powder.Identify that through XRD product is magnesium stannate (Mg
2SnO
4), emmission spectrum comprises one from 460 to 560nm arrowband.Through 254nm UV-irradiation 1 minute, luminescent material presented strong green long afterglow emission, is about 2 hours time of persistence.
Embodiment 2
Take by weighing spectroscopically pure magnesium oxide (MgO) 8.0609g, analytical pure tindioxide (SnO
2) 15.0709g, manganous oxalate (Mn (CH
3COO)
24H
2O) 0.049g, after wet method fully ground well in agate mortar, in the corundum crucible of packing into, compacting covered mouth of pot completely with dull and stereotyped crucible cover, places in the High Temperature Furnaces Heating Apparatus, is heated to 950 ℃, constant temperature 1 hour.High temperature is come out of the stove, and is cooled to room temperature and gets the pale pink powder, and it is owing to contain Mn in the synthetic sample in aerial that product becomes pale pink
4+Due to.Identify that through XRD product is magnesium stannate (Mg
2SnO
4) and a small amount of unreacted tindioxide (SnO
2), emmission spectrum comprises one from 460 to 560nm arrowband.Through 254nm UV-irradiation 1 minute, the green long afterglow emission that luminescent material presents was about 1 hour time of persistence.
Embodiment 3
Take by weighing spectroscopically pure magnesium oxide (MgO) 8.0609g, analytical pure tindioxide (SnO
2) 15.0709g, manganous oxalate (Mn (CH
3COO)
24H
2O) 0.049g, after wet method fully ground well in agate mortar, in the corundum crucible of packing into, compacting covered mouth of pot completely with dull and stereotyped crucible cover, placed in the High Temperature Furnaces Heating Apparatus, fed high-purity hydrogen, was heated to 950 ℃, constant temperature 2 hours.High temperature is come out of the stove, and is cooled to room temperature and gets the grey powder.Identify that through XRD product is magnesium stannate (Mg
2SnO
4) and magnesium oxide (MgO), also produced a spot of grey metal tin in addition.Emmission spectrum comprises one from 460 to 560nm arrowband.Through 254nm UV-irradiation 1 minute, luminescent material presented green twilight sunset emission, is about 0.5 hour time of persistence.
Embodiment 4
Take by weighing spectroscopically pure magnesium oxide (MgO) 8.0609g, analytical pure tindioxide (SnO
2) 15.0709g, manganous oxalate (Mn (CH
3COO)
24H
2O) 0.061g, after wet method fully grinds well in agate mortar, pack in the corundum crucible, compacting covers mouth of pot completely with dull and stereotyped crucible cover, put it into then in the bigger alumina crucible, and around corundum crucible, put into proper amount of active carbon, and bigger mouth of pot is covered completely with the corundum sheet, place in the High Temperature Furnaces Heating Apparatus, be heated to 1100 ℃, constant temperature 3 hours.High temperature is come out of the stove, and is cooled to room temperature and gets the near-white powder.Identify that through XRD product is magnesium stannate (Mg
2SnO
4), emmission spectrum comprises one from 460 to 560nm arrowband.Through 254nm UV-irradiation 1 minute, luminescent material presented strong green long afterglow emission, is about 4 hours time of persistence, and chromaticity coordinates is x=0.0875, y=0.6083.
Embodiment 5
Take by weighing spectroscopically pure magnesium oxide (MgO) 8.0609g, analytical pure tindioxide (SnO
2) 15.0709g, manganous oxalate (Mn (CH
3COO)
24H
2O) 0.074g, after wet method fully grinds well in agate mortar, pack in the corundum crucible, compacting covers mouth of pot completely with dull and stereotyped crucible cover, put it into then in the bigger alumina crucible, and around corundum crucible, put into proper amount of active carbon, and bigger mouth of pot is covered completely with the corundum sheet, place in the High Temperature Furnaces Heating Apparatus, be heated to 1150 ℃, constant temperature 2 hours.High temperature is come out of the stove, and is cooled to room temperature and gets the near-white powder.Identify that through XRD product is magnesium stannate (Mg
2SnO
4), emmission spectrum comprises one from 460 to 560nm arrowband.Through 254nm UV-irradiation 1 minute, luminescent material presented strong green long afterglow emission, is about 3 hours time of persistence.
Although above-mentioned embodiment has described the present invention in detail, those skilled in the art or researchist can carry out various conversion and can not break away from scope as the described patent of the present invention of claims.
Claims (2)
1. the preparation method of a manganese ion activated green long afterglow luminescent material, its material consists of: Mg
2SnO
4: Mn
2+, wherein, inverse spinel structure magnesium stannate Mg
2SnO
4Be matrix, Mn
2+Be active ions; With magnesium oxide MgO and tindioxide SnO
2Make base starting material, doping active ions Mn
2+, thorough mixing is placed in the corundum crucible, adds a cover, and calcination, cooling can obtain the near-white powdered product; It is characterized in that: described calcination temperature is 950-1150 ℃, in 1-3 hours reaction times, makes reductive agent with activated carbon; Described magnesium oxide MgO and tindioxide SnO
2Be analytical pure, take by weighing by 2:1 mole proportioning; Described activator is with manganous oxalate Mn (CH
3COO)
24H
2The O form adds.
2. the preparation method of manganese ion activated green long afterglow luminescent material according to claim 1, it is characterized in that: high temperature is come out of the stove after the calcination, cools off in air.
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| CNB2005100167956A CN100463950C (en) | 2005-05-18 | 2005-05-18 | Manganese ion activated green long afterglow luminescent material and its preparation method |
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|---|---|
| CN1865395A CN1865395A (en) | 2006-11-22 |
| CN100463950C true CN100463950C (en) | 2009-02-25 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013166661A1 (en) * | 2012-05-08 | 2013-11-14 | 海洋王照明科技股份有限公司 | Manganese-doped magnesium stannate luminescent material and preparation method therefor |
| CN106433641B (en) * | 2016-09-05 | 2018-08-21 | 中南大学 | A kind of method that low heat temperature solid state reaction prepares rear-earth-doped calcium stannate fluorescent material |
| CN108441215B (en) * | 2018-05-12 | 2019-06-28 | 井冈山大学 | A kind of solid-state lighting LED red fluorescence material and synthetic method |
| CN112961676A (en) * | 2021-02-26 | 2021-06-15 | 吉林大学 | Preparation method of manganese-doped zinc germanate nano material |
| CN114369457B (en) * | 2021-12-09 | 2023-05-16 | 江西师范大学 | Preparation method of green long-afterglow luminescent material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2542336A (en) * | 1945-05-01 | 1951-02-20 | Gen Electric | Titanium activated magnesium orthostannate |
| GB994390A (en) * | 1962-01-02 | 1965-06-10 | Sylvania Electric Prod | Magnesium orthostannate phosphors |
| US5976413A (en) * | 1998-04-28 | 1999-11-02 | Osram Sylvania Inc. | Method of preparing a lead and manganese co-activated calcium metasilicate phosphor |
| CN1345908A (en) * | 2000-09-29 | 2002-04-24 | 住友化学工业株式会社 | Fluorescent material for vacuum ultraviolet ray radiation stimulated emission lighting device |
| US6409938B1 (en) * | 2000-03-27 | 2002-06-25 | The General Electric Company | Aluminum fluoride flux synthesis method for producing cerium doped YAG |
-
2005
- 2005-05-18 CN CNB2005100167956A patent/CN100463950C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2542336A (en) * | 1945-05-01 | 1951-02-20 | Gen Electric | Titanium activated magnesium orthostannate |
| GB994390A (en) * | 1962-01-02 | 1965-06-10 | Sylvania Electric Prod | Magnesium orthostannate phosphors |
| US5976413A (en) * | 1998-04-28 | 1999-11-02 | Osram Sylvania Inc. | Method of preparing a lead and manganese co-activated calcium metasilicate phosphor |
| US6409938B1 (en) * | 2000-03-27 | 2002-06-25 | The General Electric Company | Aluminum fluoride flux synthesis method for producing cerium doped YAG |
| CN1345908A (en) * | 2000-09-29 | 2002-04-24 | 住友化学工业株式会社 | Fluorescent material for vacuum ultraviolet ray radiation stimulated emission lighting device |
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| CN1865395A (en) | 2006-11-22 |
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Granted publication date: 20090225 Termination date: 20110518 |