CN1101349C - Process for preparing yellow-green rare-earth glass with long afterglow - Google Patents
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- CN1101349C CN1101349C CN00128255A CN00128255A CN1101349C CN 1101349 C CN1101349 C CN 1101349C CN 00128255 A CN00128255 A CN 00128255A CN 00128255 A CN00128255 A CN 00128255A CN 1101349 C CN1101349 C CN 1101349C
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Abstract
The present invention provides a manufacture method for rare-earth yellow green long persistence glass. The method selects strontium oxide, aluminum oxide and boron oxide as glass matrix, a fluxing agent and doping rare-earth are also added, the mixture is uniformly ground and mixed, and the rare-earth yellow green long persistence glass is obtained via isothermal treatment. The persistence of the glass can reach 24 hours after irradiated by sun light for half an hour.
Description
The invention belongs to the preparation method of yellow-green rare-earth glass with long afterglow.
At present, both at home and abroad the long-afterglow material overwhelming majority of report is a polycrystal powder, and long afterglow glass seldom appears in the newspapers and leads.Yellow-green rare-earth glass with long afterglow is as a kind of type material, and is energy-conservation in building, medicine equipment, and aviation, Emergency Light, there is purposes widely aspects such as artistic handicraft using.
The article of exercise question for " the adulterated calcium aluminium of divalent europium boron glass long-persistence luminous " delivered in " the solid-state communication " the 795th to 798 page of 1998 106 the 12nd phases of volume.Introduced a kind of calcium aluminium boron glass in the literary composition, the molar percentage composition of this glass is: 40% calcium oxide, 30% aluminium sesquioxide, 30% boron trioxide, 0.25% europiumsesquioxide, 0.25% Dysprosium trioxide.Formation condition is at first to add platinum crucible behind the frit mixing with said ratio, in 1450 ℃ of constant temperature generation in hour glass metals in High Temperature Furnaces Heating Apparatus, glass metal is poured on is cooled to room temperature on the stainless steel plate then; The glass that obtains is put into platinum crucible, in High Temperature Furnaces Heating Apparatus, added in 5% hydrogen atmosphere constant temperature one hour, obtain yellowish green glass by quenching at last in 95% argon gas at 1450 ℃.With 2 * 10
4This glass of the white fluorescent light irradiation of lumen was removed luminescent lamp after 30 minutes, and glass has the twilight sunset phenomenon, even but spend 8 hours in the dark still naked eyes distinguish this twilight sunset.But this method obtains product in two steps, and uses platinum crucible as means of production, and cost is higher; Be not long especially the time of persistence of products obtained therefrom, and only excite with white fluorescent lamp, and it is single to exist excitaton source, the shortcoming that use range is narrow.
The preparation method who the purpose of this invention is to provide a kind of yellow-green rare-earth glass with long afterglow, this method selective oxidation strontium, aluminium sesquioxide, boron trioxide is a glass matrix, add flux and rare earth doped, after grinding mixing, constant temperature is handled and is obtained yellow-green rare-earth glass with long afterglow.This glass shines half an hour under daylight after, twilight sunset was 24 hours.
The generation of steady persistence phenomenon is to cause the generation of impurity level owing to mix, and in excitation phase, impurity level is caught hole or electronics, when excite finish after, these electronics and hole slowly discharge owing to thermal motion, and energy is emitted in electronics and hole combination, thereby produces the steady persistence phenomenon.As trivalent rare earth ions RE
3+Mix the alkaline earth aluminate SrAl that contains divalent europium
2O
4: Eu
2+When middle, trivalent rare earth ions RE
3+Non-equivalence replaces the alkaline earth ion Sr of divalence
2+Thereby, having produced trap with appropriate depth, thermoluminescence spectrum peak should be near 50 ℃; Trap can be in order to store electrons and hole, and when trap depth was too dark, electronics and hole can not discharge from trap, and when trap depth was too shallow, the d/d speed in electronics and hole was then too fast, and both of these case all is unfavorable for the generation of steady persistence phenomenon.Except requiring suitable trap depth, it is also very important that adulterated trivalent rare earth ions has suitable avidity to electronics in the trap and hole, too by force or too weak avidity twilight sunset is not all had the prolongation effect.People such as Soviet Union's clanging or clanking sound once tried to achieve trivalent rare earth ions with spectrography optics electronegativity χ is disclosed on " Chinese rare-earth journal " 1999 the 17th volume, and proof by experiment: have only λ
x=1.21～1.09 trivalent co-activation ion Dy
3+, Nd
3+, Ho
3+, Pr
3+, Er
3+Can prolong twilight sunset effectively, they are in the middle part of the light group of the lanthanides and the latter half of heavy lanthanide of forebody in the group of the lanthanides respectively, and their optics electronegativity χ is respectively 1.21,1.21,1.14,1.18,1.09.Like this, at room temperature, electronics in the trap and hole can overcome trap level, are discharged into Eu lentamente
2+5d excited state on, taking place from Eu
2+5d excited state to ground state
8S
7/2Transition, thereby can make Eu
2+The emission long-afterglow fluorescent, emission peak is at 520nm.
The glass matrix molar percentage that the present invention selects consists of: strontium oxide 44%-55%, aluminium sesquioxide 20%-29%, boron trioxide 20%-29%; The silicon-dioxide or the Quilonum Retard that add 0.5%-1% in the glass matrix are made flux.Two kinds of rare earth oxides of doping in glass matrix, first kind is europiumsesquioxide, and second kind is any one in Dysprosium trioxide, Praseodymium trioxide, erbium oxide, the holmium oxide, and rare earth doped molar content is 0.05%-0.15%.Behind glass matrix and rare earth doped grinding mixing, add in the alumina crucible, in High Temperature Furnaces Heating Apparatus, generated glass metal in 0.5 hour-3 hours in 1250 ℃ of-1500 ℃ of constant temperature, feed reducing gas simultaneously: 97% nitrogen adds 3% hydrogen, carbon monoxide or ammonia.Two kinds of heat treatment modes are arranged after glass metal is come out of the stove: first kind is to quench between 0 ℃ to 150 ℃, the glass that obtains under protection of reducing atmosphere between 600 ℃ to 900 ℃ constant temperature handled 1-6 hour; Second kind is annealing between 150 ℃ to 1000 ℃, when when annealing between 1000 ℃ for 500 ℃, protection of reducing atmosphere should be arranged.Adopt in these two kinds of heat treatment modes any one, can obtain yellow-green rare-earth glass with long afterglow.
The silicon-dioxide that adds 0.5%-1% in the preferred glass matrix of the present invention is made flux.
The Quilonum Retard that adds 0.5%-1% in the preferred glass matrix of the present invention is made flux.
The present invention preferably in glass matrix rare earth doped oxide compound be europiumsesquioxide.
The present invention preferably in glass matrix rare earth doped oxide compound be Dysprosium trioxide.
The present invention preferably in glass matrix rare earth doped oxide compound be Praseodymium trioxide.
The present invention preferably in glass matrix rare earth doped oxide compound be erbium oxide.
The present invention preferably in glass matrix rare earth doped oxide compound be holmium oxide.
Constant temperature in High Temperature Furnaces Heating Apparatus feeds reducing gas 97% nitrogen simultaneously and adds 3% hydrogen.
Constant temperature in High Temperature Furnaces Heating Apparatus feeds the reducing gas carbon monoxide simultaneously.
Constant temperature in High Temperature Furnaces Heating Apparatus feeds the reducing gas ammonia simultaneously.
The glass metal postheat treatment mode of coming out of the stove is to quench between 0 ℃ to 150 ℃, the glass that obtains under protection of reducing atmosphere between 600 ℃ to 900 ℃ constant temperature handled 1-6 hour.
Glass metal come out of the stove the postheat treatment mode be between 150 ℃ to 1000 ℃ annealing, when when between 1000 ℃, annealing for 500 ℃, use protection of reducing atmosphere.
The preparation method of yellow-green rare-earth glass with long afterglow of the present invention is simple, the glass twilight sunset that makes is bright, time of persistence is long, sunlight hits is after half an hour, the twilight sunset of glass was 24 hours, and this glass can be used fluorescent lamp, sunlight hits, and natural light also can excite this glass during the cloudy day, therefore, indoors the open air can both be used.This long afterglow glass is "dead" simultaneously, can not work the mischief to environment; The present invention adopts alumina crucible as the glass melting instrument, makes production cost use platinum crucible greatly to reduce.
Embodiment provided by the invention is as follows:
Embodiment 1:
The molar percentage of glass consists of: 20% boron trioxide, 26% aluminium sesquioxide, 54% strontium oxide, 0.15% europiumsesquioxide, 0.15% holmium oxide, 1% silicon-dioxide; The alumina crucible of packing into behind the former abrasive lapping mixing is in high temperature box furnace, under carbon monoxide atmosphere, 1250 ℃ of constant temperature 3 hours; Glass metal is come out of the stove the back 0 ℃ of quenching, and in 900 ℃ of constant temperature 1 hour, obtain outward appearance was yellowish green long afterglow glass to the glass that obtains in carbon monoxide atmosphere, and solar radiation is after half an hour, long 25 hours of twilight sunset.
Embodiment 2:
The molar percentage of glass consists of: 25% boron trioxide, 25% aluminium sesquioxide, 50% strontium oxide, 0.09% europiumsesquioxide, 0.09% Dysprosium trioxide, 0.5% silicon-dioxide; The alumina crucible of packing into behind the former abrasive lapping mixing, in high temperature box furnace, add under 3% hydrogen atmosphere in 97% nitrogen, 1300 ℃ of constant temperature 2 hours, glass metal was come out of the stove the back 60 ℃ of quenchings, is cooled to room temperature, the glass that obtains in carbon monoxide atmosphere in 600 ℃ of constant temperature 6 hours, obtain outward appearance and be green long afterglow glass, solar radiation is after half an hour, and twilight sunset is grown 27 hours.
Embodiment 3:
The molar percentage of glass consists of: 29% boron trioxide, 27% aluminium sesquioxide, 44% strontium oxide, 0.05% europiumsesquioxide, 0.05% Praseodymium trioxide, 0.5% Quilonum Retard; The alumina crucible of packing into behind the former abrasive lapping mixing in high temperature box furnace, under carbon monoxide atmosphere, 1400 ℃ of constant temperature 1 hour, is poured on after glass metal is come out of the stove in 400 ℃ the pig mold, is annealed to room temperature, obtains outward appearance and is green long afterglow glass.Solar radiation is after half an hour, and twilight sunset is grown 24 hours.
Embodiment 4:
The molar percentage of glass consists of: 26% boron trioxide, 29% aluminium sesquioxide, 45% strontium oxide, 0.12% europiumsesquioxide, 0.12% Dysprosium trioxide, 1% Quilonum Retard; The alumina crucible of packing into behind the former abrasive lapping mixing; in high temperature box furnace; add under 3% hydrogen atmosphere in 97% nitrogen; 1350 ℃ of constant temperature 1.5 hours; after coming out of the stove, glass metal under the carbon monoxide atmosphere protection, is annealed to room temperature in 500 ℃; obtaining outward appearance is yellowish green long afterglow glass, and solar radiation is after half an hour, and twilight sunset is grown 27 hours.
Embodiment 5:
The molar percentage of glass consists of: 25% boron trioxide, 20% aluminium sesquioxide, 55% strontium oxide, 0.12% europiumsesquioxide, 0.15% erbium oxide, 1% Quilonum Retard; The alumina crucible of packing into behind the former abrasive lapping mixing; in high temperature box furnace; under ammonia atmosphere; 1500 ℃ of constant temperature 0.5 hour; after coming out of the stove, glass metal under the carbon monoxide atmosphere protection, is annealed to room temperature in 1000 ℃; obtaining outward appearance is yellowish green long afterglow glass, and solar radiation is after half an hour, and twilight sunset is grown 26 hours.
Claims (13)
1. the preparation method of a yellow-green rare-earth glass with long afterglow is characterized in that the glass matrix molar percentage of selecting consists of: strontium oxide 44%-55%, aluminium sesquioxide 20%-29%, boron trioxide 20%-29%; The silicon-dioxide or the Quilonum Retard that add 0.5%-1% in the glass matrix are made flux, two kinds of rare earth oxides mix in glass matrix, first kind is europiumsesquioxide, second kind is Dysprosium trioxide, Praseodymium trioxide, erbium oxide, in the holmium oxide any one, rare earth doped molar content is 0.05%-0.15%, behind glass matrix and rare earth doped grinding mixing, add in the alumina crucible, generated glass metal in 0.5 hour-3 hours in 1250 ℃ of-1500 ℃ of constant temperature in High Temperature Furnaces Heating Apparatus, feed reducing gas simultaneously: 97% nitrogen adds 3% hydrogen, carbon monoxide or ammonia; Two kinds of heat treatment modes are arranged after glass metal is come out of the stove: first kind is to quench between 0 ℃ to 150 ℃, the glass that obtains under protection of reducing atmosphere between 600 ℃ to 900 ℃ constant temperature handled 1-6 hour; Second kind is annealing between 150 ℃ to 1000 ℃, when when annealing between 1000 ℃ for 500 ℃, uses protection of reducing atmosphere.
2. the preparation method of yellow-green rare-earth glass with long afterglow as claimed in claim 1 is characterized in that the silicon-dioxide of adding 0.5%-1% in the described glass matrix is made flux.
3. the preparation method of yellow-green rare-earth glass with long afterglow as claimed in claim 1 is characterized in that the Quilonum Retard of adding 0.5%-1% in the described glass matrix is made flux.
4. the preparation method of yellow-green rare-earth glass with long afterglow as claimed in claim 1, it is characterized in that described in glass matrix rare earth doped oxide compound be europiumsesquioxide.
5. the preparation method of yellow-green rare-earth glass with long afterglow as claimed in claim 1, it is characterized in that described in glass matrix rare earth doped oxide compound be Dysprosium trioxide.
6. the preparation method of yellow-green rare-earth glass with long afterglow as claimed in claim 1, it is characterized in that described in glass matrix rare earth doped oxide compound be Praseodymium trioxide.
7. the preparation method of yellow-green rare-earth glass with long afterglow as claimed in claim 1, it is characterized in that described in glass matrix rare earth doped oxide compound be erbium oxide.
8. the preparation method of yellow-green rare-earth glass with long afterglow as claimed in claim 1, it is characterized in that described in glass matrix rare earth doped oxide compound be holmium oxide.
9. the preparation method of yellow-green rare-earth glass with long afterglow as claimed in claim 1, it is characterized in that described in High Temperature Furnaces Heating Apparatus constant temperature, feed reducing gas 97% nitrogen simultaneously and add 3% hydrogen.
10. the preparation method of yellow-green rare-earth glass with long afterglow as claimed in claim 1, it is characterized in that described in High Temperature Furnaces Heating Apparatus constant temperature, feed the reducing gas carbon monoxide simultaneously.
11. the preparation method of yellow-green rare-earth glass with long afterglow as claimed in claim 1, it is characterized in that described in High Temperature Furnaces Heating Apparatus constant temperature, feed the reducing gas ammonia simultaneously.
12. the preparation method of yellow-green rare-earth glass with long afterglow as claimed in claim 1; it is characterized in that the described glass metal postheat treatment mode of coming out of the stove is to quench between 0 ℃ to 150 ℃, the glass that obtains under protection of reducing atmosphere between 600 ℃ to 900 ℃ constant temperature handled 1-6 hour.
13. the preparation method of yellow-green rare-earth glass with long afterglow as claimed in claim 1, it is characterized in that described glass metal come out of the stove the postheat treatment mode be between 150 ℃ to 1000 ℃ annealing, when when between 1000 ℃, annealing for 500 ℃, use protection of reducing atmosphere.
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|---|---|---|---|
| CN00128255A CN1101349C (en) | 2000-12-14 | 2000-12-14 | Process for preparing yellow-green rare-earth glass with long afterglow |
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| CN00128255A CN1101349C (en) | 2000-12-14 | 2000-12-14 | Process for preparing yellow-green rare-earth glass with long afterglow |
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| CN1305967A CN1305967A (en) | 2001-08-01 |
| CN1101349C true CN1101349C (en) | 2003-02-12 |
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| CN00128255A Expired - Fee Related CN1101349C (en) | 2000-12-14 | 2000-12-14 | Process for preparing yellow-green rare-earth glass with long afterglow |
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| CN107540227B (en) * | 2017-09-11 | 2020-07-07 | 济南大学 | Europium-doped feldspar phase-containing microcrystalline glass and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180670A (en) * | 1996-04-17 | 1998-05-06 | 康宁股份有限公司 | Rare earth doped oxyhalide laser glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180670A (en) * | 1996-04-17 | 1998-05-06 | 康宁股份有限公司 | Rare earth doped oxyhalide laser glass |
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