CN1546405A - Process for preparing rare-earth green long-lasting luminescent glass - Google Patents
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- CN1546405A CN1546405A CNA2003101159337A CN200310115933A CN1546405A CN 1546405 A CN1546405 A CN 1546405A CN A2003101159337 A CNA2003101159337 A CN A2003101159337A CN 200310115933 A CN200310115933 A CN 200310115933A CN 1546405 A CN1546405 A CN 1546405A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
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Abstract
The invention provides a process for preparing rare earth environmental protection long persistence glass comprising the steps of selecting alkaline earth oxide, boron oxide and silicon dioxde as primary hyaline, charging rare earth, grinding and mixing homogeneously, high temperature solid phase reaction, and annealing treatment.
Description
Technical field
The invention belongs to the preparation method of rare earth green long afterglow glass.
Background technology
The long afterglow material is a kind of energy-conservation low light level illumination and display material.It can be stored in luminous energy in the material after being subjected to daylight or UV-irradiation, and then slowly energy is discharged and luminous.
Traditional long-afterglow material mainly is the sulfide system, and as ZnS:Cu, Co etc. exist after-glow brightness low, and time of persistence is short, poor chemical stability, shortcomings such as easy deliquescence.In order to prolong the time of persistence of sulfide, adopted the way of adding radioelement; But the affiliation that adds of radioelement works the mischief to HUMAN HEALTH and environment, so the application of this long-afterglow material is subjected to very big restriction.The mid-90 in 20th century, found the new type long-persistence material SrAl of alkaline earth aluminate system
2O
4: Eu
2+, Dy
3+, this novel alkaline earth aluminate system long-afterglow material has been opened up the field that long-afterglow material is used.
At present, the long-afterglow material of report is polycrystal powder mostly both at home and abroad, and is also few about the report of long afterglow glass.Compare with powdered material, glass has transparent, can be made into the dull and stereotyped of bulk or is drawn into advantage such as glass fibre.The rare earth green long afterglow glass is as a kind of novel material, and the Emergency Light that can be used for building is energy-conservation, artistic handicraft using, optical storage, and aspect such as energetic ray detection.
The 185th page to 188 pages of " non-crystalline solids " magazines of 1999 the 244th phases have been delivered the article that is entitled as " blue-light-emitting of the divalent europium doped-glass that infrared femtosecond laser excites ".Introduced a kind of ca aluminosilicate glass in the literary composition, the mole of this glass consists of: 43% calcium oxide, 13% aluminum oxide, 44% silicon oxide and 0.05% europiumsesquioxide.The preparation method after above-mentioned raw material powder is mixed, puts into platinum crucible, takes out cool to room temperature under air atmosphere after 60 minutes in 1550 ℃ of constant temperature.Then glass is taken out, pulverize, put into the vitreous carbon crucible, under the reduction protection atmosphere of hydrogen, in 1550 ℃ of constant temperature 60 minutes, quench under the room temperature once more, obtain required glass.With transponder pulse is 120 femtoseconds, removes laser 200 kilo hertzs 10 seconds of laser excitation sample, and glass has blue twilight sunset phenomenon, sustainable 10 hours of this twilight sunset.This method need obtain product in two steps, and must carry out under reducing atmosphere, complex process, and cost is higher; Products obtained therefrom need use LASER Light Source to excite, and it is single to exist excitaton source, the shortcoming that use range is narrow.
Application number is that 02117958.1 Chinese patent has been reported a kind of preparation method with red long-afterglow and light stimulus long afterglow glass of memory storage function.
United States Patent (USP) 6372155 discloses a kind of glass system with steady persistence and optical stimulated luminescence phenomenon, and its green long afterglow is luminous to be realized by the doping terbium sesquioxide, and red long-afterglow is luminous to be realized by the doping manganese oxide.This glass does not have light stimulus steady persistence phenomenon, and this system is with Ga
2O
3Or Al
2O
3For main glass generates body, the rare earth element Ln that mixes altogether
2O
3(Ln=Y, La, Gd, Lu, Sm, Dy, Tm Pr) mainly is for the viscosity that improves glass and suppresses glass crystallization.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of rare earth green long afterglow glass.
The present invention selects alkaline earth metal oxide, and boron trioxide, silicon-dioxide are main glass matrix, adds rare earth ion, and after grinding mixing, high temperature constant temperature is handled and obtained the rare earth green long afterglow glass.After half an hour, twilight sunset reaches 10 hours to this glass at ultra violet lamp.After twilight sunset disappears, with long wave ultraviolet, visible light or infrared-ray irradiation monolithic glass, remove excitaton source after, green long afterglow reappears.
The glass mole that the present invention selects is formed and is represented with following formula:
aMO-bM′O-cAl
2O
3-dB
2O
3-eSiO
2：xTb，yR
Wherein M is one or more elements in alkali metal lithium (Li), sodium (Na), the potassium (K);
M ' is one or more elements in alkaline earth elements ca (Ca), strontium (Sr), barium (Ba), the magnesium (Mg);
R is one or more elements in rare-earth elements of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu) and transition metal titanium (Ti), zirconium (Zr), vanadium (V), chromium (Cr), molybdenum (Mo), manganese (Mn), copper (Cu), germanium (Ge), tin (Sn), plumbous (Pb), antimony (Sb), the bismuth (Bi);
A, b, c, d, e are mole coefficient, a:0-15%, b:20-70%, c:0-15%, d:8-70%, e:10-60%;
X is molar content 0.002-2.0mol%,
Y is molar content 0-1.0mol%;
Behind glass matrix and rare earth doped grinding mixing, add in the crucible, in High Temperature Furnaces Heating Apparatus in 1250-1500 ℃ of constant temperature 0.5 hour-3 hours, in the good mould of impouring preheating, annealing is 0.5-6 hour between 500 ℃-1000 ℃, and obtaining maximum emission wavelength is the rare earth green long afterglow glass of 543nm.With ultraviolet ray excited this glass of UV254nm 30 minutes, remove excitaton source, in the dark the green twilight sunset of glass reaches 10 hours.And the long wave ultraviolet that uses UV366nm can not excite this glass sample to produce green long afterglow.After the twilight sunset for the treatment of glass sample disappears, with long wave ultraviolet, visible light or infrared-ray irradiation monolithic glass, remove excitaton source after, green long afterglow reappears, promptly so-called light stimulus steady persistence phenomenon.
Compare with the glass system with steady persistence and optical stimulated luminescence phenomenon that aforesaid U.S. Patent is described, glass of the present invention has following characteristics: 1, and alkaline earth metal oxide M ' O (Ca, Sr, Ba, Mg), boron oxide, silicon-dioxide are that main glass generates body, do not need to add Ga
2O
32, and alkalimetal oxide MO (Li, Na, K), Al
2O
3Modify body for glass network, incorporation smaller (0-15%) mainly is in order to create suitable trap depth to improve the afterglow property of glass; 3, the rare-earth element R of mixing (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, one or more elements among the Lu) and transition metal R (Ti, Zr, V, Cr, Mo, Mn, Cu, Ge, Sn, Pb, Sb, one or more elements among the Bi) be coactivator, be used for the luminous of sensitization ion Tb and improve the afterglow property of glass; 4, rare earth green long afterglow glass of the present invention also has the light stimulus steady persistence phenomenon different with the optical stimulated luminescence phenomenon except having the steady persistence phenomenon.
The preparation method of rare earth green long afterglow glass of the present invention is simple, and the glass twilight sunset that makes is bright, and time of persistence is long.Ultra violet lamp reaches 10 hours time of persistence after half an hour.Simultaneously, this long afterglow glass is "dead", can not produce harm to environment.Reaction process of the present invention can be carried out under air atmosphere, makes production cost use hydrogen reducing atmosphere greatly to reduce.
Description of drawings
Fig. 1 is rare earth green long afterglow glass 40SrO-10B of the present invention
2O
3-50SiO
2: 0.5Tb
2O
3, 0.2Gd
2O
3Excitation spectrum
Fig. 2 is rare earth green long afterglow glass 40SrO-10B of the present invention
2O
3-50SiO
2: 0.5Tb
2O
3, 0.2Gd
2O
3Emmission spectrum
Embodiment
The present invention is described in detail below in conjunction with embodiment, but the present invention is not made by these
Embodiment limits.
Embodiment 1,
The molar percentage of glass consists of: 5% Quilonum Retard, 30% barium oxide, 5% aluminium sesquioxide, 10% boron trioxide, 50% silicon-dioxide, 0.05% terbium sesquioxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1300 ℃ of constant temperature one hour, in the mould of impouring preheating, 500 ℃ of annealing half an hour, is cooled to room temperature, obtains water white long afterglow glass.Down this glass of irradiation is after half an hour for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, the twilight sunset that stops to excite glass after 10 hours in the dark still naked eyes can distinguish.After twilight sunset disappears, be that the long wave ultraviolet light of 366nm shines 30 seconds of monolithic glass with wavelength, remove exciting light source after, the green long afterglow of glass reappears, i.e. the light stimulus steady persistence.
Embodiment 2,
The molar percentage of glass consists of: 40% barium oxide, 10% aluminium sesquioxide, 8% boron trioxide, 42% silicon-dioxide, 0.002% terbium sesquioxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1400 ℃ of constant temperature one hour, in the mould of impouring preheating, 550 ℃ of annealing 1 hour, is cooled to room temperature, obtains water white long afterglow glass.Down this glass of irradiation is after half an hour for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, the twilight sunset that stops to excite glass after 7 hours in the dark still naked eyes can distinguish.After twilight sunset disappears, be 20 seconds of laser radiation monolithic glass of 514nm with wavelength, remove laser after, the green long afterglow of glass reappears, i.e. the light stimulus steady persistence.
Embodiment 3,
The molar percentage of glass consists of: 20% barium oxide, 20% boron trioxide, 60% silicon-dioxide, 0.3% terbium sesquioxide, 0.05% Samarium trioxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1400 ℃ of constant temperature one hour, in the mould of impouring preheating, 600 ℃ of annealing 3 hours, is cooled to room temperature, obtains water white long afterglow glass.Down this glass of irradiation is after half an hour for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, the twilight sunset that stops to excite glass after 9 hours in the dark still naked eyes can distinguish.After twilight sunset disappears, be that the long wave ultraviolet light of 366nm shines 30 seconds of monolithic glass with wavelength, remove exciting light source after, the green long afterglow of glass reappears, i.e. the light stimulus steady persistence.
Embodiment 4,
The molar percentage of glass consists of: 10% calcium oxide, 35% barium oxide, 15% boron trioxide, 40% silicon-dioxide, 0.2% terbium sesquioxide, 0.1% gadolinium sesquioxide, 0.05% dysprosium oxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1400 ℃ of constant temperature one hour, in the mould of impouring preheating, 600 ℃ of annealing half an hour, is cooled to room temperature, obtains water white long afterglow glass.Down this glass of irradiation is after half an hour for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, the twilight sunset that stops to excite glass after 9 hours in the dark still naked eyes can distinguish.After twilight sunset disappears, be that the long wave ultraviolet light of 366nm shines 30 seconds of monolithic glass with wavelength, remove exciting light source after, the green long afterglow of glass reappears, i.e. the light stimulus steady persistence.
Embodiment 5,
The molar percentage of glass consists of: 10% yellow soda ash, 30% barium oxide, 20% boron trioxide, 40% silicon-dioxide, 0.3% terbium sesquioxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1350 ℃ of constant temperature one hour, in the mould of impouring preheating, 600 ℃ of annealing 2 hours, is cooled to room temperature, obtains water white long afterglow glass.Down this glass of irradiation is after half an hour for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, the twilight sunset that stops to excite glass after 8 hours in the dark still naked eyes can distinguish.After twilight sunset disappears, be 20 seconds of laser radiation monolithic glass of 488nm with wavelength, remove laser after, the green long afterglow of glass reappears, i.e. the light stimulus steady persistence.
Embodiment 6,
The molar percentage of glass consists of: 20% barium oxide, 70% boron trioxide, 10% silicon-dioxide, 0.4% terbium sesquioxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1300 ℃ of constant temperature one hour, in the mould of impouring preheating, 500 ℃ of annealing 1 hour, is cooled to room temperature, obtains water white long afterglow glass.This glass of irradiation is after half an hour down for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, sustainable 9 hours of twilight sunset.After twilight sunset disappears, be that the long wave ultraviolet light of 366nm shines 30 seconds of monolithic glass with wavelength, remove exciting light source after, the green long afterglow of glass reappears, i.e. the light stimulus steady persistence.
Embodiment 7,
The molar percentage of glass consists of: 40% Strontium carbonate powder, 10% boron trioxide, 50% silicon-dioxide, 0.5% terbium sesquioxide, 0.2% gadolinium sesquioxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1350 ℃ of constant temperature one hour, in the mould of impouring preheating, 600 ℃ of annealing 3 hours, is cooled to room temperature, obtains water white long afterglow glass.This glass of irradiation is after half an hour down for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, sustainable 10 hours of twilight sunset.After twilight sunset disappears, be 60 seconds of laser radiation monolithic glass of 980nm with wavelength, remove laser after, the green long afterglow of glass reappears, i.e. the light stimulus steady persistence.
Embodiment 8,
The molar percentage of glass consists of: 5% salt of wormwood, 35% Strontium carbonate powder, 20% boron trioxide, 40% silicon-dioxide, 0.4% terbium sesquioxide, 0.05% Neodymium trioxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1400 ℃ of constant temperature one hour, in the mould of impouring preheating, 650 ℃ of annealing 2 hours, is cooled to room temperature, obtains water white long afterglow glass.This glass of irradiation is after half an hour down for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, long 8 hours of twilight sunset.After twilight sunset disappears, be that the long wave ultraviolet light of 366nm shines 30 seconds of monolithic glass with wavelength, remove exciting light source after, the green long afterglow of glass reappears, i.e. the light stimulus steady persistence.
Embodiment 9,
The molar percentage of glass consists of: 10% barium oxide, 40% Strontium carbonate powder, 30% boron trioxide, 20% silicon-dioxide, 0.3% terbium sesquioxide, 0.05% Holmium trioxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1400 ℃ of constant temperature one hour, in the mould of impouring preheating, 650 ℃ of annealing 2 hours, is cooled to room temperature, obtains water white long afterglow glass.This glass of irradiation is after half an hour down for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, long 9 hours of twilight sunset.After twilight sunset disappears, be 60 seconds of laser radiation monolithic glass of 808nm with wavelength, remove laser after, the green long afterglow of glass reappears, i.e. the light stimulus steady persistence.
Embodiment 10,
The molar percentage of glass consists of: 70% Strontium carbonate powder, 20% boron trioxide, 10% silicon-dioxide, 0.2% terbium sesquioxide, 0.05% dysprosium oxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1400 ℃ of constant temperature one hour, in the mould of impouring preheating, 650 ℃ of annealing 3 hours, is cooled to room temperature, obtains water white long afterglow glass.This glass of irradiation is after half an hour down for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, long 8 hours of twilight sunset.After twilight sunset disappears, be that the long wave ultraviolet light of 366nm shines 30 seconds of monolithic glass with wavelength, remove exciting light source after, green long afterglow reappears, i.e. the light stimulus steady persistence.
Embodiment 11,
The molar percentage of glass consists of: 5% salt of wormwood, 10% Quilonum Retard, 30% Strontium carbonate powder, 20% boron trioxide, 35% silicon-dioxide, 0.3% terbium sesquioxide, 0.5% zirconium dioxide, 0.05% tindioxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1500 ℃ of constant temperature one hour, in the mould of impouring preheating, 650 ℃ of annealing 1 hour, is cooled to room temperature, obtains water white long afterglow glass.This glass of irradiation is after half an hour down for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, long 9 hours of twilight sunset.After twilight sunset disappears, be 20 seconds of laser radiation monolithic glass of 514nm with wavelength, remove laser after, the green long afterglow of glass reappears, i.e. the light stimulus steady persistence.
Embodiment 12,
The molar percentage of glass consists of: 30% Strontium carbonate powder, 15% aluminum oxide, 18% boron trioxide, 37% silicon-dioxide, 1.0% terbium sesquioxide, 0.3% gadolinium sesquioxide, 0.05% Praseodymium trioxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1400 ℃ of constant temperature one hour, in the mould of impouring preheating, 600 ℃ of annealing 1 hour, is cooled to room temperature, obtains water white long afterglow glass.This glass of irradiation is after half an hour down for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, long 10 hours of twilight sunset.After twilight sunset disappears, be that the long wave ultraviolet light of 366nm shines 30 seconds of monolithic glass with wavelength, remove exciting light source after, green long afterglow reappears, i.e. the light stimulus steady persistence.
Embodiment 13,
The molar percentage of glass consists of: 35% magnesium oxide, 5% aluminium sesquioxide, 18% boron trioxide, 42% silicon-dioxide, 0.2% terbium sesquioxide, 0.1% trioxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1500 ℃ of constant temperature one hour, in the mould of impouring preheating, 600 ℃ of annealing 2 hours, is cooled to room temperature, obtains water white long afterglow glass.This glass of irradiation is after half an hour down for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, long 10 hours of twilight sunset.After twilight sunset disappears, be that the long wave ultraviolet light of 366nm shines 30 seconds of monolithic glass with wavelength, remove exciting light source after, green long afterglow reappears, i.e. the light stimulus steady persistence.
Embodiment 14,
The molar percentage of glass consists of: 5% Quilonum Retard, 20% magnesium oxide, 35% boron trioxide, 40% silicon-dioxide, 0.4% terbium sesquioxide, 0.3% tindioxide, 0.1% lutecium oxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1500 ℃ of constant temperature one hour, in the mould of impouring preheating, 600 ℃ of annealing 2 hours, is cooled to room temperature, obtains water white long afterglow glass.This glass of irradiation is after half an hour down for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, long 8 hours of twilight sunset.After twilight sunset disappears, be 20 seconds of laser radiation monolithic glass of 514nm with wavelength, remove laser after, the green long afterglow of glass reappears, i.e. the light stimulus steady persistence.
Embodiment 15,
The molar percentage of glass consists of: 30% magnesium oxide, 5% aluminium sesquioxide, 25% boron trioxide, 40% silicon-dioxide, 2.0% terbium sesquioxide, 0.1% germanium oxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1450 ℃ of constant temperature one hour, in the mould of impouring preheating, 600 ℃ of annealing 6 hours, is cooled to room temperature, obtains water white long afterglow glass.This glass of irradiation is after half an hour down for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, long 8 hours of twilight sunset.After twilight sunset disappears, be 20 seconds of laser radiation monolithic glass of 488nm with wavelength, remove laser after, the green long afterglow of glass reappears, i.e. the light stimulus steady persistence.
Embodiment 16,
The molar percentage of glass consists of: 5% calcium oxide, 35% magnesium oxide, 50% boron trioxide, 10% silicon-dioxide, 0.3% terbium sesquioxide, 1.0% gadolinium sesquioxide.Raw material is after grinding mixing, and the crucible of packing in High Temperature Furnaces Heating Apparatus, in 1450 ℃ of constant temperature one hour, in the mould of impouring preheating, 600 ℃ of annealing 1 hour, is cooled to room temperature, obtains water white long afterglow glass.This glass of irradiation is after half an hour down for the UV254nm ultraviolet lamp, and glass sends bright green long afterglow, long 9 hours of twilight sunset.After twilight sunset disappears, be that the long wave ultraviolet light of 366nm shines 30 seconds of monolithic glass with wavelength, remove exciting light source after, green long afterglow reappears, i.e. the light stimulus steady persistence.
Claims (1)
1, a kind of preparation method of rare earth green long afterglow glass is characterized in that the glass mole selected is formed to represent with following formula:
aMO-bM′O-cAl
2O
3-dB
2O
3-eSiO
2：xTb，yR
Wherein M is one or more elements in alkali metal lithium, sodium, the potassium;
M ' is one or more elements in alkaline earth elements ca, strontium, barium, the magnesium;
R is one or more elements in rare-earth elements of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and transition metal titanium, zirconium, vanadium, chromium, molybdenum, manganese, copper, germanium, tin, lead, antimony, the bismuth;
A, b, c, d, e are mole coefficient, a:0-15%, b:20-70%, c:0-15%, d:8-70%, e:10-60%;
X is molar content 0.002-2.0mol%,
Y is molar content 0-1.0mol%;
Behind glass matrix and rare earth doped grinding mixing, add in the crucible, in High Temperature Furnaces Heating Apparatus in 1250-1500 ℃ of constant temperature 0.5 hour-3 hours, in the good mould of impouring preheating, annealing is 0.5-6 hour between 500 ℃-1000 ℃, and obtaining maximum emission wavelength is the rare earth green long afterglow glass of 543nm.
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| CN101830638A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Novel europium ion-doped high-brightness cyan silicate light emitting glass |
| CN101885964A (en) * | 2010-06-29 | 2010-11-17 | 上海科炎光电技术有限公司 | Green luminescent material for infrared excitation |
| CN101691279B (en) * | 2009-09-30 | 2011-12-14 | 华中科技大学 | Method for manufacturing vycor glass emitting green light |
| CN102452793A (en) * | 2010-10-19 | 2012-05-16 | 同济大学 | High-luminous-intensity terbium-activated silicate glass and preparation method thereof |
| US8431502B2 (en) | 2008-02-26 | 2013-04-30 | Corning Incorporated | Silicate glasses having low seed concentration |
| CN103073180A (en) * | 2013-01-17 | 2013-05-01 | 昆明理工大学 | Bismuth-doped silicon boron aluminate optical glass and preparation method thereof |
| CN105347673A (en) * | 2015-11-23 | 2016-02-24 | 华东理工大学 | Tin-terbium co-doped luminescent glass having excitation wavelength broadened to deep ultraviolet region |
| CN105585247A (en) * | 2015-06-11 | 2016-05-18 | 华东理工大学 | Quickly-attenuated and ultraviolet-excited terbium-ion-doped luminescent glass |
| CN108483903A (en) * | 2018-05-22 | 2018-09-04 | 广东工业大学 | A kind of fluorescence compound glass and preparation method thereof |
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