CN100398475C - Preparation method for luminous glass - Google Patents
Preparation method for luminous glass Download PDFInfo
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- CN100398475C CN100398475C CNB2005100264496A CN200510026449A CN100398475C CN 100398475 C CN100398475 C CN 100398475C CN B2005100264496 A CNB2005100264496 A CN B2005100264496A CN 200510026449 A CN200510026449 A CN 200510026449A CN 100398475 C CN100398475 C CN 100398475C
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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
Abstract
The present invention relates to a preparation method for luminescent glass. In the method, the melting preparation of the glass can be accomplished by two steps: step 1, silicate glass containing ions with luminescent activity is prepared by melting; step 2, after being crushed and added with boron oxides and ammonium salts, the silicate glass is re-melted in a crucible with a cover or a high-temperature furnace in which ammonia gas is introduced, and subsequently, borosilicate glass mixed with low-valence luminescent ions of the luminescent elements or mainly mixed with the low-valence luminescent ions is obtained by cooling and forming. The present invention is characterized in that the ions with luminescent activity comprise cerium and europium belonging to rare-earth elements and 0.1 to 2.5% of manganese belonging to transition metal elements, the ratio of the ammonium salts to the silicate glass during re-melting in step 2 needs to be higher than 0.15.
Description
Technical field
The present invention relates to fluorescent glass, particularly a kind of preparation method of fluorescent glass.
Background technology
The modern life be unable to do without luminescent material, and common phosphor has transparent luminescent material and opaque luminescent material.The fluorescent lamp that uses in the daily life is exactly by the BaMgAl that sends out blue streak
10O
17: (Ce, Gd, Tb) MgB of Eu, green light
5O
10With the Y that glows
2O
3: Eu mixes and has formed the phosphor material that emits white light; Then be to have adopted to be mixed with isoionic ZnS of Cu, Ag and Y in the chromoscope
2O
3The S:Eu luminescent material converts electron rays the visible light of various different colours to, and these luminescent materials all are some opaque powders.On the other hand, some have mixed the transparent monocrystal material of light emitting ionic, and for example ruby and yttrium aluminum garnet etc. have the excellent characteristics of luminescence and be actually used in laser working medium; The glass that mixes light emitting ionics such as Nd and Er is also as laserable material, optical fiber laser and fiber amplifier material.Powder luminous material is because opaque, and its practicality is restricted, and for example this class material just can not be used as laser medium, and monocrystal material preparation cost height is difficult to make big fast and different shape.Than powder and monocrystal material, the significant advantage of oxide glass is to have good light transmittance, high uniformity, low cost and make bulk easily and different shape comprises optical fiber etc., therefore, oxide glass is suitable as the luminous and laser medium material of rare earth and transition metal plasma doping very much.But, be subjected to the restriction of the preparation condition and the glass structure of glass, than crystalline material, a lot of luminescent active ions are in glass a little less than the luminous intensity, and are even not luminous.For example, be positioned near the 692nm ruddiness with what general method for glass preparation just can not get that trivalent chromic ion sent in ruby; Rare earth luminous ion has tens kinds, but at present the rare earth doped luminescent glass of practicability has only above-mentioned Nd and the Er ionic glass mixed.More in order to obtain with the Applied Materials of glass as the substrate material of luminescent active ion, also need to improve the luminous intensity of luminescent active ion in glass by the preparation technology who changes glass.
We find in experiment when fusion prepares multicomponent glass, divide two sections melten glass, and add ammonium salt compound when second time fusion in glass, can strengthen some light emitting ionics luminous intensities in glass at a low price.In this way, at first we have successfully realized trivalent chromic ion glow (Chen Danping, " chromium ion blended red light emitting glass and manufacture method thereof ", patent publication No.: 1587143) in oxide glass.Now, we have prepared the adulterated glass of other light emitting ionic in this way again, find can strengthen equally their luminous intensity.
Summary of the invention
The manufacture method that the purpose of this invention is to provide a kind of new fluorescent glass.
The feature of this method is the multicomponent glass that luminescent active ion is mixed in the preparation of fusion in two steps, will add ammonium salt compound during fusion for the second time in glass, and some glass also will be heat-treated, with further raising luminous intensity.
Technical scheme of the present invention is as follows:
Specific implementation method of the present invention is that the glass melting preparation is finished in two steps, and the first step is that the fusion preparation contains the silicate glass that weight ratio is 0.1～2.5% luminescent active ion, and luminescent active ion comprises rare-earth element cerium or europium or transition metal manganese.Second step was that this silicate glass is pulverized, after adding the oxide compound and ammonium salt of boron, carry out fusion again in crucible with cover or in the High Temperature Furnaces Heating Apparatus of logical ammonia, cooling forming subsequently, just can obtain mixing above-mentioned light-emitting element lower valency light emitting ionic or based on the borosilicate glass of lower valency light emitting ionic.When the fusion preparation contained the borosilicate glass of luminescent active ion, ammonium salt: the weight ratio of silicate glass must be greater than 0.15.Second step can also be to add primary ammonium phosphate again in the silicate glass after this pulverizing, primary ammonium phosphate: the weight ratio of silicate glass is 1.1,1.2,1.4, fusion again in crucible with cover or in the High Temperature Furnaces Heating Apparatus of logical ammonia just can obtain mixing the lower valency light emitting ionic of above-mentioned light-emitting element or based on the phosphosilicate glass of lower valency light emitting ionic.Because the ammonium of small amount of residual is to strengthening the luminous vital role that has in the glass, therefore attention will be carried out fusion again in crucible with cover or in the High Temperature Furnaces Heating Apparatus of logical ammonia during glass melting second step, in logical ammonia crucible with cover during fusion, fusion time can not be long, in 10～20 minutes.
Afterwards, heat-treat near again these borosilicate glasses or phosphosilicate glass being put into the transition temperature of the inherent glass of High Temperature Furnaces Heating Apparatus, can further improve its luminous intensity or change glow color.
Technique effect of the present invention:
The inventive method is particularly suitable for improving the lower valency ionic luminous intensity of the element with multiple valence state.Mixing cerium ion glass and can send strong blue light and UV-light, mix that mn ion glass can send ruddiness, europium-ion-doped glass can send strong blue light and ruddiness with the inventive method preparation.The further phase-splitting of this glass is handled, can also be improved its luminous intensity.This class glass can be used as photoluminescence glass, and might become the new working-laser material of a class.The present invention is by twice melten glass, the reduction effect that produces at glass melting liquid when utilizing the decomposition of high temperature ammonium salt, and by fusion in crucible with cover or the ammonia atmosphere, allow a spot of ammonium ion or nitrogen element etc. remain in the glass, change the lattice field intensity on every side of light emitting ionic in the glass, strengthened the luminous intensity of light emitting ionic.We have tested this method with fluorescence spectrophotometer and have strengthened luminous effect.
More particularly: this glass of mixing cerium ion just can send centre wavelength under wavelength is optical excitation about 240～330nm be visible blue and UV-light about 370nm; Europium-ion-doped glass can send centre wavelength under wavelength is optical excitation about 250nm be visible red about 613nm, and be visible blue about 420nm sending centre wavelength under the optical excitation of 300～360nm; The glass of mixing mn ion can send centre wavelength under wavelength is optical excitation about 250nm be the visible light red light in broadband about 565nm.
Description of drawings
Fig. 1 has shown three kinds of luminous intensities of mixing the cerium ion borosilicate glass, although they have identical glass to form and cerium ion content, because its preparation technology's difference under same test condition, has different luminous intensity.Curve (1) is the glass that is mixed with ammonium nitrate in a step fusion and the raw material; Curve (2) is the glass that is not mixed with ammonium nitrate in a step fusion and the raw material; When being two step fusions and fusion for the second time, mixes curve (3) glass of ammonium nitrate in the raw material.The luminescence peak of these three kinds of glass is all about 370nm, and the scope of their excitation spectrum is also roughly the same, and visibly different luminous intensity of mixing the glass of ammonium nitrate when being two step fusions and fusion for the second time in the raw material is 3～5 times of other two kinds of glass luminous intensities.
What Fig. 2 showed is the effect that thermal treatment strengthens the luminous intensity of mixing the cerium ion borosilicate glass.Mix the luminous intensity before the ammonium nitrate glass heat is handled when curve (1) is two step fusions and fusion for the second time in the raw material, curve (2) is the luminous intensity after the glass of curve (1) is handled through 600 ℃, 40 hours glass heat.The luminescence peak of these two kinds of glass and can be seen also that by Fig. 2 their scope of excitation spectrum is also roughly the same all about 370nm, but after the thermal treatment, long wavelength (320nm) is when exciting, and the luminous intensity of cerium ion has approximately increased by one times.
Fig. 3 shows mixes in the pyrex of ammonium nitrate in the raw material when being two step fusions and fusion for the second time, and trivalent europium ion glass is the excitation spectrum when 420nm (2) is luminous at 613nm (1) and divalent europium.This glass mainly shows ruddiness during with the ultra violet lamp of 254nm, and mainly apparent blue light during with the ultra violet lamp of 365nm.
Method for glass preparation of the present invention, except twice melting of needs, other technology and common glass The preparation technology of glass is basically identical, and the glass melting temperature is not high yet, and production cost is low, and this glass The various shapes such as the bulk that glass can be prepared into, bar-shaped and fiber to be adapting to the needs of various application, The glass of the present invention's preparation might become new fluorescent glass.
Embodiment
The invention will be further described by the following examples.
Contain the cerium borosilicate luminescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 1.0% cerium, then this glass is pulverized, and adds the oxide compound and the ammonium nitrate of boron, and in crucible with cover, fusion is after 15 minutes again through high temperature, and cooling is prepared into and contains the cerium borosilicate glass.Here ammonium nitrate: the weight ratio that contains the silicate glass of cerium is 0.25.Behind this glass polishing,, peak value occurs and be positioned at broad-band illumination about 370nm through fluorescence spectrophotometer test.Curve 3 is exactly the excitation spectrum of this glass 370nm when luminous among Fig. 1.This cerium borosilicate glass is put into High Temperature Furnaces Heating Apparatus after near the thermal treatment a few hours glass transformation temperature, just can strengthen its light intensity that turns blue, obtain glass excitation spectrum shown in the curve 2 among Fig. 2, show strong blue light during with the ultra violet lamp of 254nm.
Contain the cerium borosilicate luminescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 2.5% cerium, then this glass is pulverized, and adds the oxide compound and the sulfuric acid amine of boron, and in crucible with cover, fusion is after 20 minutes again through high temperature, and cooling is prepared into and contains the cerium borosilicate glass.Here sulfuric acid amine: the weight ratio that contains the silicate glass of cerium is 0.15.Behind this glass polishing,, peak value occurs and be positioned at broad-band illumination about 370nm through fluorescence spectrophotometer test.This cerium borosilicate glass is put into High Temperature Furnaces Heating Apparatus after near the thermal treatment a few hours glass transformation temperature, can strengthen its light intensity that turns blue.Show strong blue light during with the ultra violet lamp of 254nm.
Contain the cerium borosilicate luminescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 0.1% cerium, then this glass is pulverized, and adds the oxide compound and the amine acetate of boron, and in crucible with cover, fusion is after 10 minutes again through high temperature, and cooling is prepared into and contains the cerium borosilicate glass.Here amine acetate: the weight ratio that contains the silicate glass of cerium is 0.30.Behind this glass polishing,, peak value occurs and be positioned at broad-band illumination about 370nm through fluorescence spectrophotometer test.This cerium borosilicate glass is put into High Temperature Furnaces Heating Apparatus after near the thermal treatment a few hours glass transformation temperature, can strengthen its light intensity that turns blue.Show strong blue light during with the ultra violet lamp of 254nm.
Embodiment 4
Contain the cerium borosilicate luminescent glass with the scorification preparation of two steps.At first high-temperature fusion preparation contains the silicate glass that weight ratio is 1.5% cerium, then this glass is pulverized, and adds the oxide compound and the ammonium nitrate of boron, and again after the fusion, cooling is prepared into and contains the cerium borosilicate glass in being connected with the High Temperature Furnaces Heating Apparatus of ammonia.Here ammonium nitrate: the ratio that contains the silicate glass of cerium is 0.15.Behind this glass polishing,, peak value occurs and be positioned at broad-band illumination about 370nm through fluorescence spectrophotometer test.This cerium borosilicate glass is put into High Temperature Furnaces Heating Apparatus after near the thermal treatment a few hours glass transformation temperature, can strengthen its light intensity that turns blue.Show strong blue light during with the ultra violet lamp of 254nm.
Embodiment 5
Contain the europium borosilicate luminescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 0.1% europium, then this glass is pulverized, and adds the oxide compound and the ammonium nitrate of boron, and in crucible with cover, fusion is after 10 minutes again through high temperature, and cooling is prepared into and contains the europium borosilicate glass.Here ammonium nitrate: the weight ratio that contains the silicate glass of europium is 0.25.This glass polishing is after fluorescence spectrophotometer test, occur peak value be positioned at about 613nm and 420nm about broad-band illumination, Fig. 3 is exactly this glass 613nm and the 420nm excitation spectrum when luminous.Show with the ultra violet lamp of 254nm the time and glow, send out blue light strong and show with the ultra violet lamp of 365nm the time.This europium borosilicate glass is put into High Temperature Furnaces Heating Apparatus, after near the thermal treatment a few hours glass transformation temperature, can increase the contrast gradient of two kinds of glow colors.
Embodiment 6
Contain the europium borosilicate luminescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 0.8% europium, then this glass is pulverized, and adds the oxide compound and the sulfuric acid amine of boron, and in crucible with cover, fusion is after 15 minutes again through high temperature, and cooling is prepared into and contains the europium borosilicate glass.Here sulfuric acid amine: the weight ratio that contains the silicate glass of europium is 0.20.This glass polishing is after fluorescence spectrophotometer test, occur peak value be positioned at about 613nm and 420nm about broad-band illumination.Show with the ultra violet lamp of 254nm the time and glow, send out blue light strong and show with the ultra violet lamp of 365nm the time.This europium borosilicate glass is put into High Temperature Furnaces Heating Apparatus, after near the thermal treatment a few hours glass transformation temperature, can increase the contrast gradient of two kinds of glow colors.
Embodiment 7
Contain the europium borosilicate luminescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 1.6% europium, then this glass is pulverized, and adds the oxide compound and the sulfuric acid amine of boron, and in crucible with cover, fusion is after 15 minutes again through high temperature, and cooling is prepared into and contains the europium borosilicate glass.Here sulfuric acid amine: the weight ratio that contains the silicate glass of europium is 0.20.This glass polishing is after fluorescence spectrophotometer test, occur peak value be positioned at about 613nm and 420nm about broad-band illumination.Show with the ultra violet lamp of 254nm the time and glow, send out blue light strong and show with the ultra violet lamp of 365nm the time.This europium borosilicate glass is put into High Temperature Furnaces Heating Apparatus, after near the thermal treatment a few hours glass transformation temperature, can increase the contrast gradient of two kinds of glow colors
Embodiment 8
Contain the manganese borosilicate luminescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 0.05% manganese, then this glass is pulverized, and adds the oxide compound and the ammonium nitrate of boron, and in crucible with cover, fusion is after 15 minutes again through high temperature, and cooling is prepared into and contains the manganese borosilicate glass.Here ammonium nitrate: the weight ratio of manganiferous silicate glass is 0.30.This glass polishing is after fluorescence spectrophotometer test, through the fluorescence spectrophotometer test, peak value occurs and is positioned at broad-band illumination about 565nm, shows during with the ultra violet lamp of 254nm or 365nm to send out light light red.
Embodiment 9
Contain the manganese borosilicate luminescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 0.2% manganese, then this glass is pulverized, and adds the oxide compound and the ammonium nitrate of boron, and in crucible with cover, fusion is after 15 minutes again through high temperature, and cooling is prepared into and contains the manganese borosilicate glass.Here ammonium nitrate: the weight ratio of manganiferous silicate glass is 0.30.This glass polishing is after fluorescence spectrophotometer test, through the fluorescence spectrophotometer test, peak value occurs and is positioned at broad-band illumination about 565nm, shows during with the ultra violet lamp of 254nm or 365nm to send out light light red.
Embodiment 10
Contain the manganese borosilicate luminescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 1.0% manganese, then this glass is pulverized, and adds the oxide compound and the ammonium nitrate of boron, and in crucible with cover, fusion is after 15 minutes again through high temperature, and cooling is prepared into and contains the manganese borosilicate glass.Here ammonium nitrate: the weight ratio of manganiferous silicate glass is 0.30.This glass polishing is after fluorescence spectrophotometer test, through the fluorescence spectrophotometer test, peak value occurs and is positioned at broad-band illumination about 565nm, shows during with the ultra violet lamp of 254nm or 365nm to send out light light red.
Embodiment 11
Contain cerium silicophosphate fluorescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 0.1% cerium, then this glass is pulverized, and adds primary ammonium phosphate (NH
4H
2PO
3), in crucible with cover, fusion is after 15 minutes again through high temperature, and cooling is prepared into and contains the cerium borosilicate glass.Here NH
4H
2PO
3: the weight ratio that contains the silicate glass of cerium is 1.0.This glass polishing is after fluorescence spectrophotometer test, and it is luminous by force the broadband that peak value is positioned at about 330nm to occur.Compare with containing the cerium borosilicate glass, contain the luminous short wavelength of moving to of cerium phosphosilicate glass, and luminous zone narrows down, peak strength is apparently higher than containing the cerium borosilicate glass.
Embodiment 12
Contain cerium silicophosphate fluorescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 1.0% cerium, then this glass is pulverized, and adds primary ammonium phosphate (NH
4H
2PO
3), in crucible with cover, fusion is after 10 minutes again through high temperature, and cooling is prepared into and contains the cerium borosilicate glass.Here NH
4H
2PO
3: the weight ratio that contains the silicate glass of cerium is 1.1.This glass polishing is after fluorescence spectrophotometer test, and it is luminous by force the broadband that peak value is positioned at about 330nm to occur.
Embodiment 13
Contain cerium silicophosphate fluorescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 1.5% cerium, then this glass is pulverized, and adds primary ammonium phosphate (NH
4H
2PO
3), in crucible with cover, fusion is after 20 minutes again through high temperature, and cooling is prepared into and contains the cerium borosilicate glass.Here NH
4H
2PO
3: the weight ratio that contains the silicate glass of cerium is 1.2.This glass polishing is after fluorescence spectrophotometer test, and it is luminous by force the broadband that peak value is positioned at about 330nm to occur.
Embodiment 14
Contain cerium silicophosphate fluorescent glass with the scorification preparation of two steps.At first the high-temperature fusion preparation contains the silicate glass that weight ratio is 2.5% cerium, then this glass is pulverized, and adds primary ammonium phosphate (NH
4H
2PO
3), in crucible with cover, fusion is after 20 minutes again through high temperature, and cooling is prepared into and contains the cerium borosilicate glass.Here NH
4H
2PO
3: the weight ratio that contains the silicate glass of cerium is 1.4.This glass polishing is after fluorescence spectrophotometer test, and it is luminous by force the broadband that peak value is positioned at about 330nm to occur.
Claims (3)
1. the preparation method of a fluorescent glass, the glass melting preparation is finished in two steps in this method, the first step is the silicate glass that the fusion preparation contains luminescent active ion, second step was that this silicate glass is pulverized, after adding the oxide compound and ammonium salt of boron, carry out fusion again in crucible with cover or in the High Temperature Furnaces Heating Apparatus of logical ammonia, subsequently cooling forming obtain mixing above-mentioned light-emitting element lower valency light emitting ionic or based on the borosilicate glass of lower valency light emitting ionic, it is characterized in that: described luminescent active ion is rare-earth element cerium or europium or transition metal manganese, and the weight ratio content in silicate glass is 0.1～2.5%; Described second when going on foot fusion again, ammonium salt: the weight ratio of silicate glass must be greater than 0.15, and during melting, smelting time was at 10～20 minutes in logical ammonia crucible with cover.
2. the preparation method of a fluorescent glass, the glass melting preparation is finished in two steps in this method, the first step is the silicate glass that the fusion preparation contains luminescent active ion, second step was fusion again after this silicate glass is pulverized, it is characterized in that: described luminescent active ion is rare-earth element cerium or europium or transition metal manganese, and its weight ratio at described silicate glass is 0.1～2.5%; Second when going on foot fusion again, add primary ammonium phosphate, primary ammonium phosphate: the weight ratio of silicate glass is 1.1,1.2,1.4, fusion again in crucible with cover or in the High Temperature Furnaces Heating Apparatus of logical ammonia, obtain mixing the lower valency light emitting ionic of above-mentioned light-emitting element or based on the phosphosilicate glass of lower valency light emitting ionic, during fusion, the fusion time can not be long, at 10～20 minutes in logical ammonia crucible with cover.
3. the preparation method of fluorescent glass according to claim 1 and 2 heat-treats near the transition temperature that it is characterized in that the borosilicate glass or the phosphosilicate glass of gained are put into the inherent glass of High Temperature Furnaces Heating Apparatus.
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| CNB2005100264496A CN100398475C (en) | 2005-06-03 | 2005-06-03 | Preparation method for luminous glass |
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| CN100398475C true CN100398475C (en) | 2008-07-02 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| JP5569942B2 (en) * | 2009-10-27 | 2014-08-13 | 学校法人東京理科大学 | Luminescent glass, light-emitting device provided with the luminescent glass, and method for producing the luminescent glass |
| CN102241480B (en) * | 2010-05-11 | 2013-01-02 | 海洋王照明科技股份有限公司 | Elemental silver-doped rare earth ion luminescent glass and preparation method thereof |
| CN102745902B (en) * | 2012-06-28 | 2014-07-09 | 吉林大学 | Ion-exchange glass substrate and its preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU1799851C (en) * | 1991-03-19 | 1993-03-07 | Гомельский государственный университет им.Ф.Скорины | Glass |
| JP2002030272A (en) * | 2000-07-19 | 2002-01-31 | Fujimi Inc | Abrasive composition and method of grinding silicon oxide material using the same |
| JP2004323297A (en) * | 2003-04-24 | 2004-11-18 | Central Glass Co Ltd | Low melting point glass |
| CN1587143A (en) * | 2004-09-28 | 2005-03-02 | 中国科学院上海光学精密机械研究所 | Chromium ion blended red light emitting glass and its producing method |
-
2005
- 2005-06-03 CN CNB2005100264496A patent/CN100398475C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU1799851C (en) * | 1991-03-19 | 1993-03-07 | Гомельский государственный университет им.Ф.Скорины | Glass |
| JP2002030272A (en) * | 2000-07-19 | 2002-01-31 | Fujimi Inc | Abrasive composition and method of grinding silicon oxide material using the same |
| JP2004323297A (en) * | 2003-04-24 | 2004-11-18 | Central Glass Co Ltd | Low melting point glass |
| CN1587143A (en) * | 2004-09-28 | 2005-03-02 | 中国科学院上海光学精密机械研究所 | Chromium ion blended red light emitting glass and its producing method |
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