CN104355539B - A kind of rare earth ion doped glass ceramic composition - Google Patents
A kind of rare earth ion doped glass ceramic composition Download PDFInfo
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- CN104355539B CN104355539B CN201410568330.0A CN201410568330A CN104355539B CN 104355539 B CN104355539 B CN 104355539B CN 201410568330 A CN201410568330 A CN 201410568330A CN 104355539 B CN104355539 B CN 104355539B
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- rare earth
- earth ion
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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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
Abstract
The present invention relates to a kind of rare earth ion doped rare earth ion doped glass ceramic composition, the ceramic composition includes 30~40 mass % magnesia borosilicate glass powder, 30~50 mass % alumina packing powder, 10~30 mass % Y2O3With 10 15 mass % rare earth ion, the magnesia borosilicate glass powder contains 40~70 mass %SiO with oxide conversion2, 8~25 mass %B2O3, 5~30 mass %Al2O3, 20~30 mass %MgO.The glass ceramic baseplate that the rare earth ion doped glass ceramic composition of the present invention is made has high reflectance and the percent crystallization in massecuite of glass phase is low, with excellent luminescent properties.
Description
Technical field
It is especially a kind of to can be applied to the rare earth ion doped of optical glass the present invention relates to a kind of glass ceramic composition
Glass ceramic composition and its application.
Background technology
With developing rapidly for information technology and photoelectric technology, the property of phosphor is increasingly subject to people's
Pay attention to, its existing forms has polycrystal powder, monocrystalline, film, ceramics, glass etc..Due to glass have it is uniform, transparent, be easy to plus
Work can carry out the doping of higher concentration into variously-shaped advantage, therefore be increasingly becoming the good matrix of inorganic light-emitting
Material, its purposes is also more and more extensive.
Light source is generally divided into discharge lamp and solid state lamp, in solid state lamp, and heat radiator is in general illumination and automobile application
Occupy an leading position, for example Halogen lamp LED.In addition, the solid state light emitter of light emitting deivce form, such as inorganic light-emitting diode (LED) one
Plant common form.
LED has many excellent performances, and electric energy can be converted into luminous energy by it, therefore with higher efficiency,
Small volume, and possess a variety of different colours, therefore as a kind of wide variety of luminescent material.
Rare earth ion has good fluorescent characteristic due to its special 4f electronic structure, and such as luminescent chromaticity is pure, materialization
Property stabilization, conversion efficiency height etc..In recent years, rare earth ion doped Novel luminous glass turns into the focus of R and D,
Its application covers the fields such as fluorescence equipment, laser, fiber amplifier, white light LEDs.Wherein, due to rare earth Eu2+Ground state level
It is 4f7 (8S7/2), infrared band, Eu is arrived ultraviolet2+It can be excited, so on Eu2+Adulterate inorganic non-metallic material
The luminescent properties of material, lot of domestic and international scholar has carried out substantial amounts of basic research；Further, with B2O3-SiO2System is matrix
Rare-earth Optic Glass have higher chemical strength, good dielectricity, higher chemical stability and excellent rare earth from
Sub- solvability, is the Major Systems that current people study Rare-earth Optic Glass.
At present, the research using the luminescent properties of single rare earth ion pair pyrex is more universal, however, few
Document report can study the influence of its luminescent properties to pyrex using the combination of a variety of rare earth ions.
The content of the invention
It is an object of the invention to provide a kind of rare earth ion doped glass ceramic composition, this is rare earth ion doped
Glass ceramic composition is fitted entirely into higher level doping with rare-earth ions, is conducive to coming as far as possible so that it is resulted in
From the luminescent properties of the conversion of the light of cold light source (LED or discharge lamp), the rare earth ion doped glass ceramic composition is made
Glass ceramic baseplate there is high reflectance and the percent crystallization in massecuite of glass phase is low.
To reach this goal of the invention, the present invention uses following technical scheme：
In a first aspect, the invention provides a kind of rare earth ion doped glass ceramic composition, said composition includes 30
~40 mass % magnesia borosilicate glass powder, 30~50 mass % alumina packing powder, 10~30 mass % Y2O3With
10-15 mass % rare earth ion, the magnesia borosilicate glass powder contains 40~70 mass %SiO with oxide conversion2、8
~25 mass %B2O3, 5~30 mass %Al2O3, 20~30 mass %MgO.
The content of magnesia borosilicate glass powder in the present invention is 30~40 mass %, for example, can be 30 mass %, 31
Quality %, 32 mass %, 33 mass %, 34 mass %, 35 mass %, 36 mass %, 37 mass %, 38 mass %, 39 matter
Measure %, 40 mass %, more preferably preferably 32~38 mass %, 35 mass %.
The content of alumina packing powder in the present invention is 30~50 mass %, for example, can be 30 mass %, 32 matter
Measure %, 35 mass %, 38 mass %, 40 mass %, 45 mass %, 48 mass %, preferably 50 mass %, 35~45 matter
Measure %, more preferably 35 mass %.
Y in the present invention2O3Content be 10~30 mass %, for example can be 10 mass %, 12 mass %, 15 matter
Measure %, 18 mass %, 20 mass %, 22 mass %, 25 mass %, 28 mass %, preferably 30 mass %, 12~25 matter
Measure %, more preferably 15 mass %.
Rare earth ion in the present invention is 10-15 mass %, for example can be 10 mass %, 11 mass %, 12 mass %,
13 mass %, 14 mass %, 15 mass %, more preferably preferably 12-15 mass %, 15 mass %.
In the advantageous modification of the present invention, the composition includes 32~38 mass % magnesia borosilicate glass powder
End, 35~45 mass % alumina packing powder, 12~25 mass % Y2O3With 12-15 mass % rare earth ion, it is described
Magnesia borosilicate glass powder contains 48~68 mass %SiO with oxide conversion2, 10~20 mass %B2O3, 10~25 mass %
Al2O3, 22~28 mass %MgO.
In another advantageous modification of the present invention, the composition includes 35 mass % magnesia borosilicate glass powder
End, 35 mass % alumina packing powder, 15 mass % Y2O3With 15 mass % rare earth ion, the magnesium borocitrate glass
Glass powder contains 50 mass %SiO with oxide conversion2, 10 mass %B2O3, 15 mass %Al2O3, 25 mass %MgO.
Rare earth ion in the present invention is any in Ce, Pr, Nd, Sm, Eu, Gd, Tb, Er, Tm, Yb, Ho, Dy or La
It is a kind of or at least two mixture.
In the advantageous modification of the present invention, the rare earth ion is in Ce, Eu, Ho, Tm, Tb, Dy or Yb
Any one or at least two mixture.
In another advantageous modification of the present invention, the rare earth ion is in Ce/Eu, Ho/Tm/Yb or Tb/Dy
Any one mixture, preferably Ho/Tm/Yb mixture.
Second aspect, present invention also offers a kind of application of composition as described in relation to the first aspect in optical glass.
The third aspect, present invention also offers a kind of fluorescent glass, the light source is comprising LED and as described in relation to the first aspect
Composition.
Compared with prior art, the invention has the advantages that：
The glass ceramic baseplate that is made of rare earth ion doped glass ceramic composition of the present invention have high reflectance and
The percent crystallization in massecuite of glass phase is low, and its insulating reliability is high, with high-flexural strength, wherein, ceramic post sintering obtained from by burning till
The percent crystallization in massecuite of glass phase in body reaches less than 55% with volume basis, and high index of refraction filler powder is refractive index more than 1.95
Ceramics.
Embodiment
Technical scheme is further illustrated below by embodiment.
Those skilled in the art it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to this hair
Bright concrete restriction.
Embodiment 1
The first glass melting of following component (quality %, in terms of oxide) will be included：
30 mass % magnesia borosilicate glass powder, 30 mass % alumina packing powder, 30 mass % Y2O3With 10
Quality % rare earth ion Ce/Eu mixture, the magnesia borosilicate glass powder contains 68 mass % with oxide conversion
SiO2, 10 mass %B2O3, 10 mass %Al2O3, 22 mass %MgO.Wherein, Ce and Eu molar fraction is 0.5%.
Glass is heated into about 1550 DEG C in platinum crucible to melt and homogenize；It is cooled to after room temperature and has obtained clean transparent
Glass.Excited with ultraviolet light, spectral emissions peak shows as a stronger broad peak, emission spectrum peak is located at 470nm
Left and right, material of the invention can send the light of blueness in vitreousness and ceramic state.
After tested, by burning till obtained from the percent crystallization in massecuite of glass phase in ceramic sintered bodies reached with volume basis
55%, high index of refraction filler powder is ceramics of the refractive index more than 1.95.
Embodiment 2
The first glass melting of following component (quality %, in terms of oxide) will be included：
32 mass % magnesia borosilicate glass powder, 35 mass % alumina packing powder, 20 mass % Y2O3With 13
Quality % rare earth ion Ce/Eu mixture, the magnesia borosilicate glass powder contains 68 mass % with oxide conversion
SiO2, 10 mass %B2O3, 10 mass %Al2O3, 22 mass %MgO.Wherein, Ce and Eu molar fraction is 1.0%.
Glass is heated into about 1600 DEG C in platinum crucible to melt and homogenize；It is cooled to after room temperature and has obtained clean transparent
Glass.Excited with ultraviolet light, spectral emissions peak shows as a stronger broad peak, emission spectrum peak is located at 480nm
Left and right, material of the invention can send the light of blueness in vitreousness and ceramic state.
After tested, by burning till obtained from the percent crystallization in massecuite of glass phase in ceramic sintered bodies reached with volume basis
52%, high index of refraction filler powder is ceramics of the refractive index more than 1.95.
Embodiment 3
The first glass melting of following component (quality %, in terms of oxide) will be included：
34 mass % magnesia borosilicate glass powder, 38 mass % alumina packing powder, 16 mass % Y2O3With 12
Quality % rare earth ion Ho/Tm/Yb mixture, the magnesia borosilicate glass powder contains 60 mass % with oxide conversion
SiO2, 10 mass %B2O3, 10 mass %Al2O3, 20 mass %MgO.Wherein, Ho, Tm and Yb molar fraction are 1.0%.
Glass is heated into about 1600 DEG C in platinum crucible to melt and homogenize；It is cooled to after room temperature and has obtained clean transparent
Glass.Excited with ultraviolet light, spectral emissions peak shows as a stronger broad peak, emission spectrum peak is located at 480nm
Left and right, material of the invention can send the light of blueness in vitreousness and ceramic state.
After tested, by burning till obtained from the percent crystallization in massecuite of glass phase in ceramic sintered bodies reached with volume basis
53%, high index of refraction filler powder is ceramics of the refractive index more than 1.97.
Embodiment 4
The first glass melting of following component (quality %, in terms of oxide) will be included：
35 mass % magnesia borosilicate glass powder, 35 mass % alumina packing powder, 15 mass % Y2O3With 15
Quality % rare earth ion Ho/Tm/Yb mixture, the magnesia borosilicate glass powder contains 68 mass % with oxide conversion
SiO2, 10 mass %B2O3, 10 mass %Al2O3, 22 mass %MgO.Wherein, Ho, Tm, Yb molar fraction are 1.5%.
Glass is heated into about 1600 DEG C in platinum crucible to melt and homogenize；It is cooled to after room temperature and has obtained clean transparent
Glass.Excited with ultraviolet light, spectral emissions peak shows as a stronger broad peak, emission spectrum peak is located at 490nm
Left and right, material of the invention can send the light of blueness in vitreousness and ceramic state.
After tested, by burning till obtained from the percent crystallization in massecuite of glass phase in ceramic sintered bodies reached with volume basis
50%, high index of refraction filler powder is ceramics of the refractive index more than 1.95.
Embodiment 5
The first glass melting of following component (quality %, in terms of oxide) will be included：
38 mass % magnesia borosilicate glass powder, 32 mass % alumina packing powder, 20 mass % Y2O3With 10
Quality % rare earth ion Tb/Dy mixture, the magnesia borosilicate glass powder contains 68 mass % with oxide conversion
SiO2, 10 mass %B2O3, 10 mass %Al2O3, 22 mass %MgO.Wherein, Tb and Dy molar fraction is 0.5%.
Glass is heated into about 1550 DEG C in platinum crucible to melt and homogenize；It is cooled to after room temperature and has obtained clean transparent
Glass.Excited with ultraviolet light, spectral emissions peak shows as a stronger broad peak, emission spectrum peak is located at 470nm
Left and right, material of the invention can send the light of blueness in vitreousness and ceramic state.
After tested, by burning till obtained from the percent crystallization in massecuite of glass phase in ceramic sintered bodies reached with volume basis
55%, high index of refraction filler powder is ceramics of the refractive index more than 1.98.
Embodiment 6
The first glass melting of following component (quality %, in terms of oxide) will be included：
37 mass % magnesia borosilicate glass powder, 30 mass % alumina packing powder, 22 mass % Y2O3With 11
Quality % rare earth ion Tb/Dy mixture, the magnesia borosilicate glass powder contains 68 mass % with oxide conversion
SiO2, 10 mass %B2O3, 10 mass %Al2O3, 22 mass %MgO.Wherein, Tb and Dy molar fraction is 2.0%.
Glass is heated into about 1550 DEG C in platinum crucible to melt and homogenize；It is cooled to after room temperature and has obtained clean transparent
Glass.Excited with ultraviolet light, spectral emissions peak shows as a stronger broad peak, emission spectrum peak is located at 500nm
Left and right, material of the invention can send the light of blueness in vitreousness and ceramic state.
After tested, by burning till obtained from the percent crystallization in massecuite of glass phase in ceramic sintered bodies reached with volume basis
51%, high index of refraction filler powder is ceramics of the refractive index more than 1.96.
The present invention is can be seen that under UV, visible light light irradiation from above-described embodiment 1-6, rare earth ion doped borosilicic acid
Magnesium glass can be excited well, and have very wide excitation wavelength range, and emission spectra is broadband peak.Simultaneously with rare earth
The increase of ion concentration, its launching centre is gradually moved to long wave direction, and obvious red shift occurs for the launching centre of maximum emission peak,
500nm or so is gradually moved to from 470nm, and intensity of emission spectra then gradually weakens, moreover, being mixed using the rare earth ion of the present invention
The glass ceramic baseplate that miscellaneous glass ceramic composition is made has high reflectance and the percent crystallization in massecuite of glass phase is low, with excellent
Luminescent properties, can be widely applied to industrial production.
Applicant states that the present invention illustrates the process of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (3)
1. a kind of rare earth ion doped glass ceramic composition, it is characterised in that the composition includes 32~38 mass %
Magnesia borosilicate glass powder, 35~45 mass % alumina packing powder, 12~25 mass % Y2O3With 12-15 matter
% rare earth ion is measured, the magnesia borosilicate glass powder contains 48~68 mass %SiO with oxide conversion2, 10~20 matter
Measure %B2O3, 10~25 mass %Al2O3, 22~28 mass %MgO, the rare earth ion be Ce/Eu, Ho/Tm/Yb or Tb/Dy
In any one mixture.
2. composition as claimed in claim 1, it is characterised in that the composition includes 35 mass % magnesia borosilicate glass
Powder, 35 mass % alumina packing powder, 15 mass % Y2O3With 15 mass % rare earth ion, the magnesium borocitrate
Glass powder contains 50 mass %SiO with oxide conversion2, 10 mass %B2O3, 15 mass %Al2O3, 25 mass %MgO.
3. application of the composition as described in any one of claim 1 or 2 in optical glass.
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| CN201410568330.0A CN104355539B (en) | 2014-10-22 | 2014-10-22 | A kind of rare earth ion doped glass ceramic composition |
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| CN201410568330.0A CN104355539B (en) | 2014-10-22 | 2014-10-22 | A kind of rare earth ion doped glass ceramic composition |
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| CN104355539B true CN104355539B (en) | 2017-09-12 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769231A (en) * | 2004-09-29 | 2006-05-10 | 肖特股份公司 | Glass or glass ceremic |
| CN101543151A (en) * | 2007-04-20 | 2009-09-23 | 株式会社村田制作所 | Multilayered ceramic substrate, process for producing the multilayered ceramic substrate, and electronic component |
| CN102030477A (en) * | 2009-10-07 | 2011-04-27 | 旭硝子株式会社 | Ceramic material composition |
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- 2014-10-22 CN CN201410568330.0A patent/CN104355539B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769231A (en) * | 2004-09-29 | 2006-05-10 | 肖特股份公司 | Glass or glass ceremic |
| CN101543151A (en) * | 2007-04-20 | 2009-09-23 | 株式会社村田制作所 | Multilayered ceramic substrate, process for producing the multilayered ceramic substrate, and electronic component |
| CN102030477A (en) * | 2009-10-07 | 2011-04-27 | 旭硝子株式会社 | Ceramic material composition |
Non-Patent Citations (1)
| Title |
|---|
| Eu2+掺杂硼硅酸镁玻璃的发光性能;李彩霞、李强;《发光学报》;20110215;第32卷(第2期);第149-151页 * |
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Inventor after: Cao Wei Inventor before: Hua Wenwei |
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Effective date of registration: 20170711 Address after: The new town of Rudong County in Jiangsu province 226432 Nantong Sun Qiao Cun Group No. 51 nine Applicant after: Cao Wei Address before: Lake Town, Xishan District People's road 214000 Jiangsu city of Wuxi province and red Ju Wei Village No. 100 Applicant before: Hua Wenwei |
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