CN1263694C - Preparation method of neodymium doped high silica blue light glass - Google Patents

Preparation method of neodymium doped high silica blue light glass Download PDF

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Publication number
CN1263694C
CN1263694C CN 200410067896 CN200410067896A CN1263694C CN 1263694 C CN1263694 C CN 1263694C CN 200410067896 CN200410067896 CN 200410067896 CN 200410067896 A CN200410067896 A CN 200410067896A CN 1263694 C CN1263694 C CN 1263694C
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glass
neodymium
micropore
high silica
temperature
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CN1618760A (en
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陈丹平
夏金安
杨旅云
彭明营
邱建荣
朱从善
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Shanghai Institute of Optics and Fine Mechanics of CAS
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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
    • 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
    • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz

Abstract

The present invention relates to a method for preparing neodymium-doped high silica glass emitting blue light. The present invention is characterized in that the method comprises the following steps that (1) high silica micropore glass is prepared by a conventional method, and is made from at least 95 wt% of SiO2, 1 to 2 wt% of B2O3 and 1 to 3 wt% of Al2O3; the pore diameter of the micropore glass is from 1.0 to 10 nanometers; the small pores accounts for 23 to 35% of the volume of the glass; (2) neodymium ions are led to high silica micropore glass with the nanometer pores by an immersion method of neodymium ion liquor, and the content of SiO2 in the high silica micropore glass is greater than 95%; the weight percentage of Nd2O3 in the sintered glass is from 0.1 to 1.5 wt%; (3) after the neodymium ions are led, the high silica micropore glass doped with neodymium ions is put in a high-temperature furnace, and is sintered at the temperature of 1000 to 1200DEGC at the reducing atmosphere in a solid phase way, the micropores are eliminated, and thus, the compact and transparent high silica glass is formed.

Description

The preparation method of neodymium doped high silicate oxygen blue light-emitting glass
Technical field
The present invention relates to neodymium doped high silicate oxygen blue light-emitting glass, particularly a kind of preparation method of neodymium doped high silicate oxygen blue light-emitting glass.
Background technology
The modern life be unable to do without luminescent material, the fluorescent lamp that uses in the daily life the most commonly, it is that the short wavelength's that mercuryvapour is sent of the mixture by the phosphor material that is mixed with rare earth ion ultraviolet ray converts the visible white light to, for example the BaMgAl of blue light-emitting 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 fluorescent lamp emits white light, and in the teletron of the color TV of using in the daily life also is to have adopted to be mixed with isoionic ZnS of Cu, Ag and Y 2O 3S:Eu changes electron rays into the visible light of various different colours.But these luminescent materials all are some opaque powders, but need transparent luminescent material when some special purposes, for example prepare laser medium material.In order to obtain transparent luminescent material, people mix light emitting ionic in transparent monocrystal material, for example ruby and yttrium aluminum garnet etc. have the excellent characteristics of luminescence to be actually used in Laser Devices, but monocrystal material preparation cost height, be difficult to be prepared into material bulk and that have different shape, can not become the material that fluoresces commonly used.
Oxide glass has good light transmittance, chemical stability, low cost and makes advantage such as different shape easily, is suitable as very much the substrate material of light emitting ionics such as rare earth and transition metal, and people's more efficient fluorescent glass that waits in expectation is applied.But light emitting ionic luminescent properties in glass is often not so good, and a major reason is exactly that these ions prepare in the glass process in high-temperature fusion, be not homodisperse often in glass structure, and easy spontaneous formation is trooped, and produces the concentration delustring.Many rare earth ions only contain a hundreds of ppm at oxide glass and just begin to produce the significant concn delustring.About how eliminating the concentration delustring, scientists both domestic and external has been done a large amount of research, but the breakthrough with practical value of still being unrealized, therefore the actual glass that contains rare earth ion that is employed only has the Nd of containing and Er glass to serve as laser glass and optical fiber laser and image intensifer so far, does not up to the present still have glass-based material to become the material that fluoresces commonly used.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of neodymium doped high silicate oxygen blue light-emitting glass.
Basis of the present invention is:
The inventor thinks that micropore is evenly distributed in the micropore glass with nano grade pore, specific surface is active big, light emitting ionics such as rare earth and transition metal are fully disperseed in glass, burn till through the solid phase lower again and just can eliminate micropore and obtain closely knit transparent glass than glass melting temperature.Owing to there is not the high-temperature fusion process, rare earth and transition metal ion migration difficulty are difficult to produce the spontaneous behavior of trooping.Might prevent the concentration delustring to a certain extent in this way, improve the luminous intensity of doped-glass.From the eighties to the nineties, once there was the minority scientist in this sintered glass, to immerse rare earth ion, study carefully rare earth ion luminous in sintered glass with different destination packet spotting-ins, with rare earth ion luminous in sintered glass is that the instrument surface property that characterizes sintered glass etc. has been studied its luminosity, but does not find that the sintered glass of not mixing light emitting ionic can produce the performance of sending out high light.
The present inventor thinks that the luminous not strong important reasons of rare earth ion in sintered glass is impurity, and particularly a large amount of residual OH key in the sintered glass can produce matting effect too, reduces the luminous intensity of rare earth ion.Therefore, eliminate the luminescent properties that these OH keys just might improve this glass.Rare earth of the same race has different valence states with transition metal, the ion of different valence states has different level structures, the different characteristics of luminescences is also just arranged, therefore the nanometer porous glass that contains light emitting ionic such as rare earth by sintering under specific atmosphere, luminous intensity that on the one hand can reinforcing glass can be prepared the luminescent material of different colours on the other hand again.The applicant prepares the novel high-efficient transparent fluorescent glass of a class (DanpingChen etc., Patent NO:WO2003024879-A1) in Japan with the top fundamental research that is envisioned for; Again this method is used to prepare novel neodymium doped high silicate oxygen laser glass afterwards, in research neodymium doped high silicate oxygen laser glass process, find: the neodymium doped high silicate oxygen glass of preparing under the reducing atmosphere, can produce under the UV-irradiation of 250 nanometers that to be positioned at ultraviolet-visible light band center wavelength be the hyperfluorescence of 395 nanometers, its luminescent spectrum is shown as the curve 1 (solid line) among Fig. 1, and Fig. 2 is that this glass sends the excitation spectrum that centre wavelength is 395 nano fluorescents.The neodymium doped high silicate oxygen laser glass of preparing under reducing atmosphere of sending out blue light strong is inventor's discovery first, and applicant's the patent and the patent of applying for did not relate to the content of this respect in the past.In addition in common neodymium-doped silicate laser glass, in same wavelength region, fluorescence is arranged although also can measure it with fluorescence spectrophotometer, but its fluorescence very a little less than, as the curve among Fig. 12 (dotted line), approximately be about 1/20th of the luminous intensity of glass of the present invention in its luminous intensity under the same test condition.Because the low-pressure mercury-vapor in the normally used fluorescent lamp is luminous about 250 nanometers, therefore, but glass of the present invention might become the transparent material of the new blue light-emitting of practicability, also might become a kind of new laser glass of ultraviolet-visible optical band that is positioned at.
Technical solution of the present invention:
A kind of preparation method of neodymium doped high silicate oxygen blue light-emitting glass is characterized in that comprising the following steps:
1. adopt ordinary method to prepare high silica micropore glass, the consisting of of this glass:
Form wt%
SiO 2 95-97
B 2O 3 1-2
Al 2O 3 1-3
The aperture of this sintered glass is the 1.0-10 nanometer, and aperture accounts for the 23-35% of the volume of glass;
2. neodymium ion is to adopt the pickling process mode of neodymium ion solution to introduce above-mentioned have nano grade pore, SiO 2Content be in the glass of 95-97wt%, the Nd in the glass behind the sintering 2O 3Weight percent is 0.1-1.5wt%;
3. after introducing neodymium ion, the high silica micropore glass that is mixed with neodymium ion is put into High Temperature Furnaces Heating Apparatus, through the solid state sintering of 1000-1200 ℃ of temperature, eliminating micropore becomes closely knit transparent vagcor in reducing atmosphere.
The pickling process of described neodymium ion solution is that neodymium nitrate or Neodymium trioxide, Neodymium trichloride, neodymium acetate are dissolved in water, salpeter solution, hydrochloric acid soln, sulfuric acid, ethanol or acetone soln fully, micropore glass is immersed in this solution then, neodymium ion enters this micropore glass with solution.
The process of described solid state sintering is: from room temperature to 400 ℃, heat up with the speed of per minute below 5 ℃, be warmed up to 950 ℃ with the speed of per minute below 10 ℃ then; Then be raised to 1100-1200 ℃ and after insulation under this temperature is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling with the speed of per minute below 5 ℃.
Description of drawings
Fig. 1 is a neodymium doped high silicate oxygen glass, can produce under the UV-irradiation of 250 nanometers that to be positioned at ultraviolet-visible light band center wavelength be the luminescent spectrum of the hyperfluorescence of 395 nanometers
Fig. 2 is that neodymium doped high silicate oxygen glass sends the excitation spectrum that centre wavelength is 395 nano fluorescents
Embodiment
The invention will be further described below in conjunction with accompanying drawing.
The middle SiO of sintered glass of the present invention 2Content be 95-97wt% (wt% by weight percentage), also contain the B of 1-2% in addition in the sintered glass 2O 3And 1-3%Al 2O 3The aperture of sintered glass is the 1.0-10 nanometer, and the volume that aperture accounts for glass is 23-35% (percent by volume).
Neodymium ion is to adopt the pickling process mode of neodymium ion solution to introduce to have nano grade pore SiO 2Content surpass in 95% the high silica micropore glass Nd in the glass behind the glass sintering 2O 3Weight percent is 0.1-1.5wt%.Specifically be with neodymium nitrate or Neodymium trioxide, Neodymium trichloride, neodymium acetate etc. can by water, acid (comprising salpeter solution, hydrochloric acid soln, sulfuric acid), ethanol and acetone soln dissolves fully and high temperature oxidation atmosphere under can decompose and form the neodymium ion oxide compound fully material dissolve in the above-mentioned solution, be prepared into water, acid solution (comprising salpeter solution, hydrochloric acid soln, sulphuric acid soln), ethanolic soln and the acetone soln of Nd ion doped solution; Then micropore glass is immersed in this solution, neodymium ion enters sintered glass with solution.After introducing neodymium ion, the high silica micropore glass that is mixed with neodymium ion is put into High Temperature Furnaces Heating Apparatus, through the solid state sintering of 1000-1200 ℃ of temperature, eliminating micropore becomes closely knit transparent vagcor in reducing atmosphere.In sintering process, ℃ to heat up at a slow speed to avoid the cracking of micropore glass, from heating up at a slow speed to 1050-1200 ℃ of degree about 950 ℃ to avoid glass deformation from room temperature to 400.This glass can be that central wavelength is produced strong broad-band illumination with 395nm under the irradiation of the UV-light about 250nm.Below be described with regard to embodiments of the invention:
Embodiment 1
The Nd of 0.05g will be equivalent to after decomposing 2O 3The analytically pure Nd (NO of 0.13g 3) 36H 2O puts into 10 milliliters deionized water solution, is made into be weight percentage 1.0% Nd (NO of concentration fully after the dissolving 3) 3Solution is 5 * 5 * 3mm, SiO with size again 2The content sintered glass that surpasses 95% (wt% by weight percentage) put into this solution and soak more than 10 minutes; Afterwards, the high silica micropore glass that is mixed with neodymium ion is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; With the solid state sintering of 1050-1200 ℃ of temperature of process in the reducing atmosphere, eliminating micropore becomes closely knit transparent vagcor in High Temperature Furnaces Heating Apparatus.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling with the speed of per minute below 5 ℃.This glass can with 395nm be the broad-band illumination that central wavelength is produced under the irradiation of the UV-light about 250nm.
Embodiment 2
The Nd of 0.4g will be equivalent to after decomposing 2O 3The analytically pure Nd (NO of 1.04g 3) 36H 2O puts into a normal salpeter solution of 10 milliliters, is made into be weight percentage 7.84% Nd (NO of concentration fully after the dissolving 3) 3Salpeter solution, be 5 * 5 * 3mm, SiO with size again 2The content sintered glass that surpasses 96% (wt% by weight percentage) put into this solution and soak more than 10 minutes; Afterwards, the high silica micropore glass that is mixed with neodymium ion is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; With the solid state sintering of 1050-1200 ℃ of degree of process temperature in the reducing atmosphere, eliminating micropore becomes closely knit transparent vagcor in High Temperature Furnaces Heating Apparatus.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling with the speed of per minute below 5 ℃.This glass can with 395nm be the broad-band illumination that central wavelength is produced under the irradiation of the UV-light about 250nm.
Embodiment 3
The Nd of 0.75g will be equivalent to after decomposing 2O 3The analytically pure Nd (NO of 1.95g 3) 36H 2O puts into 10 milliliters ethanolic soln, is made into be weight percentage 14.7% Nd (NO of concentration fully after the dissolving 3) 3Ethanolic soln, be 5 * 5 * 3mm, SiO with size again 2The content sintered glass that surpasses 97% (wt% by weight percentage) put into this solution and soak more than 10 minutes; Afterwards, the high silica micropore glass that is mixed with neodymium ion is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; With the solid state sintering of 1050-1200 ℃ of degree of process temperature in the reducing atmosphere, eliminating micropore becomes closely knit transparent vagcor in High Temperature Furnaces Heating Apparatus.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling with the speed of per minute below 5 ℃.This glass can with 395nm be the broad-band illumination that central wavelength is produced under the irradiation of the UV-light about 250nm.

Claims (3)

1, a kind of preparation method of neodymium doped high silicate oxygen blue light-emitting glass is characterized in that comprising the following steps:
1. adopt ordinary method to prepare high silica micropore glass, the consisting of of this glass:
Form wt%
SiO 2 95-97
B 2O 3 1-2
Al 2O 3 1-3
The aperture of this sintered glass is the 1.0-10 nanometer, and aperture accounts for the 23-35% of the volume of glass;
2. neodymium ion is to adopt the pickling process mode of neodymium ion solution to introduce the above-mentioned nano grade pore SiO that has 2Content be in the high silica micropore glass of 95-97wt%, the Nd in the glass behind the sintering 2O 3Weight percent is 0.1-1.5wt%;
3. after introducing neodymium ion, the high silica micropore glass that is mixed with neodymium ion is put into High Temperature Furnaces Heating Apparatus, through the solid state sintering of 1000-1200 ℃ of temperature, eliminating micropore becomes closely knit transparent vagcor in reducing atmosphere.
2, the preparation method of neodymium doped high silicate oxygen blue light-emitting glass according to claim 1, the pickling process that it is characterized in that described neodymium ion solution is that neodymium nitrate or Neodymium trioxide, Neodymium trichloride, neodymium acetate are dissolved in water, salpeter solution, hydrochloric acid soln, sulfuric acid, ethanol or acetone soln fully, micropore glass is immersed in this solution then, neodymium ion enters this micropore glass with solution.
3, the preparation method of neodymium doped high silicate oxygen blue light-emitting glass according to claim 1, the process that it is characterized in that described solid state sintering is: from room temperature to 400 ℃, heat up with the speed of per minute below 5 ℃, be warmed up to 950 ℃ with the speed of per minute below 10 ℃ then; Then be raised to 1100-1200 ℃ and after insulation under this temperature is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling with the speed of per minute below 5 ℃.
CN 200410067896 2004-11-05 2004-11-05 Preparation method of neodymium doped high silica blue light glass Expired - Fee Related CN1263694C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100484896C (en) * 2005-07-15 2009-05-06 中国科学院上海光学精密机械研究所 Geen light emitting vycor glass production method
CN100378020C (en) * 2005-07-20 2008-04-02 中国科学院上海光学精密机械研究所 Manufacturing method of high silica blue light emitting glass
CN1308255C (en) * 2005-10-21 2007-04-04 中国科学院上海光学精密机械研究所 Manufacturing method of erbium doped high silicon oxygen infrared luminous glass
CN102712525A (en) * 2010-03-05 2012-10-03 海洋王照明科技股份有限公司 Luminous nano-glass-ceramics used as white LED source and preparing method of luminous nano-glass-ceramics
CN106396378B (en) * 2016-09-08 2019-04-19 中国科学院上海光学精密机械研究所 A kind of Nd3+The preparation method of Uniform Doped quartz glass

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