CN100378021C - Manufacturing method of high silica red light emitting glass - Google Patents

Manufacturing method of high silica red light emitting glass Download PDF

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CN100378021C
CN100378021C CNB2005100279097A CN200510027909A CN100378021C CN 100378021 C CN100378021 C CN 100378021C CN B2005100279097 A CNB2005100279097 A CN B2005100279097A CN 200510027909 A CN200510027909 A CN 200510027909A CN 100378021 C CN100378021 C CN 100378021C
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glass
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europium
high silica
temperature
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CN1752042A (en
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陈丹平
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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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Abstract

The present invention relates to a manufacturing method of red light emitting shrunk glass, which is characterized in that shrunk cellular glass is dipped into solution which comprises europium ions, yttrium ions and vanadium ions, or europium ions, gadolinium ions and vanadium ions, and sintered at the high temperature of 1050 DEG C. to 1150 DEG C. in an oxygen atmosphere to form the red light emitting shrunk glass. The red strong light emitting glass can be obtained by utilizing the method of the present invention, and the glass can be new laser glass positioned at a visual light waveband.

Description

The manufacture method of high silica red light emitting glass
Technical field
The present invention relates to vagcor, particularly a kind of manufacture method of high silica red light emitting glass.
Background technology
Oxide glass is owing to have good light transmittance, chemical stability, particularly low-cost and make advantage such as different shape easily, through there is years of researches, the people light emitting materials of glass that waits in expectation to become efficient fluorescent glass and be widely used among the daily life always.But experiment is found the luminous efficiency of light emitting ionic in glass far below crystalline material, and a major reason is exactly that these ions prepare in the glass process in high-temperature fusion, and easy spontaneous formation is trooped and produced the concentration delustring.Many rare earth ions have only a hundreds of ppm just to begin to produce the concentration delustring at oxide glass.How addressing this problem, scientists both domestic and external has been done a large amount of research, but the breakthrough with practical value of still being unrealized.So far, only have and contain Nd and Er glass is used as laser glass and optical fiber laser and these special occasions of image intensifer.Develop new fluorescent glass preparation method, might develop novel light emitting materials of glass, widen the fluorescent glass range of application.The present inventor thinks and utilizes glass to divide having in the nanometer level microporous sintered glass that phase method prepares, and its micropore is evenly distributed, and specific surface is active big, helps light emitting ionics such as rare earth and transition metal and disperses and uniform distribution in glass.This micropore can burn till by the solid phase lower than glass melting temperature and eliminate, thereby becomes closely knit transparent glass.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.According to this imagination, the present inventor has proposed the manufacture method of neodymium doped high silicate oxygen laser glass with this method, and (application number is 200410024820.0, the applying date: 20040601) and the preparation method of neodymium doped high silica blue light glass (application number is 200410067896.1, the applying date: 20041105), specifically be to adopt SiO 2Content surpass the sintered glass of 95% (weight percent) (aperture of sintered glass be 1.0～10 nanometers, the volume that aperture accounts for glass is 23～28%), pickling process by solution, the acid solution of rare earth ion is immersed in the sintered glass, behind high temperature (more than 1050 ℃) sintering, just can obtain the adulterated vagcor fluorescent glass of the rare earth luminous active ion of atresia.
Summary of the invention
The manufacture method that the purpose of this invention is to provide a kind of high silica red light emitting glass, so that obtain can rubescent high light glass, this glass also may become a kind of new laser glass of visible light wave range that is positioned at.
Technical solution of the present invention is:
A kind of manufacture method of high silica red light emitting glass is characterized in that SiO 2The high silica porous glass immersion that content surpasses 96wt% contains europium ion, ruthenium ion and vanadium ion; Or in the solution of europium ion, gadolinium ion and vanadium ion, in oxygen atmosphere, form through 1050 ℃ of-1150 ℃ of high temperature sinterings.
The concrete steps of this method are as follows:
1. europium nitrate, Yttrium trinitrate and vanadylic sulfate water, salpeter solution, hydrochloric acid soln, sulphuric acid soln are dissolved fully, and the material that decomposes fully under the high temperature and form these ionic oxide compounds dissolves in the above-mentioned solution, correspondingly makes the aqueous solution, salpeter solution, hydrochloric acid soln, the sulphuric acid soln that contain europium, yttrium and vanadium ion;
2. with SiO 2The content high silica porous glass that surpasses 96wt% put into described solution and soak more than 10 minutes, to mix europium, yttrium and vanadium ion;
3. will be mixed with described ionic high silica porous glass and put into High Temperature Furnaces Heating Apparatus, in oxygen atmosphere, pass through 1050-1150 ℃ solid state sintering, in the sintering process, with the speed of per minute below 5 ℃, be raised to 400 ℃ from room temperature after, speed with 10 ℃ of per minutes is raised to 950 ℃ of front and back, then, be raised to 1050-1150 ℃ of sintering temperature from this temperature, and be incubated more than 30 minutes in this sintering temperature with the speed of per minute below 5 ℃, the power supply of turning off High Temperature Furnaces Heating Apparatus allows the glass furnace cooling.
Another concrete steps of this method are as follows:
1. europium nitrate, Gadolinium trinitrate and vanadylic sulfate water, salpeter solution, hydrochloric acid soln, sulphuric acid soln are dissolved fully, and the material that decomposes fully under the high temperature and form these ionic oxide compounds dissolves in the above-mentioned solution, correspondingly makes the aqueous solution, salpeter solution, hydrochloric acid soln, the sulphuric acid soln that contain europium, gadolinium and vanadium ion;
2. with SiO 2The content high silica porous glass that surpasses 96wt% put into described solution and soak more than 10 minutes, to mix europium, gadolinium and vanadium ion;
3. will be mixed with described ionic high silica porous glass and put into High Temperature Furnaces Heating Apparatus, in oxygen atmosphere, pass through 1050-1150 ℃ solid state sintering, in the sintering process, with the speed of per minute below 5 ℃, be raised to 400 ℃ from room temperature after, speed with 10 ℃ of per minutes is raised to 950 ℃ of front and back, then, be raised to 1050-1150 ℃ of sintering temperature from this temperature, and be incubated more than 30 minutes in this sintering temperature with the speed of per minute below 5 ℃, the power supply of turning off High Temperature Furnaces Heating Apparatus allows the glass furnace cooling.
The present invention can obtain the vagcor that the irradiation with the ultraviolet lamp of 356 nanometers can glow.If only be mixed with europium ion in sintered glass, the glass emitting red light that obtains behind oversintering is very weak, mix ruthenium ion and vanadium ion or gadolinium ion and vanadium ion altogether after, shift by interionic energy, can strengthen rubescent light intensity significantly.Shown in Figure 1 is the high silica fluorescent glass that glows of the present invention, and two of the left side curves are represented excitation spectrum among Fig. 1, and two curves on the right are represented luminescent spectrum.Dotted line shows is luminous situation when only being mixed with europium ion, solid line shows be europium ion and vanadium ion and ruthenium ion is mixed altogether and in oxygen the luminous situation behind the sintering, mix altogether and in oxygen behind the sintering, the intensity enhancing that glows about 20 times.
Embodiment
The invention will be further described below in conjunction with embodiment, but should not limit protection scope of the present invention with this.
Embodiment 1
The Eu of 0.4g will be equivalent to after decomposing 2O 3The analytically pure Eu (NO of 1.152g 3) 39H 2Be equivalent to Y O.05g after O and the decomposition 2O 3The analytically pure Y (NO of 0.17g 3) 39H 2O is equivalent to the V of 0.2g after the decomposition 2O 5The analytically pure VOSO of 0.36g 4Putting into the hydrochloric acid soln of 25 milliliters 0.5 volumetric molar concentration, after the dissolving, is 5 * 5 * 3mm, SiO with size fully again 2The content sintered glass that surpasses 97wt% put into this solution and soak more than 10 minutes; Afterwards, will be mixed with the high silica micropore glass of these ionic and put into High Temperature Furnaces Heating Apparatus, through the solid state sintering of 1100 ℃ of degree, the elimination micropore becomes the closely knit transparent concentration total of mixing various oxide compounds and is about 0.6% vagcor in oxygen.In sintering process, with the speed of per minute below 5 ℃, after being raised to 400 ℃ from room temperature, speed with 10 ℃ of per minutes is raised to 950 ℃ of front and back, then, be raised to 1100 ℃ and after the insulation of this temperature is more than 30 minutes with the speed of per minute below 5 ℃ from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling.This glass under the irradiation of ultraviolet lamp, near generation emitting red light 613 nanometers.Solid line among Fig. 1 is exactly the luminescent spectrum curve of this glass.
Embodiment 2
The Eu of 0.05g will be equivalent to after decomposing 2O 3The analytically pure Eu (NO of 0.142g 3) 39H 2The Y that is equivalent to 0.02g after O and the decomposition 2O 3The analytically pure Y (NO of 0.07g 3) 39H 2O is equivalent to the V of 0.03g after the decomposition 2O 5The analytically pure VOSO of 0.05g 4Putting into the hydrochloric acid soln or the aqueous solution of 25 milliliters 0.3 volumetric molar concentration, after the dissolving, is 5 * 5 * 3mm, SiO with size fully again 2The content sintered glass that surpasses 96wt% put into this solution and soak more than 10 minutes; Afterwards, will be mixed with the high silica micropore glass of these ionic and put into High Temperature Furnaces Heating Apparatus, through 1150 ℃ solid state sintering, the elimination micropore becomes the closely knit transparent concentration total of mixing various oxide compounds and is about 0.1% vagcor in oxygen.In sintering process, with the speed of per minute below 5 ℃, after being raised to 400 ℃ from room temperature, speed with 10 ℃ of per minutes is raised to 950 ℃ of front and back, then, be raised to 1150 ℃ and after the insulation of this temperature is more than 30 minutes with the speed of per minute below 5 ℃ from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling.This glass under the irradiation of ultraviolet lamp, near generation emitting red light 613 nanometers.
Embodiment 3
The Eu of 0.7g will be equivalent to after decomposing 2O 3The analytically pure Eu (NO of 2.0g 3) 39H 2The Y that is equivalent to 0.03g after O and the decomposition 2O 3The analytically pure Y (NO of 0.1g 3) 39H 20, be equivalent to the V of 0.5g after the decomposition 2O 5The analytically pure VOSO of 0.9g 4Putting into the sulphuric acid soln of 25 milliliters 1.5 volumetric molar concentrations, after the dissolving, is 5 * 5 * 3mm, SiO with size fully again 2The content sintered glass that surpasses 98wt% put into this solution and soak more than 10 minutes; Afterwards, will be mixed with these ionic high silica porous glass and put into High Temperature Furnaces Heating Apparatus, through 1080 ℃ solid state sintering, the elimination micropore becomes the closely knit transparent concentration total of mixing various oxide compounds and is about 1.2% vagcor in oxygen.In sintering process, with the speed of per minute below 5 ℃, after being raised to 400 ℃ from room temperature, speed with 10 ℃ of per minutes is raised to 950 ℃ of front and back, then, be raised to 1080 ℃ and after the insulation of this temperature is more than 30 minutes with the speed of per minute below 5 ℃ from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling.This glass under the irradiation of ultraviolet lamp, near generation emitting red light 613 nanometers.
Embodiment 4
The Eu of 0.05g will be equivalent to after decomposing 2O 3The analytically pure Eu (NO of 0.142g 3) 39H 2The Gd that is equivalent to 0.1g after O and the decomposition 2O 3The analytically pure Gd (NO of 0.28g 3) 39H 2O is equivalent to the V of 0.05g after the decomposition 2O 5The analytically pure VOSO of 0.09g 4Putting into the salpeter solution of 25 milliliters 0.5 volumetric molar concentration, after the dissolving, is 5 * 5 * 3mm, SiO with size fully again 2The content sintered glass that surpasses 96wt% put into this solution and soak more than 10 minutes; Afterwards, will be mixed with these ionic high silica porous glass and put into High Temperature Furnaces Heating Apparatus, through 1150 ℃ solid state sintering, the elimination micropore becomes the closely knit transparent concentration total of mixing various oxide compounds and is about 0.2% vagcor in oxygen.In sintering process, with the speed of per minute below 5 ℃, after being raised to 400 ℃ from room temperature, speed with 10 ℃ of per minutes is raised to 950 ℃ of front and back, then, be raised to 1150 ℃ from this temperature with the speed of per minute below 5 ℃, and after this temperature insulation is more than 30 minutes, the power supply of turning off High Temperature Furnaces Heating Apparatus allows the glass furnace cooling.This glass under the irradiation of ultraviolet lamp, near generation emitting red light 613 nanometers.
Embodiment 5
The Eu of 0.5g will be equivalent to after decomposing 2O 3The analytically pure Eu (NO of 1.42g 3) 39H 2The Gd that is equivalent to 2.0g after O and the decomposition 2O 3The analytically pure Gd (NO of 5.6g 3) 39H 2O is equivalent to the V of 0.5g after the decomposition 2O 5The analytically pure VOSO of 0.9g 4Putting into the salpeter solution of 25 milliliters 3.0 volumetric molar concentrations, after the dissolving, is 5 * 5 * 3mm, SiO with size fully again 2The content sintered glass that surpasses 98wt% put into this solution and soak more than 10 minutes; Afterwards, will be mixed with these ionic high silica porous glass and put into High Temperature Furnaces Heating Apparatus, through 1050 ℃ solid state sintering, the elimination micropore becomes the closely knit transparent concentration total of mixing various oxide compounds and is about 3.0% vagcor in oxygen.In sintering process, with the speed of per minute below 5 ℃, after being raised to 400 ℃ from room temperature, speed with 10 ℃ of per minutes is raised to 950 ℃ of front and back, then, be raised to 1050 ℃ and after the insulation of this temperature is more than 30 minutes with the speed of per minute below 5 ℃ from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling.This glass under the irradiation of ultraviolet lamp, near generation emitting red light 613 nanometers.
Embodiment 6
The Eu of 0.1g will be equivalent to after decomposing 2O 3The analytically pure Eu (NO of 0.28g 3) 39H 2The Gd that is equivalent to 0.5g after O and the decomposition 2O 3The analytically pure Gd (NO of 1.4g 3) 39H 2O is equivalent to the V of 0.1g after the decomposition 2O 5The analytically pure VOSO of 0.18g 4Putting into 25 milliliters water or ethanol and acetone, after the dissolving, is 5 * 5 * 3mm, SiO with size fully again 2The content sintered glass that surpasses 95wt% put into this solution and soak more than 10 minutes; Afterwards, will be mixed with these ionic high silica porous glass and put into High Temperature Furnaces Heating Apparatus, through the solid state sintering of 1100 ℃ of degree, the elimination micropore becomes the closely knit transparent concentration total of mixing various oxide compounds and is about 0.7% vagcor in oxygen.In sintering process, with the speed of per minute below 5 ℃, after being raised to 400 ℃ from room temperature, speed with 10 ℃ of per minutes is raised to 950 ℃ of front and back, then, be raised to 1100 ℃ and after the insulation of this temperature is more than 30 minutes with the speed of per minute below 5 ℃ from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling.This glass under the irradiation of ultraviolet lamp, near generation emitting red light 613 nanometers.

Claims (3)

1. the manufacture method of a high silica red light emitting glass is characterized in that SiO 2The high silica porous glass immersion that content surpasses 96wt% contains europium ion, ruthenium ion and vanadium ion; Or in the solution of europium ion, gadolinium ion and vanadium ion, in oxygen atmosphere, form through 1050 ℃ of-1150 ℃ of high temperature sinterings.
2. the manufacture method of high silica red light emitting glass according to claim 1 is characterized in that the concrete steps of this method are as follows:
1. europium nitrate, Yttrium trinitrate and vanadylic sulfate water, salpeter solution, hydrochloric acid soln, sulphuric acid soln are dissolved fully, correspondingly make the aqueous solution, salpeter solution, hydrochloric acid soln, the sulphuric acid soln that contain europium, yttrium and vanadium ion;
2. with SiO 2The content high silica porous glass that surpasses 96wt% put into described solution and soak more than 10 minutes, to mix europium, yttrium and vanadium ion;
3. will be mixed with described ionic high silica porous glass and put into High Temperature Furnaces Heating Apparatus, in oxygen atmosphere, pass through 1050-1150 ℃ solid state sintering, in the sintering process, with the speed of per minute below 5 ℃, be raised to 400 ℃ from room temperature after, speed with 10 ℃ of per minutes is raised to 950 ℃, then, be raised to 1050-1150 ℃ of sintering temperature from this temperature, and be incubated more than 30 minutes in this sintering temperature with the speed of per minute below 5 ℃, the power supply of turning off High Temperature Furnaces Heating Apparatus allows the glass furnace cooling.
3. the manufacture method of high silica red light emitting glass according to claim 1 is characterized in that the concrete steps of this method are as follows:
1. europium nitrate, Gadolinium trinitrate and vanadylic sulfate water, salpeter solution, hydrochloric acid soln, sulphuric acid soln are dissolved fully, correspondingly make the aqueous solution, salpeter solution, hydrochloric acid soln, the sulphuric acid soln that contain europium, gadolinium and vanadium ion;
2. with SiO 2The content high silica porous glass that surpasses 96wt% put into described solution and soak more than 10 minutes, to mix europium, gadolinium and vanadium ion;
3. will be mixed with described ionic high silica porous glass and put into High Temperature Furnaces Heating Apparatus, in oxygen atmosphere, pass through 1050-1150 ℃ solid state sintering, in the sintering process, with the speed of per minute below 5 ℃, be raised to 400 ℃ from room temperature after, speed with 10 ℃ of per minutes is raised to 950 ℃, then, be raised to 1050-1150 ℃ of sintering temperature from this temperature, and be incubated more than 30 minutes in this sintering temperature with the speed of per minute below 5 ℃, the power supply of turning off High Temperature Furnaces Heating Apparatus allows the glass furnace cooling.
CNB2005100279097A 2005-07-20 2005-07-20 Manufacturing method of high silica red light emitting glass Expired - Fee Related CN100378021C (en)

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CN101215093B (en) * 2007-12-26 2010-06-09 中国科学院上海光学精密机械研究所 Method for manufacturing integrated colorful luminous vycor glass

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004050576A1 (en) * 2002-11-29 2004-06-17 Japan Science And Technology Agency Luminescent glass
CN1587136A (en) * 2004-09-02 2005-03-02 中国科学院上海光学精密机械研究所 Method for preparing bismuth blended high silicon oxygen and infrared broad band luminous glass

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004050576A1 (en) * 2002-11-29 2004-06-17 Japan Science And Technology Agency Luminescent glass
CN1587136A (en) * 2004-09-02 2005-03-02 中国科学院上海光学精密机械研究所 Method for preparing bismuth blended high silicon oxygen and infrared broad band luminous glass

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Co/Ce共掺杂高硅氧玻璃的制备和光谱性能. 谢康等.硅酸盐学报，第29卷第5期. 2001 *
YVO_4:Eu—高亮度效率红色萤光粉. 发光学报，第01期. 1971 *
稀土元素发光特性及其应用. 苏文斌等.化学研究，第12卷第4期. 2001 *

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