WO2012006779A1 - 掺入稀土离子的碱金属硅酸盐发光玻璃及其制备方法 - Google Patents

掺入稀土离子的碱金属硅酸盐发光玻璃及其制备方法 Download PDF

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WO2012006779A1
WO2012006779A1 PCT/CN2010/075157 CN2010075157W WO2012006779A1 WO 2012006779 A1 WO2012006779 A1 WO 2012006779A1 CN 2010075157 W CN2010075157 W CN 2010075157W WO 2012006779 A1 WO2012006779 A1 WO 2012006779A1
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glass
alkali metal
cerium
preparation
ions
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PCT/CN2010/075157
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English (en)
French (fr)
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周明杰
乔延波
马文波
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海洋王照明科技股份有限公司
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Priority to CN201080068026XA priority Critical patent/CN102985383A/zh
Priority to PCT/CN2010/075157 priority patent/WO2012006779A1/zh
Priority to US13/810,008 priority patent/US9156733B2/en
Priority to JP2013518928A priority patent/JP2013538170A/ja
Priority to EP10854572.4A priority patent/EP2594537A4/en
Publication of WO2012006779A1 publication Critical patent/WO2012006779A1/zh

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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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/005—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to introduce in the glass such metals or metallic ions as Ag, Cu
    • 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
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/77742—Silicates
    • 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
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/08—Doped silica-based glasses containing boron or halide
    • C03C2201/10—Doped silica-based glasses containing boron or halide containing boron
    • 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
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
    • C03C2201/3423—Cerium
    • 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
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
    • C03C2201/3458—Terbium
    • 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
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
    • C03C2201/36—Doped silica-based glasses containing metals containing rare earth metals containing rare earth metals and aluminium, e.g. Er-Al co-doped
    • 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
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/54—Doped silica-based glasses containing metals containing beryllium, magnesium or alkaline earth metals
    • 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
    • C03C2203/00—Production processes
    • C03C2203/50—After-treatment

Definitions

  • the invention relates to a luminescent material and a preparation method thereof, in particular to an alkali metal silicate luminescent glass doped with two kinds of rare earth ions and a preparation method thereof.
  • luminescent glass there are many preparation methods for luminescent glass, one of which is to obtain a dense and transparent rare earth by introducing rare earth ions into the micropores of the nanoporous glass and then shrinking the micropores of the microporous glass by high temperature solid phase sintering.
  • Ion doped high silica light luminescent glass Ion doped high silica light luminescent glass.
  • the luminescent glass prepared by this method has many advantages, such as: excellent chemical stability, high mechanical strength, good thermal shock resistance and high energy ion irradiation resistance, high transmittance of ultraviolet and visible light, and good Machinability and the like.
  • the luminescence intensity of this material is not high, which greatly limits its application in the fields of illumination and display.
  • many studies at home and abroad also focus on how to enhance the luminescence intensity of rare earth ion doped high silica glass.
  • the technical problem to be solved by the present invention is to provide an alkali metal silicate luminescent glass doped with rare earth ions and a preparation method thereof with good stability and continuous improvement of luminescence intensity.
  • a technical solution to solve the technical problem of the present invention is to provide a method for preparing an alkali metal silicate luminescent glass doped with rare earth ions, which comprises the following steps:
  • Step 1 mixing a source compound of hydrazine, a source compound of hydrazine, and a source compound of an alkali metal into a solvent to form a mixed solution;
  • Step 2 immersing the nanoporous glass into the mixed solution in the first step
  • Step 3 The nanoporous glass after the immersion in the second step is sintered in a reducing atmosphere, and after cooling to room temperature, a cerium and lanthanum co-doped alkali metal silicate luminescent glass is obtained.
  • the source compound of the cerium is at least one of oxides, nitrates, chlorides, and acetates of cerium; the source compound of the cerium is oxidized by cerium At least one of a substance, a nitrate, a chloride, a sulfate, and an acetate; the source compound of the alkali metal is at least one of a nitrate, a chloride, a carbonate, and an acetate of an alkali metal
  • the solvent is one of water, nitric acid, hydrochloric acid, and acetic acid.
  • the alkali metal ion is at least one of a calcium ion, a cerium ion, and a cerium ion.
  • the concentration of cerium ions in the mixed solution is 0.001 to 0.1 mol/L, the concentration of cerium ions is 0.001 to 0.1 mol/L, and the concentration of alkali metal ions is 0.1 to 1 mol/L.
  • the nanoporous glass comprises the following components by weight: SiO 2 accounts for 94.0-98.0%; B 2 O 3 accounts for 1.0-3.0%; and Al 2 O 3 accounts for 1.0. ⁇ 3.0%.
  • the nanoporous glass has a micropore diameter of 4 to 30 nm, and the micropore volume accounts for 25 to 40% of the total volume of the glass.
  • the soaking time is 0.5 to 50 hours.
  • the nanoporous glass after the second step is air-dried at room temperature, and then gradually heated up, and raised to a sintering temperature during the temperature rise to 400 ° C at room temperature and 900 ° C.
  • the heating rate is not higher than 15 ° C / min
  • the temperature is raised to the sintering temperature for 1 to 20 hours
  • the sintering temperature is 1100 ° C to 1300 ° C.
  • the sintering temperature is preferably from 1150 ° C to 1250 ° C.
  • an alkali metal silicate luminescent glass doped with a rare earth ion prepared by the above preparation method.
  • the present invention introduces cerium ions (Tb 3+ ), cerium ions (Ce 3+ ) and alkali metal ions into the nanoporous glass by the immersion method, and is subjected to high-temperature solid phase sintering in a reducing atmosphere. After the micropores shrink, they become dense and non-porous transparent high-alumina glass. In the high-temperature heat treatment process, cerium ions, cerium ions and alkali metal ions are combined with SiO 2 matrix to form Ce, Tb co-doped alkali metal silicate luminescent nanometer.
  • the luminescence property is compared with that of Tb-doped glass, and the energy absorbed by Ce ions under ultraviolet excitation
  • the Tb ions are given, so that the green light of the Tb ions is greatly enhanced, thereby having a higher luminous intensity.
  • the high silica glass matrix has good permeability to ultraviolet light, which is beneficial to the absorption of the excitation wavelength by the luminescent ions, thereby improving the luminous efficiency.
  • the selected nanoporous glass matrix has a content of SiO 2 of not less than 94%, and its composition is similar to that of quartz glass, and has excellent physical and chemical properties similar to quartz glass, such as good chemical stability, high mechanical strength, and thermal expansion coefficient. Low, heat shock resistance, etc.
  • the invention also provides a preparation method of Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass, the preparation method co-doping Ce ion into Tb ion doped high silica glass, using Ce ion to Tb ion
  • the luminescence sensitization enhances the green luminescence of Tb to obtain a green luminescent glass excellent in luminescent properties.
  • the preparation method of the invention is convenient to operate and easy to implement, and the preparation method of the invention has the advantages of simple steps, easy operation, low calcination temperature and low cost.
  • FIG. 1 is a flow chart of a method for preparing an alkali metal silicate luminescent glass incorporating rare earth ions according to the present invention
  • Example 2 is a comparison diagram of excitation spectra of Ce, Tb co-doped alkali metal silicate luminescent nanocrystalline glass and single erbium doped high silica glass prepared in Example 1 of the present invention
  • Example 3 is a comparison diagram of emission spectra of Ce, Tb co-doped alkali metal silicate luminescent nanocrystalline glass and single erbium-doped high silica glass prepared in Example 1 of the present invention.
  • FIG. 1 shows a flow of a method for preparing an alkali metal silicate luminescent glass incorporating rare earth ions according to the present invention.
  • the preparation method comprises the following steps:
  • Step S01 mixing a source compound of hydrazine, a source compound of hydrazine, and a source compound of an alkali metal into a solvent to form a mixed solution;
  • Step S02 immersing the nanoporous glass into the mixed solution in step S01;
  • Step S03 The nanoporous glass after the immersion in the step S02 is sintered in a reducing atmosphere, and after cooling to room temperature, a cerium and lanthanum co-doped alkali metal silicate luminescent glass is obtained.
  • the source compound of the cerium is at least one of oxides, nitrates, chlorides, and acetates of cerium; the source compound of cerium is oxidized by cerium At least one of a substance, a nitrate, a chloride, a sulfate, and an acetate; the source compound of the alkali metal is at least one of a nitrate, a chloride, a carbonate, and an acetate of an alkali metal
  • the solvent is one of water, nitric acid, hydrochloric acid, and acetic acid.
  • the alkali metal ion is at least one of a calcium ion, a cerium ion, and a cerium ion.
  • the concentration of cerium ions in the mixed solution is 0.001 to 0.1 mol/L, the concentration of cerium ions is 0.001 to 0.1 mol/L, and the concentration of alkali metal ions is 0.1 to 1 mol/L.
  • the nanoporous glass comprises the following components by weight: SiO 2 accounts for 94.0-98.0%; B 2 O 3 accounts for 1.0-3.0%; and Al 2 O 3 accounts for 1.0. ⁇ 3.0%.
  • the nanoporous glass has a micropore diameter of 4 to 30 nm, and the micropore volume accounts for 25 to 40% of the total volume of the glass.
  • the soaking time is 0.5 to 50 hours.
  • step S03 the nanoporous glass after the step S02 is dried at room temperature, and then gradually heated up, and raised to a sintering temperature during the temperature rise to 400 ° C at room temperature and 900 ° C.
  • the heating rate is not higher than 15 ° C / min
  • the temperature is raised to the sintering temperature for 1 to 20 hours
  • the sintering temperature is 1100 ° C to 1300 ° C.
  • the sintering temperature is from 1150 ° C to 1250 ° C.
  • the present invention also provides an alkali metal silicate luminescent glass doped with rare earth ions prepared by the above preparation method.
  • the invention introduces cerium ions (Tb 3+ ), cerium ions (Ce 3+ ) and alkali metal ions into the nanoporous glass by the immersion method, and is sintered at a high temperature in a reducing atmosphere, and the micropores of the glass shrink and become dense.
  • Non-porous transparent high-alumina glass in the high-temperature heat treatment process, cerium ions, cerium ions and alkali metal ions together with SiO 2 matrix to form Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass, in the present invention
  • Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass due to the co-doping of Ce ions, under the excitation of ultraviolet light, the energy absorbed by Ce ions is transmitted to the Tb ions, thereby expressing Tb ion green. The light is greatly enhanced, so the luminescence performance has higher luminescence intensity than the Tb single-doped glass.
  • the invention adopts nano microporous glass as a matrix material, and the luminescent particles can be well dispersed in the micropores of the nano microporous glass, thereby avoiding the concentration quenching effect caused by the cluster, and the porosity of up to 25-40% is guaranteed.
  • the material contains a sufficient amount of nano-fine crystal grains to give the luminescent glass good luminescence properties.
  • the high silica glass matrix has good permeability to ultraviolet light, which is beneficial to the absorption of the excitation wavelength by the luminescent ions, thereby improving the luminous efficiency.
  • the selected nanoporous glass matrix has a content of SiO 2 of not less than 94%, and its composition is similar to that of quartz glass, and has excellent physical and chemical properties similar to quartz glass, such as good chemical stability, high mechanical strength, and thermal expansion coefficient. Low, heat shock resistance, etc.
  • the invention also provides a preparation method of Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass, the preparation method co-doping Ce ion into Tb ion doped high silica glass, using Ce ion to Tb ion
  • the luminescence sensitization enhances the green luminescence of Tb to obtain a green luminescent glass excellent in luminescent properties. Due to the excellent chemical stability, thermal stability and machinability of this material, as well as good green luminescent properties, the Ce, Tb co-doped alkali metal silicate luminescent nano-ceramics of the present invention are illuminated, displayed, laser and information
  • the field of optoelectronics has a good application prospect.
  • the preparation method of the invention is convenient to operate and easy to implement, and the preparation method of the invention has the advantages of simple steps, easy operation, low calcination temperature and low cost.
  • the Ce, Tb co-doped alkali metal silicate luminescent nanocrystalline glass of the present invention is prepared.
  • FIG. 2 is a comparison diagram of the excitation spectra of the glass prepared by the present embodiment and the high-silica glass doped with ytterbium
  • FIG. 3 is the high silicon of the glass prepared by the present embodiment and ytterbium doped with yttrium.
  • the comparison of the emission spectra of the oxygen glass, the excitation and emission spectra of the present invention were measured under a normal temperature condition using a Shimadzu RF-5301 fluorescence spectrometer.
  • Curve 21 in Fig. 2 shows the excitation spectrum of the glass prepared in this example
  • curve 22 shows the excitation spectrum of the single erbium-doped high silica glass
  • curve 31 in Fig. 3 shows the glass prepared in this example.
  • the emission spectrum, curve 32 shows the emission spectrum of a single erbium-doped high silica glass. It can be seen from FIG. 2 and FIG. 3 that the excitation and emission intensity of the Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass prepared in this embodiment is significantly enhanced than that of the erbium-doped high-silicate glass.
  • the high temperature furnace first rises to 400 ° C at a speed of 15 ° C / min, then rises to 900 ° C at a rate of 15 ° C / min, then rises to 1250 ° C at a rate of 5 ° C / min, and is sintered at 1250 ° C.
  • the sintered glass is taken out to the room temperature with the furnace, and after cutting and polishing, the Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass of the present invention is prepared.
  • the high temperature furnace is first raised to 400 ° C at a rate of 15 ° C / min, then raised to 900 ° C at a rate of 15 ° C / min, then raised to 1100 ° C at 5 ° C / min, and sintered at 1100 ° C 1h, the sintered glass was taken out to the room temperature with the furnace, and after cutting and polishing, the Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass of the present invention was prepared.
  • the high temperature furnace first rises to 400 ° C at a speed of 15 ° C / min, then rises to 900 ° C at a speed of 15 ° C / min, then rises to 1300 ° C at 5 ° C / min, and is sintered at 1300 ° C for 20 h.
  • the sintered glass is taken out to the room temperature with the furnace, and after cutting and polishing, the Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass of the present invention is prepared.
  • the high temperature furnace is first raised to 400 ° C at a rate of 12 ° C / min, then raised to 900 ° C at a rate of 15 ° C / min, then raised to 1220 ° C at 5 ° C / min, and sintered at 1220 ° C for 5 h
  • the sintered glass is taken out to the room temperature with the furnace, and after cutting and polishing, the Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass of the present invention is prepared.
  • the high temperature furnace is first raised to 400 ° C at a rate of 12 ° C / min, then raised to 900 ° C at a rate of 15 ° C / min, then raised to 1220 ° C at 5 ° C / min, and sintered at 1220 ° C for 5 h
  • the sintered glass is taken out to the room temperature with the furnace, and after cutting and polishing, the Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass of the present invention is prepared.
  • Medium temperature furnace first rises to 400 ° C at 15 ° C / min, then rises to 900 ° C at 15 ° C / min, then rises to 1250 ° C at 5 ° C / min, and is sintered at 1250 ° C for 6 h
  • the sintered glass is taken out to the room temperature with the furnace, and after cutting and polishing, the Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass of the present invention is prepared.
  • the high temperature furnace first rises to 400 ° C at a rate of 15 ° C / min, then rises to 900 ° C at a rate of 15 ° C / min, then rises to 1210 ° C at 5 ° C / min, and is sintered at 1210 ° C for 3 h
  • the sintered glass is taken out to the room temperature with the furnace, and after cutting and polishing, the Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass of the present invention is prepared.
  • the high temperature furnace first rises to 400 ° C at 15 ° C / min, then rises to 900 ° C at 15 ° C / min, then rises to 1180 ° C at 5 ° C / min, and is sintered at 1180 ° C for 3 h
  • the sintered glass is taken out to the room temperature with the furnace, and after cutting and polishing, the Ce, Tb co-doped alkali metal silicate luminescent nano-ceramic glass of the present invention is prepared.

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Abstract

一种掺入稀土离子的碱金属硅酸盐发光玻璃的制备方法，其包括如下步骤:步骤一：将铈的源化合物，铽的源化合物以及碱金属的源化合物混合溶入溶剂中形成混合溶液；步骤二：将纳米微孔玻璃浸入到步骤一中的混合溶液浸泡；步骤三：将步骤二中浸泡之后的纳米微孔玻璃在还原气氛中烧结，冷却至室温后，即制得铈和铽共掺碱金属硅酸盐发光玻璃。以及，一种通过以上制备方法制备的掺入稀土离子的碱金属硅酸盐发光玻璃。在所制备的发光玻璃中，由于共掺入了铈离子，在紫外光激发下，铈离子将吸收的能量传递给铽离子，因而，该发光玻璃与铽单掺的玻璃相比具有更高的发光强度。

Description

掺入稀土离子的碱金属硅酸盐发光玻璃及其制备方法 技术领域
本发明涉及一种发光材料及其制备方法，具体涉及一种掺入两种稀土离子的碱金属硅酸盐发光玻璃及其制备方法。
背景技术
目前，发光玻璃具有许多种制备方法，其中一种方法是通过向纳米微孔玻璃的微孔中引入稀土离子，再经过高温固相烧结使微孔玻璃的微孔收缩，可得到密实透明的稀土离子掺杂高硅氧发光玻璃。这种方法制备的发光玻璃具有很多优点，例如：优异的化学稳定性、较高的机械强度、较好的耐热冲击性能和耐高能离子辐照性能、紫外与可见光高透过率以及良好的可加工性等。然而，这种材料的发光强度不高，极大地限制了它在照明及显示等领域的应用，目前国内外很多研究也围绕着如何增强稀土离子掺杂高硅氧玻璃的发光强度积极展开工作。
2005年日本产业技术综合研究所就报道了利用纳米微孔玻璃制备铽掺杂绿色发光高硅氧玻璃的研究。他们用浸泡法向纳米微孔玻璃中引入铽离子，然后在空气或还原气氛中1100℃进行烧结得到无色透明的类石英绿色发光玻璃。有些研究方法是向纳米微孔玻璃中同时引入碱金属离子和铽离子，经过高温烧结与热处理，在纳米微孔玻璃纳米孔中生长出铽掺杂碱金属硅酸盐纳米微晶，实现了玻璃绿色发光的增强。然而，发光玻璃在实际应用中的潜在需求依然迫切需要发光玻璃的发光性能的持续增强。因此，研究出一种能够使得发光玻璃的发光性能持续增强的发光材料已经成为研究工作者研究的必然趋势。
 技术问题
本发明所要解决的技术问题是提供一种稳定性好以及发光强度持续增强的掺入稀土离子的碱金属硅酸盐发光玻璃及其制备方法。
 技术解决方案
解决本发明技术问题的技术方案是：提供一种掺入稀土离子的碱金属硅酸盐发光玻璃的制备方法，其包括如下步骤：
步骤一：将铈的源化合物，铽的源化合物以及碱金属的源化合物混合溶入溶剂中形成混合溶液；
步骤二：将纳米微孔玻璃浸入到步骤一中的混合溶液浸泡；
步骤三：将步骤二中浸泡之后的纳米微孔玻璃在还原气氛中烧结，冷却至室温后，即制得铈和铽共掺碱金属硅酸盐发光玻璃。
在本发明的方法中，在步骤一中，所述铽的源化合物为铽的氧化物、硝酸盐、氯化物、及乙酸盐中的至少一种；所述铈的源化合物为铈的氧化物、硝酸盐、氯化物、硫酸盐、及乙酸盐中的至少一种；所述碱金属的源化合物为碱金属的硝酸盐、氯化物、碳酸盐、及乙酸盐中的至少一种，所述溶剂为水、硝酸、盐酸、及乙酸中的一种。所述碱金属离子为钙离子、锶离子和钡离子中的至少一种。所述混合溶液中铽离子的浓度为0.001~0.1mol/L，铈离子的浓度为0.001~0.1mol/L，碱金属离子的浓度为0.1~1mol/L。
在本发明的方法中，在步骤二中，所述纳米微孔玻璃包括下列重量百分比的组分：SiO2占94.0~98.0%；B2O3占1.0~3.0% ；Al2O3占1.0~3.0%。所述纳米微孔玻璃的微孔孔径为4~30纳米，微孔体积占玻璃总体积的25~40%。所述浸泡时间为0.5~50小时。
在本发明的方法中，在步骤三中，将步骤二浸泡之后的纳米微孔玻璃在室温下晾干，然后再逐步升温，在室温升至400℃过程中和900℃升至烧结温度的过程中，升温速度不高于15℃/分钟，升温至烧结温度烧结1~20小时，烧结温度为1100℃~1300℃。所述烧结温度优选为1150℃~1250℃。
以及，一种通过以上制备方法制备的掺入稀土离子的碱金属硅酸盐发光玻璃。
 有益效果
相较于现有技术，本发明通过浸泡法向纳米微孔玻璃中引入铽离子(Tb3+)，铈离子（Ce3+）和碱金属离子，经过还原气氛中高温固相烧结，玻璃的微孔发生收缩后成为密实无孔的透明高硅氧玻璃，在高温热处理过程中，铽离子，铈离子和碱金属离子一起与SiO2基质结合生成Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃，在该碱金属硅酸盐发光纳米微晶玻璃中，由于共掺入了Ce离子，发光性能与Tb单掺的玻璃相比，在紫外光激发下，Ce离子将吸收的能量传递给Tb离子，从而表现为Tb离子发绿光大幅增强了，从而具有更高的发光强度。此外，高硅氧玻璃基质对紫外光有良好的透过性能，有利于发光离子对激发波长的吸收，从而提高了发光效率。选用的纳米微孔玻璃基质中SiO2的含量不低于94%，其成分类似于石英玻璃，具有类似于石英玻璃的优异的物理和化学性能，例如化学稳定性好、机械强度高、热膨胀系数低、耐热冲击等。
本发明还提供了一种Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃的制备方法，该制备方法向Tb离子掺杂高硅氧玻璃中共掺入Ce离子，利用Ce离子对Tb离子的发光敏化，增强Tb的绿色发光，得到一种发光性能优异的绿色发光玻璃。此外，本发明的制备方法操作方便、易于实施、本发明制备方法步骤简单、易于操作、煅烧温度低以及成本低廉。
 附图说明
下面将结合附图及实施例对本发明作进一步说明，附图中：
图1为本发明掺入稀土离子的碱金属硅酸盐发光玻璃的制备方法的流程图；
图2是本发明实施例1制备的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃与单掺铽的高硅氧玻璃的激发光谱的对比图；
图3是本发明实施例1制备的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃与单掺铽的高硅氧玻璃的发射光谱的对比图。
 本发明的实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
请参阅图1，图1显示了本发明掺入稀土离子的碱金属硅酸盐发光玻璃的制备方法的流程，该制备方法包括如下步骤：
步骤S01：将铈的源化合物，铽的源化合物以及碱金属的源化合物混合溶入溶剂中形成混合溶液；
步骤S02：将纳米微孔玻璃浸入到步骤S01中的混合溶液浸泡；
步骤S03：将步骤S02中浸泡之后的纳米微孔玻璃在还原气氛中烧结，冷却至室温后，即制得铈和铽共掺碱金属硅酸盐发光玻璃。
在本发明的方法中，在步骤S01中，所述铽的源化合物为铽的氧化物、硝酸盐、氯化物、及乙酸盐中的至少一种；所述铈的源化合物为铈的氧化物、硝酸盐、氯化物、硫酸盐、及乙酸盐中的至少一种；所述碱金属的源化合物为碱金属的硝酸盐、氯化物、碳酸盐、及乙酸盐中的至少一种，所述溶剂为水、硝酸、盐酸、及乙酸中的一种。所述碱金属离子为钙离子、锶离子和钡离子中的至少一种。所述混合溶液中铽离子的浓度为0.001~0.1mol/L，铈离子的浓度为0.001~0.1mol/L，碱金属离子的浓度为0.1~1mol/L。
在本发明的方法中，在步骤S02中，所述纳米微孔玻璃包括下列重量百分比的组分：SiO2占94.0~98.0%；B2O3占1.0~3.0% ；Al2O3占1.0~3.0%。所述纳米微孔玻璃的微孔孔径为4~30纳米，微孔体积占玻璃总体积的25~40%。所述浸泡时间为0.5~50小时。
在本发明的方法中，在步骤S03中，将步骤S02浸泡之后的纳米微孔玻璃在室温下晾干，然后再逐步升温，在室温升至400℃过程中和900℃升至烧结温度的过程中，升温速度不高于15℃/分钟，升温至烧结温度烧结1~20小时，烧结温度为1100℃~1300℃。优选地，所述烧结温度为1150℃~1250℃。
本发明还提供了一种通过以上制备方法制备的掺入稀土离子的碱金属硅酸盐发光玻璃。
本发明通过浸泡法向纳米微孔玻璃中引入铽离子(Tb3+)，铈离子（Ce3+）和碱金属离子，经过还原气氛中高温固相烧结，玻璃的微孔发生收缩后成为密实无孔的透明高硅氧玻璃，在高温热处理过程中，铽离子，铈离子和碱金属离子一起与SiO2基质结合生成Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃，在本发明制备的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃中，由于共掺入了Ce离子，在紫外光激发下，Ce离子将吸收的能量传递给Tb离子，从而表现为Tb离子绿光的大幅增强，故发光性能与Tb单掺的玻璃相比，具有更高的发光强度。
本发明选用纳米微孔玻璃作为基质材料，发光粒子在纳米微孔玻璃的微孔中能够被良好地分散，避免了团簇引起的浓度猝灭效应，高达25~40%的占孔率保证了该材料中含有足够数量的纳米微晶粒子，使发光玻璃具有良好的发光性能。此外，高硅氧玻璃基质对紫外光有良好的透过性能，有利于发光离子对激发波长的吸收，从而提高了发光效率。选用的纳米微孔玻璃基质中SiO2的含量不低于94%，其成分类似于石英玻璃，具有类似于石英玻璃的优异的物理和化学性能，例如化学稳定性好、机械强度高、热膨胀系数低、耐热冲击等。
本发明还提供了一种Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃的制备方法，该制备方法向Tb离子掺杂高硅氧玻璃中共掺入Ce离子，利用Ce离子对Tb离子的发光敏化，增强Tb的绿色发光，得到一种发光性能优异的绿色发光玻璃。由于这种材料优异的化学稳定性、热稳定性和机械加工性，以及良好绿色发光性能，本发明的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃在照明、显示、激光和信息等光电子领域均有较好的应用前景。此外，本发明的制备方法操作方便、易于实施、本发明制备方法步骤简单、易于操作、煅烧温度低以及成本低廉。
以下通过多个实施例来举例说明本发明不同制备方法以及其他特征等。
实施例1
使用分析天平称取0.423克（g）分析纯的硝酸锶(Sr(NO3)2), 0.0434克 （g）分析纯的六水合硝酸铈(Ce(NO3)3·6H2O)和0.0453g分析纯的六水合硝酸铽 (Tb(NO3)3·6H2O)溶于10ml的蒸馏水中，配制成浓度为0.20mol/L Sr2+,0.01mol/L Ce3+和0.01mol/L Tb3+的混合溶液。将纳米微孔玻璃（本发明中采用的纳米微孔玻璃为常见的商用材料，可直接在市面上采购得到。）浸泡到混合溶液中3小时（h）后取出，在室温下晾至表面干燥后置于通有氮气和氢气的混合气（体积比为：氮气：氢气 =95:5）的高温炉中，高温炉先以15℃/分钟（min）的速度升到400℃，再以15℃/min的速度升到900℃，之后以5℃/min的速度升到1200℃,在1200℃下保温烧结2h，烧结后的玻璃随炉冷却至室温取出，经过切割和抛光，即制备出本发明的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃。
如图2和图3所示，图2为本实施例制备的玻璃与单掺铽的高硅氧玻璃的激发光谱的对比图，图3为本实施例制备的玻璃与单掺铽的高硅氧玻璃的发射光谱的对比图，本发明的激发和发射光谱是采用岛津RF-5301荧光光谱仪在常温条件下进行测量得到。在图2中的曲线21表示本实施例制备的玻璃的激发光谱，曲线22表示的是单掺铽的高硅氧玻璃的激发光谱，图3中曲线31表示的是本实施例制备的玻璃的发射光谱，曲线32表示的是单掺铽的高硅氧玻璃的发射光谱。从图2和图3中可以看出，本实施例制备的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃的激发和发射强度比铽掺杂高硅氧玻璃的发光强度明显增强。
实施例2
使用分析天平称取1.181g分析纯的硝酸钙(Ca(NO3)2), 0.217g分析纯的六水合硝酸铈和0.0906g分析纯的六水合硝酸铽溶于10ml的蒸馏水中，配制成浓度为0.50mol/L Ca2+,0.05mol/L Ce3+和0.02mol/L Tb3+的混合溶液。将纳米微孔玻璃浸泡到混合溶液中10h后取出，在室温下晾至表面干燥后置于通有氮气和氢气的混合气（体积比为：N2: H2=95:5）的高温炉中，高温炉先以15℃/min的速度升到400℃，再以15℃/min的速度升到900℃，之后以5℃/min的速度升到1250℃,在1250℃下保温烧结4小时（h），烧结后的玻璃随炉冷却至室温取出，经过切割和抛光，即制备出本发明的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃。
实施例3
使用分析天平称取0.2613g分析纯的硝酸钡(Ba(NO3)2), 0.0043g分析纯的六水合硝酸铈和0.0045g分析纯的六水合硝酸铽溶于10ml的蒸馏水中，配制成浓度为0.1mol/L Ba2+,0.001mol/L Ce3+和0.001mol/L Tb3+的混合溶液。将纳米微孔玻璃浸泡到混合溶液中0.5h后取出，在室温下晾至表面干燥后置于通有氮气和氢气的混合气（体积比为：N2: H2=95:5）的高温炉中，高温炉先以15℃/min的速度升到400℃，再以15℃/min的速度升到900℃，之后以5℃/min的速度升到1100℃,在1100℃下保温烧结1h，烧结后的玻璃随炉冷却至室温取出，经过切割和抛光，即制备出本发明的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃。
实施例4
使用分析天平称取2.116g分析纯的硝酸锶(Sr(NO3)2), 0.4342g分析纯的六水合硝酸铈和0.4530g分析纯的六水合硝酸铽溶于10ml的蒸馏水中，配制成浓度为1mol/L Sr2+,0.1mol/L Ce3+和0.1mol/L Tb3+的混合溶液。将纳米微孔玻璃浸泡到混合溶液中50h后取出，在室温下晾至表面干燥后置于通有氮气和氢气的混合气（体积比为：N2: H2=95:5）的高温炉中，高温炉先以15℃/min的速度升到400℃，再以15℃/min的速度升到900℃，之后以5℃/min的速度升到1300℃,在1300℃下保温烧结20h，烧结后的玻璃随炉冷却至室温取出，经过切割和抛光，即制备出本发明的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃。
实施例5
使用分析天平称取0.3542g分析纯的四水合硝酸钙(Ca(NO3)2·4H2O)，0.3174g分析纯的硝酸锶(Sr(NO3)3)，0.1303g分析纯的六水合硝酸铈和0.0453g分析纯的六水合硝酸铽 溶于10ml的蒸馏水中，配制成浓度为0.15mol/L Ca2+，0.15mol/L Sr2+,0.03mol/L Ce3+和0.01mol/L Tb3+的混合溶液。将纳米微孔玻璃浸泡到混合溶液中12h后取出，在室温下晾至表面干燥后置于通有氮气和氢气的混合气（体积比为：N2: H2=95:5）的高温炉中，高温炉先以12℃/min的速度升到400℃，再以15℃/min的速度升到900℃，之后以5℃/min的速度升到1220℃,在1220℃下保温烧结5h，烧结后的玻璃随炉冷却至室温取出，经过切割和抛光，即制备出本发明的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃。
实施例6
使用分析天平称取0.2362g分析纯的四水合硝酸钙(Ca(NO3)2·4H2O)，0.2116g分析纯的硝酸锶，0.2613g分析纯的硝酸钡，0.0868g分析纯的六水合硝酸铈和0.0906g分析纯的六水合硝酸铽 溶于10ml的蒸馏水中，配制成浓度为0.10mol/L Ca2+、0.10mol/L Sr2+，0.10mol/L Ba2+，0.02mol/L Ce3+和0.02mol/L Tb3+的混合溶液。将纳米微孔玻璃浸泡到混合溶液中12h后取出，在室温下晾至表面干燥后置于通有氮气和氢气的混合气（体积比为：N2: H2=95:5）的高温炉中，高温炉先以12℃/min的速度升到400℃，再以15℃/min的速度升到900℃，之后以5℃/min的速度升到1220℃,在1220℃下保温烧结5h，烧结后的玻璃随炉冷却至室温取出，经过切割和抛光，即制备出本发明的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃。
实施例7
使用分析天平称取0.2775g分析纯的氯化钙(CaCl2)，0.0466g分析纯的七水合氯化铈 (CeCl3·7H2O)和0.0466g分析纯的六水合氯化铽 (TbCl3·6H2O)溶于10ml的蒸馏水中，配制成浓度为0.25mol/L Ca2+，0.0125mol/L Ce3+和0.0125mol/L Tb3+的混合溶液。将纳米微孔玻璃浸泡到混合溶液中24h后取出，在室温下晾至表面干燥后置于通有氮气和氢气的混合气（体积比为：N2：H2=95:5）的高温炉中，高温炉先以15℃/min的速度升到400℃，再以15℃/min的速度升到900℃，之后以5℃/min的速度升到1250℃,在1250℃下保温烧结6h，烧结后的玻璃随炉冷却至室温取出，经过切割和抛光，即制备出本发明的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃。
实施例8
使用分析天平称取1.3672g分析纯的乙酸钡(Ba(CH3COO)2) ，0.1221g分析纯的五水合乙酸铈(Ce(CH3COO)3·5H2O)和0.0708g分析纯的一水合乙酸铽 (Tb(CH3COO)3·H2O)溶于10ml的蒸馏水中，配制成浓度为0.50mol/L Ba2+，0.03mol/L Ce3+和0.02mol/L Tb3+的混合溶液。将纳米微孔玻璃浸泡到混合溶液中12h后取出，在室温下晾至表面干燥后置于通有氮气和氢气的混合气（体积比为：N2: H2=95:5）的高温炉中，高温炉先以15℃/min的速度升到400℃，再以15℃/min的速度升到900℃，之后以5℃/min的速度升到1210℃,在1210℃下保温烧结3h，烧结后的玻璃随炉冷却至室温取出，经过切割和抛光，即制备出本发明的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃。
实施例9
使用分析天平称取0.1845g分析纯的碳酸锶(SrCO3)，0.2467g分析纯的碳酸钡(BaCO3)，0.0344g分析纯的氧化铈 (CeO2) 和0.0366g分析纯的氧化铽(Tb2O3)溶于10ml的硝酸中，配制成浓度为0.125mol/L Sr2+，0.125mol/L Ba2+，0.02mol/L Ce3+和0.02mol/L Tb3+的混合溶液。将纳米微孔玻璃浸泡到混合溶液中6h后取出，在室温下晾至表面干燥后置于通有氮气和氢气的混合气（体积比为：N2: H2=95:5）的高温炉中，高温炉先以15℃/min的速度升到400℃，再以15℃/min的速度升到900℃，之后以5℃/min的速度升到1180℃,在1180℃下保温烧结3h，烧结后的玻璃随炉冷却至室温取出，经过切割和抛光，即制备出本发明的Ce，Tb共掺碱金属硅酸盐发光纳米微晶玻璃。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种掺入稀土离子的碱金属硅酸盐发光玻璃的制备方法，其包括如下步骤：
    步骤一：将铈的源化合物，铽的源化合物以及碱金属的源化合物混合溶入溶剂中形成混合溶液；
    步骤二：将纳米微孔玻璃浸入到步骤一中的混合溶液浸泡；
    步骤三：将步骤二中浸泡之后的纳米微孔玻璃在还原气氛中烧结，冷却至室温后，即制得铈和铽共掺碱金属硅酸盐发光玻璃。
  2. 如权利要求1所述的制备方法，其特征在于：在步骤一中，所述铽的源化合物为铽的氧化物、硝酸盐、氯化物、及乙酸盐中的至少一种；所述铈的源化合物为铈的氧化物、硝酸盐、氯化物、硫酸盐、及乙酸盐中的至少一种；所述碱金属的源化合物为碱金属的硝酸盐、氯化物、碳酸盐、及乙酸盐中的至少一种，所述溶剂为水、硝酸、盐酸、及乙酸中的一种。
  3. 如权利要求2所述的制备方法，其特征在于：所述碱金属离子为钙离子、锶离子和钡离子中的至少一种。
  4. 如权利要求1所述的制备方法，其特征在于：在步骤一中，所述混合溶液中铽离子的浓度为0.001~0.1mol/L，铈离子的浓度为0.001~0.1mol/L，碱金属离子的浓度为0.1~1mol/L。
  5. 如权利要求4所述的制备方法，其特征在于：在步骤二中，所述纳米微孔玻璃包括下列重量百分比的组分：SiO2占94.0~98.0%；B2O3占1.0~3.0% ；Al2O3占1.0~3.0%。
  6. 如权利要求5所述的制备方法，其特征在于：所述纳米微孔玻璃的微孔孔径为4~30纳米，微孔体积占玻璃总体积的25~40%。
  7. 如权利要求1所述的制备方法，其特征在于：在步骤二中，浸泡时间为0.5~50小时。
  8. 如权利要求1所述的制备方法，其特征在于：在步骤三中，将步骤二浸泡之后的纳米微孔玻璃在室温下晾干，然后再逐步升温，在室温升至400℃过程中和900℃升至烧结温度的过程中，升温速度不高于15℃/分钟，升温至烧结温度烧结1~20小时，烧结温度为1100℃~1300℃。
  9. 如权利要求8所述的制备方法，其特征在于：所述烧结温度为1150℃~1250℃。
  10. 一种根据权利要求1至9任意一项权利要求所述的制备方法制备的掺入稀土离子的碱金属硅酸盐发光玻璃。
PCT/CN2010/075157 2010-07-14 2010-07-14 掺入稀土离子的碱金属硅酸盐发光玻璃及其制备方法 WO2012006779A1 (zh)

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US13/810,008 US9156733B2 (en) 2010-07-14 2010-07-14 Rare earth ions doped alkali metal silicate luminescent glass and the preparation method thereof
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