CN101613183A - Multifunctional luminescent glass excited by long-wave broadband ultraviolet and its preparation method - Google Patents
Multifunctional luminescent glass excited by long-wave broadband ultraviolet and its preparation method Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 26
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 26
- 239000010457 zeolite Substances 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- -1 europium ion Chemical class 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 8
- 150000000918 Europium Chemical class 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 150000001217 Terbium Chemical class 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 2
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical group Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 2
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 2
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical group Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000003086 colorant Substances 0.000 abstract description 2
- 238000000921 elemental analysis Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000012190 activator Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005304 optical glass Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及长波宽带紫外激发的多功能发光玻璃及其制备方法。该发光玻璃的组成为SiO2·aAl2O3·bB2O3·cRexOy，其中，x＝1或2；y＝1或3；a＝0.05～0.5；b＝0～2.5；c－0.01～0.2；均为摩尔比；RexOy为EuO、Eu2O3或Tb2O3。本发明在比较简单的工艺条件下，制备出高透明度的多功能发光玻璃，该发光玻璃对250nm～420nm的紫外光区间有很强的吸收，通过调节其制备工艺可以实现红、绿、蓝及白光的发射。该发光玻璃可用于370－420nm激发的白光发光器件(LED)、激光二极管(LD)和显示器中的三基色的来源，有可能在超大屏幕彩色显示器中获得应用。
The invention relates to a long-wave broadband ultraviolet excited multifunctional luminescent glass and a preparation method thereof. The composition of the luminescent glass is SiO 2 ·aAl 2 O 3 ·bB 2 O 3 ·cRe x O y , where x=1 or 2; y=1 or 3; a=0.05-0.5; b=0-2.5; c-0.01-0.2; both are molar ratios; Re x O y is EuO, Eu 2 O 3 or Tb 2 O 3 . The present invention prepares a high-transparency multifunctional luminescent glass under relatively simple process conditions. The luminescent glass has a strong absorption of ultraviolet light in the range of 250nm to 420nm. By adjusting its preparation process, red, green, blue and Emission of white light. The luminescent glass can be used as a source of three primary colors in a white light emitting device (LED) excited by 370-420nm, a laser diode (LD) and a display, and may be applied in an ultra-large-screen color display.
Description
技术领域 technical field
本发明涉及发光材料技术领域，具体地说是长波宽带紫外激发的多功能发光玻璃及其制备方法。The invention relates to the technical field of luminescent materials, in particular to a long-wave broadband ultraviolet excited multifunctional luminescent glass and a preparation method thereof.
背景技术 Background technique
玻璃具有均匀、透明、坚硬、良好的耐腐蚀性和电学、光学等一系列特性，能够用多种成形和加工方法制成各种形状和大小的制品，可以通过调整化学组成改变其性质，以适应不同的使用要求。在现代信息产业中许多关键的光电子元件，如存储显示器件、放大器件、展示器件等都是由具有特殊光学功能的玻璃制成。另外，由于其特殊的网络结构是近有序而长程无序的，所以稀土离子在玻璃中的掺杂分散性相对较好，发光很均匀。自从美国康宁公司首次制成含镧、钍、钽等高折射、低散射的新型光学玻璃以后，稀土光学玻璃获得了很快的发展，通过稀土离子的掺杂可以制得不同用途的特种玻璃。但是，目前合成的发光玻璃主要为稀土离子掺杂的硅酸盐玻璃，吸收光谱较窄且亮度不高，在应用方面受到了很大的限制。Glass has a series of characteristics such as uniformity, transparency, hardness, good corrosion resistance, electricity, and optics. It can be made into products of various shapes and sizes by various forming and processing methods. Its properties can be changed by adjusting the chemical composition. Adapt to different usage requirements. Many key optoelectronic components in the modern information industry, such as storage display devices, amplification devices, display devices, etc., are made of glass with special optical functions. In addition, because its special network structure is near-ordered and long-range disordered, the doping dispersion of rare earth ions in the glass is relatively good, and the luminescence is very uniform. Since Corning Corporation of the United States made the first high-refraction and low-scattering new optical glass containing lanthanum, thorium, and tantalum, rare earth optical glass has developed rapidly, and special glasses for different purposes can be produced by doping rare earth ions. However, the currently synthesized luminescent glass is mainly silicate glass doped with rare earth ions, which has a narrow absorption spectrum and low brightness, which is greatly limited in application.
发明内容 Contents of the invention
本发明的目的在于制备一种吸收长波宽带紫外光发出红、绿、蓝及白光的多功能发光玻璃，它发光效率高，制备方法简单，成本低廉。The purpose of the present invention is to prepare a multifunctional luminescent glass which absorbs long-wave broadband ultraviolet light and emits red, green, blue and white light. It has high luminous efficiency, simple preparation method and low cost.
本发明提供一种长波宽带紫外激发的多功能发光玻璃，其组成由以下通式表示：SiO2·aAl2O3·bB2O3·cRexOy，其中，a＝0.05～0.5，b＝0～2.5，c＝0.01～0.2，均为摩尔比；RexOy为EuO、Eu2O3或Tb2O3。The invention provides a multifunctional luminescent glass excited by long-wave broadband ultraviolet rays, whose composition is represented by the following general formula: SiO 2 ·aAl 2 O 3 ·bB 2 O 3 ·cRe x O y , wherein, a=0.05-0.5, b =0~2.5, c=0.01~0.2, both are molar ratios; Re x O y is EuO, Eu 2 O 3 or Tb 2 O 3 .
在本发明的发光玻璃中，以沸石作为基质原料，利用铕离子、亚铕离子或铽离子取代介孔沸石中的钠离子，铕元素或铽元素作为发光激活剂，能在长波宽带紫外激发下发出红、绿、蓝及白光。In the luminescent glass of the present invention, zeolite is used as the matrix material, and the sodium ions in the mesoporous zeolite are replaced by europium ions, sub-europium ions or terbium ions. Emit red, green, blue and white light.
为达到上述发明目的，本发明通过以下具体方法予以实现：In order to achieve the above-mentioned purpose of the invention, the present invention is realized by the following specific methods:
(1)将介孔沸石与铕盐或铽盐溶液混合均匀，介孔沸石中的钠元素与铕离子或铽离子的摩尔比为1∶(0.5～2)；搅拌0.5～2小时后，在60～90℃下保温12～48小时，使铕离子或铽离子替换介孔沸石中的钠元素；离心分离去除上清液，取沉淀烘干得到前驱物；(1) Mesoporous zeolite and europium salt or terbium salt solution are mixed evenly, and the mol ratio of sodium element in mesoporous zeolite and europium ion or terbium ion is 1: (0.5～2); After stirring for 0.5～2 hours, in Incubate at 60-90°C for 12-48 hours to replace the sodium element in the mesoporous zeolite with europium ions or terbium ions; centrifuge to remove the supernatant, take the precipitate and dry it to obtain the precursor;
(2)将得到的前驱物与SiO2或H3BO3充分混合，在1300～1600℃下烧结6～10h后即得目标产物；前驱物以介孔沸石计，与SiO2或H3BO3摩尔比为1∶(1～10)。(2) Fully mix the obtained precursor with SiO 2 or H 3 BO 3 , and sinter at 1300-1600°C for 6-10 hours to obtain the target product ; 3 molar ratio is 1: (1～10).
所述的烧结在空气氛或N2/H2混合气体气氛下进行。The sintering is carried out under air atmosphere or N 2 /H 2 mixed gas atmosphere.
具体地说，在在空气氛下烧结得到SiO2·aAl2O3·bB2O3·cEu2O3或SiO2·aAl2O3·bB2O3·cTb2O3；N2/H2混合气体气氛烧结得到SiO2·aAl2O3·bB2O3·cEuO；N2/H2混合气体中，H2体积百分比为5％～20％。Specifically, SiO 2 ·aAl 2 O 3 ·bB 2 O 3 ·cEu 2 O 3 or SiO 2 ·aAl 2 O 3 ·bB 2 O 3 ·cTb 2 O 3 are obtained by sintering in an air atmosphere ; N 2 / SiO 2 ·aAl 2 O 3 ·bB 2 O 3 ·cEuO is obtained by sintering in an H 2 mixed gas atmosphere; in the N 2 /H 2 mixed gas, the volume percentage of H 2 is 5% to 20%.
所述的铕盐为氯化铕或硝酸铕，所述的铽盐为氯化铽或硝酸铽。The europium salt is europium chloride or europium nitrate, and the terbium salt is terbium chloride or terbium nitrate.
所述的铕盐或铽盐溶液浓度为0.05～1M。The concentration of the europium salt or terbium salt solution is 0.05-1M.
所述的介孔沸石为13X或4A型沸石。The mesoporous zeolite is 13X or 4A type zeolite.
本发明采用液相法结合高温固相法，得到一种吸收长波宽带紫外光发出红、绿、蓝及白光的多功能发光玻璃，该发光玻璃发光效率高，而且具有很高的化学及光学稳定性，可用于370-420nm激发的白光发光器件(LED)、激光二极管(LD)和显示器中的三基色的来源，能在超大屏幕彩色显示器中获得应用。The invention adopts a liquid phase method combined with a high temperature solid phase method to obtain a multifunctional luminescent glass that absorbs long-wave broadband ultraviolet light and emits red, green, blue and white light. The luminescent glass has high luminous efficiency and has high chemical and optical stability. It can be used in 370-420nm excited white light-emitting device (LED), laser diode (LD) and the source of the three primary colors in the display, and can be applied in the ultra-large-screen color display.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1)本发明首次实现了沸石为基质的长波宽带紫外激发的多功能发光玻璃。沸石是一种介孔材料，具有高的比表面积和特殊的孔结构，把稀土激活剂离子组装到沸石中，能够有效的避免激活剂的团聚引起的荧光浓度淬灭，可有效的提高激活剂和基质之间能量转换效率和发光效率。1) The present invention realizes for the first time a multifunctional luminescent glass with long-wave broadband ultraviolet excitation as a matrix. Zeolite is a kind of mesoporous material with high specific surface area and special pore structure. The assembly of rare earth activator ions into zeolite can effectively avoid the quenching of fluorescence concentration caused by the agglomeration of activators, and can effectively increase the concentration of activators. Energy conversion efficiency and luminous efficiency between substrate and matrix.
2)本发明的长波宽带紫外激发的多功能发光玻璃透明度高，对紫外区的吸收较宽可以拓展到长波紫外区，发光效率和应用范围高于目前一般的商用发光玻璃。2) The long-wave broadband ultraviolet-excited multifunctional luminescent glass of the present invention has high transparency, broad absorption in the ultraviolet region and can be extended to the long-wave ultraviolet region, and its luminous efficiency and application range are higher than that of the current general commercial luminescent glass.
3)本发明的制备工艺简单易操作，原料价廉易得，适合工业化生产，反应过程基本没有工业三废，具有绿色环保、低能耗、高效益等特点。3) The preparation process of the present invention is simple and easy to operate, the raw materials are cheap and easy to obtain, and is suitable for industrial production. The reaction process basically does not have three industrial wastes, and has the characteristics of environmental protection, low energy consumption, and high efficiency.
附图说明 Description of drawings
图1为实施例7宽带紫外激发的蓝色发光玻璃荧光光谱图Fig. 1 is the blue luminescent glass fluorescence spectrum figure excited by embodiment 7 broadband ultraviolet
图2为实施例8宽带紫外激发的绿色发光玻璃荧光光谱图Fig. 2 is the fluorescence spectrogram of green luminescent glass excited by broadband ultraviolet of embodiment 8
图3为实施例1宽带紫外激发的红色发光玻璃荧光光谱图Fig. 3 is the red luminescent glass fluorescent spectrum figure excited by embodiment 1 broadband ultraviolet
图4为实施例6宽带紫外激发的白色发光玻璃荧光光谱图Fig. 4 is the white luminous glass fluorescent spectrum figure excited by embodiment 6 broadband ultraviolet
(上述谱图中，左边的线代表激发光谱，右边的线代表发射光谱)(In the above spectrogram, the left line represents the excitation spectrum, and the right line represents the emission spectrum)
具体实施方式 Detailed ways
以下通过实施例进一步说明本发明。但应理解，这些实例只是示例性的，本发明不局限于此。The present invention is further illustrated by the following examples. However, it should be understood that these examples are illustrative only, and the present invention is not limited thereto.
实施例1Example 1
取0.0035mol 13X型沸石(Na2O·Al2O3·2.8SiO2·6H2O)投入30ml的0.1mol/L EuCl3溶液中，搅拌1小时，置于80℃水浴24小时，离心分离去除上清液，放入100℃的烘箱中烘干。将得到的前驱物与0.4211gSiO2充分混合后，放入30mL坩埚中，置于高温炉中空气氛1500℃下烧结8h后即得目标产物。用元素分析(ICP)测定其组成为：SiO2·0.21Al2O3·0.08Eu2O3，具有高透明度，380nm紫外光照射下发红光。Take 0.0035mol 13X zeolite (Na 2 O Al 2 O 3 2.8SiO 2 6H 2 O) into 30 ml of 0.1 mol/L EuCl 3 solution, stir for 1 hour, place in 80°C water bath for 24 hours, and centrifuge Remove the supernatant and dry in an oven at 100°C. After fully mixing the obtained precursor with 0.4211g SiO 2 , put it into a 30mL crucible, place it in a high-temperature furnace and sinter at 1500°C for 8 hours to obtain the target product. Its composition is determined by elemental analysis (ICP): SiO 2 ·0.21Al 2 O 3 ·0.08Eu 2 O 3 . It has high transparency and emits red light under 380nm ultraviolet light.
实施例2Example 2
取0.0035mol 13X型沸石Na2O·Al2O3·2.8SiO2·6H2O投入30ml的0.5mol/L EuCl3溶液中，搅拌1小时，置于80℃水浴20小时，离心分离去除上清液，放入100℃的烘箱中烘干。将得到的前驱物与0.4211g SiO2充分混合后，放入30mL坩埚中，置于高温炉中空气氛1450℃下烧结10h后即得目标产物。用元素分析(ICP)测定其组成为其组成为SiO2·0.21Al2O3·0.12Eu2O3，380nm紫外光照射下发红光。Take 0.0035mol 13X type zeolite Na 2 O·Al 2 O 3 2.8SiO 2 ·6H 2 O and put it into 30ml of 0.5mol/L EuCl 3 solution, stir for 1 hour, place in 80°C water bath for 20 hours, centrifuge to remove the above The clear liquid was dried in an oven at 100°C. The obtained precursor was fully mixed with 0.4211g SiO 2 , put into a 30mL crucible, placed in a high-temperature furnace and sintered at 1450°C for 10h to obtain the target product. Its composition is determined by elemental analysis (ICP), and its composition is SiO 2 ·0.21Al 2 O 3 ·0.12Eu 2 O 3 , and it emits red light under 380nm ultraviolet light irradiation.
实施例3Example 3
取0.004mol 4A型沸石Na2O·Al2O3·2SiO2·4.5H2O投入30ml的0.1mol/L EuCl3溶液中，搅拌1小时，置于80℃水浴24小时，离心分离去除上清液，放入100℃的烘箱中烘干。将得到的前驱物与0.004mol SiO2充分混合后，放入30mL坩埚中，置于高温炉中空气氛1450℃下烧结10h后即得目标产物。用元素分析(ICP)测定其组成为SiO2·0.33Al2O3·0.11Eu2O3，380nm紫外光照射下发红光。Take 0.004mol 4A zeolite Na 2 O · Al 2 O 3 · 2SiO 2 · 4.5H 2 O and put it into 30ml of 0.1mol/L EuCl 3 solution, stir for 1 hour, place in 80℃ water bath for 24 hours, centrifuge to remove the above The clear liquid was dried in an oven at 100°C. The obtained precursor was fully mixed with 0.004mol SiO 2 , put into a 30mL crucible, placed in a high-temperature furnace and sintered at 1450°C for 10 hours to obtain the target product. Its composition is determined by elemental analysis (ICP) to be SiO 2 ·0.33Al 2 O 3 ·0.11Eu 2 O 3 , and it emits red light under 380nm ultraviolet light irradiation.
实施例4Example 4
取0.004mol 4A型沸石Na2O·Al2O3·2SiO2·4.5H2O投入30ml的0.1mol/L EuCl3溶液中，搅拌1小时，置于80℃水浴24小时，离心分离去除上清液，放入100℃的烘箱中烘干。将得到的前驱物与0.004mol SiO2充分混合后，放入30mL坩埚中，置于高温炉中在N2/H2(5％H2+95％N2)气氛下1500℃下烧结8h后即得目标产物。用元素分析(ICP)测定其组成为SiO2·0.33Al2O3·0.092EuO，380nm紫外光照射下发蓝光。Take 0.004mol 4A zeolite Na 2 O · Al 2 O 3 · 2SiO 2 · 4.5H 2 O and put it into 30ml of 0.1mol/L EuCl 3 solution, stir for 1 hour, place in 80℃ water bath for 24 hours, centrifuge to remove the above The clear liquid was dried in an oven at 100°C. After fully mixing the obtained precursor with 0.004mol SiO 2 , put it into a 30mL crucible, place it in a high-temperature furnace and sinter at 1500°C for 8 hours under the atmosphere of N 2 /H 2 (5% H 2 +95% N 2 ) The target product is obtained. Its composition is determined by elemental analysis (ICP) to be SiO 2 ·0.33Al 2 O 3 ·0.092EuO, and it emits blue light under the irradiation of 380nm ultraviolet light.
实施例5Example 5
取0.0035mol 13X型沸石Na2O·Al2O3·2.8SiO2·6H2O投入30ml的0.1mol/L EuCl3溶液中，搅拌1小时，置于80℃水浴24小时，离心分离去除上清液，放入100℃的烘箱中烘干。将得到的前驱物与0.4333gH3BO3(0.007mol)充分混合后，放入30mL坩埚中，置于高温炉中1300℃下烧结10h后即得目标产物。用元素分析(ICP)测定其组成为SiO2·0.36Al2O3·0.357B2O3·0.061 Eu2O3，380nm紫外光照射下发红光。Take 0.0035mol 13X zeolite Na 2 O·Al 2 O 3 2.8SiO 2 6H 2 O and put it into 30ml of 0.1mol/L EuCl 3 solution, stir for 1 hour, place in 80°C water bath for 24 hours, centrifuge to remove the above The clear liquid was dried in an oven at 100°C. The obtained precursor was fully mixed with 0.4333gH 3 BO 3 (0.007mol), put into a 30mL crucible, and placed in a high-temperature furnace for sintering at 1300°C for 10h to obtain the target product. Its composition is determined by elemental analysis (ICP) to be SiO 2 ·0.36Al 2 O 3 ·0.357B 2 O 3 ·0.061 Eu 2 O 3 , and it emits red light under 380nm ultraviolet light irradiation.
实施例6Example 6
取0.0035mol 13X型沸石投入30ml的0.1mol/L EuCl3溶液中，搅拌1小时，置于80℃水浴18小时，离心分离去除上清液，放入100℃的烘箱中烘干。将得到的前驱物与0.4211gSiO2(0.007mol)充分混合后，放入30mL坩埚中，置于高温炉中在N2/H2(15％H2+85％N2)气氛下1500℃下烧结8h后即得目标产物。用元素分析(ICP)测定其组成为SiO2·0.21Al2O3·0.16EuO，380nm紫外光照射下发白光。Take 0.0035mol 13X type zeolite and put it into 30ml of 0.1mol/L EuCl 3 solution, stir for 1 hour, place in 80°C water bath for 18 hours, centrifuge to remove the supernatant, put it in an oven at 100°C for drying. After fully mixing the obtained precursor with 0.4211g SiO 2 (0.007mol), put it into a 30mL crucible, place it in a high-temperature furnace at 1500°C under the atmosphere of N 2 /H 2 (15% H 2 +85% N 2 ) The target product was obtained after sintering for 8h. Its composition is determined by elemental analysis (ICP) to be SiO 2 ·0.21Al 2 O 3 ·0.16EuO, and it emits white light under the irradiation of 380nm ultraviolet light.
实施例7Example 7
取13X型沸石0.0035mol投入30ml的0.5mol/L EuCl3溶液中，搅拌1小时，置于80℃水浴20小时，离心分离去除上清液，放入100℃的烘箱中烘干。将得到的前驱物与0.2106gSiO2(0.0035mol)充分混合后，放入30mL坩埚中，置于高温炉中在N2/H2(20％H2+80％N2)气氛下1450℃下烧结8h后即得目标产物。用元素分析(ICP)测定其组成为SiO2·0.26Al2O3·0.18EuO，380nm紫外光照射下发蓝光。Take 0.0035mol of 13X-type zeolite and put it into 30ml of 0.5mol/L EuCl 3 solution, stir for 1 hour, place in 80°C water bath for 20 hours, centrifuge to remove the supernatant, and put it in an oven at 100°C for drying. After fully mixing the obtained precursor with 0.2106g SiO 2 (0.0035mol), put it into a 30mL crucible, place it in a high-temperature furnace at 1450°C under the atmosphere of N 2 /H 2 (20% H 2 +80% N 2 ) The target product was obtained after sintering for 8h. Its composition is determined by elemental analysis (ICP) to be SiO 2 ·0.26Al 2 O 3 ·0.18EuO, and it emits blue light under the irradiation of 380nm ultraviolet light.
实施例8Example 8
取13X型沸石0.0035mol投入35ml的0.1mol/L Tb(NO3)3溶液中，搅拌1小时，置于80℃水浴18小时，离心分离去除上清液，放入100℃的烘箱中烘干。将得到的前驱物与0.4211gSiO2(0.007mol)充分混合后，放入30mL坩埚中，置于高温炉中空气氛1500℃下烧结8h后即得目标产物。用元素分析(ICP)测定其组成为：SiO2·0.21Al2O3·0.072Tb2O3，380nm紫外光照射下发绿光。Take 0.0035mol of 13X-type zeolite and put it into 35ml of 0.1mol/L Tb(NO 3 ) 3 solution, stir for 1 hour, place in 80°C water bath for 18 hours, centrifuge to remove the supernatant, put it in an oven at 100°C for drying . The obtained precursor was fully mixed with 0.4211g SiO 2 (0.007mol), put into a 30mL crucible, placed in a high-temperature furnace and sintered at 1500°C for 8 hours to obtain the target product. Its composition is determined by elemental analysis (ICP): SiO 2 ·0.21Al 2 O 3 ·0.072Tb 2 O 3 , and emits green light under 380nm ultraviolet light irradiation.
实施例9Example 9
取13X型沸石0.0035mol投入35ml的0.1mol/L Tb(NO3)3溶液中，搅拌1小时，置于80℃水浴20小时，离心分离去除上清液，放入100℃的烘箱中烘干。将得到的前驱物与0.6317gSiO2(0.0105mol)充分混合后，放入30mL坩埚中，置于高温炉中空气氛1500℃下烧结10h后即得目标产物。用元素分析(ICP)测定其组成为：SiO2·0.172Al2O3·0.043Tb2O3，380nm紫外光照射下发绿光。Take 0.0035mol of 13X-type zeolite and put it into 35ml of 0.1mol/L Tb(NO 3 ) 3 solution, stir for 1 hour, place in 80°C water bath for 20 hours, centrifuge to remove the supernatant, put it in an oven at 100°C for drying . The obtained precursor was fully mixed with 0.6317g SiO 2 (0.0105mol), put into a 30mL crucible, placed in a high-temperature furnace and sintered at 1500°C for 10 hours to obtain the target product. Its composition is determined by elemental analysis (ICP): SiO 2 ·0.172Al 2 O 3 ·0.043Tb 2 O 3 , and emits green light under 380nm ultraviolet light irradiation.
实施例10Example 10
取13X型沸石Na2O·Al2O3·2.8SiO2·6H2O 0.0035mol投入35ml的0.1mol/L Eu(NO3)3溶液中，搅拌1小时，置于80℃水浴30小时，离心分离去除上清液，放入100℃的烘箱中烘干。将得到的前驱物与0.4211gSiO2(0.007mol)充分混合后，放入30mL坩埚中，置于高温炉中空气氛1550℃下烧结6h后即得目标产物。用元素分析(ICP)测定其组成为SiO2·0.21Al2O3·0.063Eu2O3，380nm紫外光照射下发红光。Take 0.0035 mol of 13X zeolite Na 2 O·Al 2 O 3 2.8SiO 2 6H 2 O and put it into 35 ml of 0.1 mol/L Eu(NO 3 ) 3 solution, stir for 1 hour, place in 80°C water bath for 30 hours, The supernatant was removed by centrifugation, and dried in an oven at 100°C. The obtained precursor was fully mixed with 0.4211g SiO 2 (0.007mol), put into a 30mL crucible, placed in a high-temperature furnace and sintered at 1550°C for 6 hours to obtain the target product. Its composition is determined by elemental analysis (ICP) to be SiO 2 ·0.21Al 2 O 3 ·0.063Eu 2 O 3 , and it emits red light under 380nm ultraviolet light irradiation.
实施例11Example 11
取13X型沸石Na2O·Al2O3·2.8SiO2·6H2O 0.0035mol投入35ml的0.1mol/L EuCl3溶液中，搅拌2小时，置于80℃水浴30小时，离心分离去除上清液，放入100℃的烘箱中烘干。将得到的前驱物与1.8951gSiO2(0.0315mol)充分混合后，放入30mL坩埚中，置于高温炉中空气氛1500℃下烧结9h后即得目标产物。用元素分析(ICP)测定其组成为SiO2·0.085Al2O3·0.024Eu2O3，380nm紫外光照射下发红光。Take 0.0035 mol of 13X zeolite Na 2 O·Al 2 O 3 2.8SiO 2 6H 2 O and put it into 35ml of 0.1mol/L EuCl 3 solution, stir for 2 hours, place in a water bath at 80°C for 30 hours, and centrifuge to remove the above The clear liquid was dried in an oven at 100°C. The obtained precursor was fully mixed with 1.8951g SiO 2 (0.0315mol), put into a 30mL crucible, placed in a high-temperature furnace and sintered at 1500°C for 9 hours to obtain the target product. Its composition is determined by elemental analysis (ICP) to be SiO 2 ·0.085Al 2 O 3 ·0.024Eu 2 O 3 , and it emits red light under the irradiation of 380nm ultraviolet light.
实施例12Example 12
取4A型沸石0.004mol(Na2O·Al2O3·2SiO2·4.5H2O)投入30ml的0.1mol/L EuCl3溶液中，搅拌1小时，置于80℃水浴24小时，离心分离去除上清液，放入100℃的烘箱中烘干。将得到的前驱物与0.036mol H3BO3充分混合后，放入30mL坩埚中，置于高温炉中在空气氛下1500℃下烧结8h后即得目标产物。用元素分析(ICP)测定其组成为SiO2·0.5Al2O3·2.25B2O3·0.1 Eu2O3，380nm紫外光照射下发红光。Take 0.004mol of 4A-type zeolite (Na 2 O Al 2 O 3 2SiO 2 4.5H 2 O) and put it into 30 ml of 0.1 mol/L EuCl 3 solution, stir for 1 hour, place in 80°C water bath for 24 hours, and centrifuge Remove the supernatant and dry in an oven at 100°C. The obtained precursor was fully mixed with 0.036mol H 3 BO 3 , put into a 30mL crucible, placed in a high-temperature furnace and sintered at 1500°C for 8 hours in an air atmosphere to obtain the target product. Its composition is determined by elemental analysis (ICP) to be SiO 2 ·0.5Al 2 O 3 ·2.25B 2 O 3 ·0.1 Eu 2 O 3 , and it emits red light under 380nm ultraviolet light irradiation.
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| CN102173583A (en) * | 2010-11-29 | 2011-09-07 | 天津理工大学 | Rare earth activated white light luminescent glass material as well as preparation method and application thereof |
| CN111646703A (en) * | 2020-05-18 | 2020-09-11 | 东华大学 | Fluoride/oxyfluoride fluorescent glass ceramic and preparation method and application thereof |
| CN111847883A (en) * | 2020-08-31 | 2020-10-30 | 贵州赛义光电科技有限公司 | Fluorescent glass ceramic and preparation method thereof |
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| CN1035549C (en) * | 1991-12-29 | 1997-08-06 | 中国科学院西安光学精密机械研究所 | Preparation method of magnetosensitive optical rotation glass with high Verdet constant |
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| CN102173583B (en) * | 2010-11-29 | 2013-02-20 | 天津理工大学 | Rare earth activated white light luminescent glass material as well as preparation method and application thereof |
| CN111646703A (en) * | 2020-05-18 | 2020-09-11 | 东华大学 | Fluoride/oxyfluoride fluorescent glass ceramic and preparation method and application thereof |
| CN111847883A (en) * | 2020-08-31 | 2020-10-30 | 贵州赛义光电科技有限公司 | Fluorescent glass ceramic and preparation method thereof |
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