CN1880277A - Nanostructured glass ceramics and its sol-gelatin preparation method - Google Patents
Nanostructured glass ceramics and its sol-gelatin preparation method Download PDFInfo
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- CN1880277A CN1880277A CN 200510078781 CN200510078781A CN1880277A CN 1880277 A CN1880277 A CN 1880277A CN 200510078781 CN200510078781 CN 200510078781 CN 200510078781 A CN200510078781 A CN 200510078781A CN 1880277 A CN1880277 A CN 1880277A
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- 239000002241 glass-ceramic Substances 0.000 title abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920000159 gelatin Polymers 0.000 title 1
- 239000008273 gelatin Substances 0.000 title 1
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 abstract description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229940046892 lead acetate Drugs 0.000 description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- 229910052691 Erbium Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- DBUHPIKTDUMWTR-UHFFFAOYSA-K erbium(3+);triacetate Chemical compound [Er+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBUHPIKTDUMWTR-UHFFFAOYSA-K 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- -1 rare earth erbium ions Chemical class 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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Abstract
一种纳米结构玻璃陶瓷及其溶胶—凝胶制备方法，涉及一种氟化铅二氧化硅玻璃陶瓷及其制备。制备出的PbF2·SiO2纳米结构玻璃陶瓷块体纯度高、均匀性好，直径达30mm，厚度达1－5mm，呈高度透明性，并具有良好的机械性能(显微硬度达150kg/mm2)。A nanostructured glass ceramic and a sol-gel preparation method thereof relate to a lead fluoride silica glass ceramic and its preparation. The prepared PbF 2 ·SiO 2 nanostructured glass-ceramic block has high purity and good uniformity, with a diameter of 30mm and a thickness of 1-5mm. It is highly transparent and has good mechanical properties (microhardness of 150kg/mm 2 ).
Description
技术领域Technical field
本发明涉及玻璃陶瓷领域，尤其是涉及一种氟化铅二氧化硅玻璃陶瓷及其制备。The invention relates to the field of glass ceramics, in particular to a lead fluoride silica glass ceramic and its preparation.
背景技术 Background technique
玻璃陶瓷是玻璃相通过部分晶化而得，是玻璃和晶体的复合体；通过控制晶化过程，可得到透明的玻璃陶瓷，它是一种很好的发光基质。PbF2·SiO2纳米结构玻璃陶瓷是一种兼有氟化物低声子能量和氧化物机械强度与热稳定性的新型发光材料，在光通讯领域具有极大的应用前景，受到国内外学者的特别关注。目前制备PbF2·SiO2玻璃陶瓷材料的方法是熔融淬冷法，其制备条件要求高温，给研究和生产都带来不便；另外，用该法制备的材料组分分布不够均匀，且由于高温熔融时部分原料蒸发，导致最终材料组分偏离设计值。Glass-ceramic is obtained by partial crystallization of the glass phase, and is a composite of glass and crystal; by controlling the crystallization process, transparent glass-ceramic can be obtained, which is a good luminescent substrate. PbF 2 ·SiO 2 nanostructured glass-ceramic is a new type of luminescent material with low phonon energy of fluoride and mechanical strength and thermal stability of oxide. Special attention. At present, the method of preparing PbF 2 ·SiO 2 glass ceramics is the melting and quenching method, which requires high temperature for its preparation, which brings inconvenience to both research and production; Part of the raw material evaporates during melting, causing the final material composition to deviate from the design value.
发明内容Contents of Invention
本发明提出了一种PbF2·SiO2纳米结构玻璃陶瓷及其溶胶-凝胶制备工艺。The invention proposes a PbF 2 ·SiO 2 nanostructured glass ceramic and a sol-gel preparation process thereof.
本发明制备的PbF2·SiO2纳米结构玻璃陶瓷的组分为：XPbF2-YSiO2-ZErF3(X＝5-10mol％，Y＝(100-X-Z)mol％，Z＝0-1mol％)。The composition of the PbF 2 ·SiO 2 nanostructure glass ceramics prepared by the present invention is: XPbF 2 -YSiO 2 -ZErF 3 (X=5-10mol%, Y=(100-XZ)mol%, Z=0-1mol% ).
本发明采用如下制备工艺：将醋酸铅(Pb(AC)2·3H2O)、醋酸铒(Er(AC)3)、三氟乙酸(TFA)和水在烧杯中混合，并加热溶解，得到透明溶液(下面简称Pb/TFA溶液)；在另一烧杯中加入正硅酸乙酯(TEOS)、无水乙醇和水混合搅拌(下面简称TEOS/H2O溶液)，而后滴入水解催化剂，如HNO3、CH3COOH等。将Pb/TFA溶液滴加到TEOS/H2O溶液中，搅拌得到均匀透明的溶胶。将该溶胶在室温陈化后缓慢升温至120℃，干燥得到透明的干凝胶；将干凝胶在加热炉中以1-10℃/min的速率升温至350℃-550℃，得到PbF2·SiO2纳米结构玻璃陶瓷块体。The present invention adopts the following preparation process: lead acetate (Pb(AC) 2 3H 2 O), erbium acetate (Er(AC) 3 ), trifluoroacetic acid (TFA) and water are mixed in a beaker and heated to dissolve to obtain a transparent solution (hereinafter referred to as Pb/TFA solution); in another beaker, add tetraethyl orthosilicate (TEOS), absolute ethanol and water and mix and stir (hereinafter referred to as TEOS/H 2 O solution), and then drop in a hydrolysis catalyst, such as HNO 3 , CH 3 COOH, etc. The Pb/TFA solution was added dropwise to the TEOS/H 2 O solution, and stirred to obtain a uniform and transparent sol. After the sol is aged at room temperature, the temperature is slowly raised to 120°C, and dried to obtain a transparent xerogel; the xerogel is heated to 350°C-550°C at a rate of 1-10°C/min in a heating furnace to obtain PbF 2 · SiO2 nanostructured glass-ceramic bulk.
制备出的PbF2·SiO2纳米结构玻璃陶瓷块体纯度高、均匀性好，直径达30mm，厚度达1-5mm，呈高度透明性，并具有良好的机械性能(显微硬度达150kg/mm2)。掺杂少量的发光稀土铒离子后，玻璃陶瓷块体的外观及机械性能基本保持不变。The prepared PbF 2 ·SiO 2 nanostructured glass-ceramic block has high purity and good uniformity, with a diameter of 30mm and a thickness of 1-5mm, which is highly transparent and has good mechanical properties (microhardness of 150kg/mm 2 ). After doping a small amount of luminescent rare earth erbium ions, the appearance and mechanical properties of the glass ceramic block basically remain unchanged.
本发明材料制备工艺简单，对所需设备的要求不严格，成本较低，可以得到圆形或方形等各种符合使用要求的形状；本发明所采用的溶胶-凝胶制备方法，与目前制备PbF2·SiO2玻璃陶瓷材料采用的熔融淬冷法相比，制备温度大大降低，且制备出的玻璃陶瓷块体纯度高、均匀性好；由于无原料蒸发，最终组分与设计值基本一致。所以本发明的PbF2·SiO2纳米结构玻璃陶瓷块体将成为一种优良的新型发光基质。The preparation process of the material of the present invention is simple, the requirements for the required equipment are not strict, the cost is low, and various shapes that meet the requirements of use such as round or square can be obtained; the sol-gel preparation method adopted in the present invention is different from the current preparation Compared with the melting and quenching method adopted by PbF 2 ·SiO 2 glass-ceramic material, the preparation temperature is greatly reduced, and the prepared glass-ceramic block has high purity and good uniformity; because there is no raw material evaporation, the final composition is basically consistent with the design value. Therefore, the PbF 2 ·SiO 2 nanostructure glass ceramic block of the present invention will become an excellent new luminescent substrate.
具体实施方式 Detailed ways
实例1：将0.005mol醋酸铅(Pb(AC)2·3H2O)、0.03mol三氟乙酸(TFA)和0.02mol水在烧杯中混合，并加热溶解，得到透明溶液(下面简称Pb/TFA溶液)；在另一烧杯中加入0.1mol正硅酸乙酯(TEOS)、0.4mol无水乙醇和0.02mol水，滴入水解催化剂CH3COOH，混合搅拌30min(下面简称TEOS/H2O溶液)。将Pb/TFA溶液滴加到TEOS/H2O溶液中，调节溶液的pH值至2，然后盖上保鲜膜搅拌4小时，得到均匀透明溶胶。Example 1: Mix 0.005mol lead acetate (Pb(AC) 2 3H 2 O), 0.03mol trifluoroacetic acid (TFA) and 0.02mol water in a beaker, and heat to dissolve to obtain a transparent solution (hereinafter referred to as Pb/TFA solution ); in another beaker, add 0.1mol tetraethyl orthosilicate (TEOS), 0.4mol absolute ethanol and 0.02mol water, drop into the hydrolysis catalyst CH 3 COOH, mix and stir for 30min (hereinafter referred to as TEOS/H 2 O solution) . The Pb/TFA solution was added dropwise to the TEOS/H 2 O solution, the pH of the solution was adjusted to 2, and then covered with plastic wrap and stirred for 4 hours to obtain a uniform transparent sol.
将均匀溶胶倒入玻璃培养皿中，盖上保鲜膜。严格控制其干燥速度——室温陈化1周后，在保鲜膜上均匀地刺上若干个小孔，加快其形成凝胶过程，同时又保证凝胶不破裂；再经过1周陈化后，缓慢升温至120℃干燥7天，得到透明的干凝胶；将干凝胶在马弗炉中以5℃/min速率升温至500℃，得到PbF2·SiO2玻璃陶瓷块体，在JEM2010透射电子显微镜下观察其显微结构，其PbF2晶粒尺寸约为10-30nm，达到纳米量级。在HX-1000显微硬度计上测量其显微硬度为150kg/mm2。Pour the homogeneous sol into a glass petri dish and cover with plastic wrap. Strictly control its drying speed - after aging at room temperature for 1 week, puncture several small holes evenly on the plastic wrap to speed up the gel forming process and ensure that the gel does not break; after aging for 1 week, Slowly increase the temperature to 120°C and dry for 7 days to obtain a transparent xerogel; heat the xerogel to 500°C at a rate of 5°C/min in a muffle furnace to obtain a PbF 2 ·SiO 2 glass-ceramic block, which was transmitted in JEM2010 Observing its microstructure under an electron microscope, its PbF 2 grain size is about 10-30nm, reaching the nanometer level. The microhardness measured on HX-1000 microhardness tester was 150kg/mm 2 .
实例2：将0.005mol醋酸铅(Pb(AC)2·3H2O)、0.03mol三氟乙酸(TFA)、0.00025mol醋酸铒(Er(AC)3)和0.02mol水在烧杯中混合，并加热溶解，得到透明溶液(下面简称Pb/TFA溶液)；在另一烧杯中加入0.1mol正硅酸乙酯(TEOS)、0.4mol乙醇(CH3CH2OH)和0.02mol水，滴入水解催化剂CH3COOH，混合搅拌30min(下面简称TEOS/H2O溶液)。将Pb/TFA溶液滴加到TEOS/H2O溶液中，调节溶液的pH值至2，然后盖上保鲜膜搅拌4小时，得到均匀透明溶胶。Example 2: Mix 0.005mol lead acetate (Pb(AC) 2 3H 2 O), 0.03mol trifluoroacetic acid (TFA), 0.00025mol erbium acetate (Er(AC) 3 ) and 0.02mol water in a beaker, and heat Dissolve to obtain a transparent solution (hereinafter referred to as Pb/TFA solution); add 0.1mol tetraethyl orthosilicate (TEOS), 0.4mol ethanol (CH 3 CH 2 OH) and 0.02mol water in another beaker, drop into the hydrolysis catalyst CH 3 COOH, mixed and stirred for 30 minutes (hereinafter referred to as TEOS/H 2 O solution). The Pb/TFA solution was added dropwise to the TEOS/H 2 O solution, the pH of the solution was adjusted to 2, and then covered with plastic wrap and stirred for 4 hours to obtain a uniform transparent sol.
经过与实例1相同的干燥和热处理过程后，得到掺有0.5％铒离子的PbF2·SiO2纳米结构玻璃陶瓷块体，在JEM2010透射电子显微镜下观察其显微结构，其PbF2晶粒尺寸约为5-20nm。在HX-1000显微硬度计上测量其显微硬度为123kg/mm2。After the same drying and heat treatment process as in Example 1, a PbF 2 ·SiO 2 nanostructured glass-ceramic block doped with 0.5% erbium ions was obtained, and its microstructure was observed under a JEM2010 transmission electron microscope, and its PbF 2 grain size About 5-20nm. The microhardness measured on HX-1000 microhardness tester was 123kg/mm 2 .
实例3：将0.005mol醋酸铅(Pb(AC)2·3H2O)、0.03mol三氟乙酸(TFA)、0.0005mol醋酸铒(Er(AC)3)和0.02mol水在烧杯中混合，并加热溶解，得到透明溶液(下面简称Pb/TFA溶液)；在另一烧杯中加入0.1mol正硅酸乙酯(TEOS)、0.4mol乙醇(CH3CH2OH)和0.02mol水，滴入水解催化剂CH3COOH，混合搅拌30min(下面简称TEOS/H2O溶液)。将Pb/TFA溶液滴加到TEOS/H2O溶液中，调节溶液的pH值至2，然后盖上保鲜膜搅拌4小时，得到均匀透明溶胶。Example 3: Mix 0.005mol lead acetate (Pb(AC) 2 3H 2 O), 0.03mol trifluoroacetic acid (TFA), 0.0005mol erbium acetate (Er(AC) 3 ) and 0.02mol water in a beaker, and heat Dissolve to obtain a transparent solution (hereinafter referred to as Pb/TFA solution); add 0.1mol tetraethyl orthosilicate (TEOS), 0.4mol ethanol (CH 3 CH 2 OH) and 0.02mol water in another beaker, drop into the hydrolysis catalyst CH 3 COOH, mixed and stirred for 30 minutes (hereinafter referred to as TEOS/H 2 O solution). The Pb/TFA solution was added dropwise to the TEOS/H 2 O solution, the pH of the solution was adjusted to 2, and then covered with plastic wrap and stirred for 4 hours to obtain a uniform transparent sol.
经过与实例1相同的干燥和热处理过程后要，得到掺有1％铒离子的PbF2·SiO2纳米结构玻璃陶瓷块体，在JEM2010透射电子显微镜下观察其显微结构，其PbF2晶粒尺寸约为5-15nm。在HX-1000显微硬度计上测量其显微硬度为112kg/mm2。After the same drying and heat treatment process as in Example 1, the PbF 2 SiO 2 nanostructured glass-ceramic block doped with 1% erbium ions was obtained, and its microstructure was observed under a JEM2010 transmission electron microscope, and its PbF 2 crystal grains The size is about 5-15nm. The microhardness measured on HX-1000 microhardness tester was 112kg/mm 2 .
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| CN101840011A (en) * | 2010-04-15 | 2010-09-22 | 上海聚恒太阳能有限公司 | Manufacture method for nanometer self-cleaning spotlight solar energy Fresnel lens |
| CN101641155B (en) * | 2007-02-14 | 2013-07-10 | 皮埃尔-玛丽-居里大学 | Hybrid material, and method for the production |
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| CN101641155B (en) * | 2007-02-14 | 2013-07-10 | 皮埃尔-玛丽-居里大学 | Hybrid material, and method for the production |
| CN101840011A (en) * | 2010-04-15 | 2010-09-22 | 上海聚恒太阳能有限公司 | Manufacture method for nanometer self-cleaning spotlight solar energy Fresnel lens |
| CN101840011B (en) * | 2010-04-15 | 2012-03-28 | 上海聚恒太阳能有限公司 | Manufacture method for nanometer self-cleaning spotlight solar energy Fresnel lens |
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