澄清剂对高硼硅平板玻璃结构与性能的影响研究
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摘要
高硼硅玻璃是指SiO_2>78%,B_2O_3>10%的硼硅酸盐玻璃。它是美国CORNING公司研究人员Sullivan于1915年发明的,并取得专利。基于浮法技术制备的高硼硅平板玻璃,由于具有优异的抗热震性和化学稳定性、极佳的光透过率、良好的玻璃表面面形、较低的热膨胀系数、厚度规格品种多样化等优点,而广泛应用于平面显示器(如LCD)、生物DNA芯片、光电池以及高档防弹玻璃和高级防火玻璃等领域。
由于高硼硅玻璃特殊的工艺特点(熔化温度高、澄清困难、硼挥发、易分层分相)难以满足浮法成形工艺,目前国际上能生产高硼硅平板玻璃的只有德国Schott公司,国内该领域尚属空白。高硼硅平板玻璃难于生产的主要原因之一是它的澄清非常困难。气泡的存在影响了玻璃的光学均匀性、机械强度等性能,对平板玻璃来说,属于严重的质量缺陷。因此,高硼硅平板玻璃的澄清研究具有十分重要的意义。
本论文从探索高硼硅玻璃的制备工艺出发,对实验室里用坩埚熔化高硼硅玻璃的特点进行了研究,确定了最佳的配方和合理的熔制制度。本论文主要针对高硼硅平板玻璃的澄清进行研究。选择在玻璃成分中加入少量的氯化钠、氧化铈、氧化镧、焦锑酸钾作澄清剂。通过比较几种澄清剂的澄清效果,找出了最佳的澄清剂种类及含量。研究表明,单一澄清剂无法达到高硼硅平板玻璃澄清的要求。用稀土氧化物配合氯化钠用作高硼硅玻璃的澄清剂,前者主要用于澄清玻璃中的灰泡,后者主要用于消除尺寸较大的气泡,澄清效果显著,玻璃外观质量和透明度明显提高。而焦锑酸钾不适宜作高硼硅玻璃的澄清剂。
为了深入研究高硼硅玻璃的结构,采用红外吸收光谱、透射电镜等分析手段,研究各种澄清剂对玻璃微观结构的影响。红外吸收光谱的研究发现,高硼硅玻璃中[SiO_4]、[AlO_4]、[BO_4]共同组成架状结构。由于[BO_4]本身带负电,需要不带电的[BO_3]进行隔离,因此在结构中存在少量硼酸盐基团。加入各种澄清剂没有造成玻璃结构明显的变化。这是因为无机玻璃的振动光谱主要取决于网络结构,而网络外离子的影响是次要的。残余的Cl~-和稀土离子处在结构网络空隙中;而Sb在结构中则形成了(Sb_3O_9)~(3-)环。另外,通过透射电镜观察到了高硼硅玻璃在局
Pyrex glass is a kind of borosilicate which contains above 78% SiO_2 and 13% B2O3. It was invented and granted patent by Sullivan in 1915, researcher of Corning Inc. America. Pyrex flat glass, produced based on floating technology, has a lot of advantages, such as high thermal shock resistance, good chemical resistance, excellent transmissivity, fine level surface, low thermal expansion coefficient and various thickness-standards, therefore it is widely used in plane display(for example LCD), biologic DNA CMOS chip, photoelectric cell, superior quality bulletproof glass and fireproof glass, etc.Pyrex glass is hard to satisfy float-shaping technics because of special technical characteristics (high melting temperature, hard to fining, boron volatilization, layering and phase separation). Now, only Schott Inc. of Germany can produce Pyrex flat glass, while it is a gap in our country. As Pyrex glass is hard to fining, there will be many bubbles in glass, which are considered as serious defects of flat glass and can induce negative effects on properties of glass, such as optical uniformity, mechanical strength, etc. Therefore, it is very important to research fining of Pyrex flat glass.In this essay, starting from preparation processes of Pyrex glass, the characteristics of melting Pyrex glass with crucible in lab were researched, and the optimal composition of glass and proper melting system were determined. The topic of this paper was about fining of Pyrex flat glass. Little NaCl, CeO_2, La_2O_3 and K_2H_2Sb_2O_7.4H_2O were chosen as fining agents. The optimal kind of fining agent and content were determined by comparison with the fining effects. The study suggested that using single fining agent couldn't satisfy the fining require of Pyrex flat glass. When rare earth oxide was compounded with NaCl used as fining agents, the fining effect, apparent quality and transmissivity could be greatly improved. This was because rare earth oxide was mainly used to eliminate fmeseeds while the function of NaCl was to remove bubbles. However, K_2H_2Sb_2O_7.4H_2O was found unfit for fining
of Pyrex glass.Furtherly, FTIR and TEM measurements were adopted to research the influence of fining agents on the microstructure of Pyrex glass. By FTIR, it was found that in Pyrex glass, [SiO4], [BO4] and [A1O4] formed the frame structure together. As [BO4] is negatively charged, it needs [BO3] to isolate and there were borate group in the structure of glass. The addition of fining agents didn't induce the change of glass structure. This is because FTIR of inorganic glass is mainly determined by the network-structure while not extra-network ions. The remaining Cl" and rare earth ions were located in the interstices of network, while antimony ions formed the (SbaOg) " rings in the structure. By TEM, a small amount of crystals were observed due to phase separation existed on the slight local area of Pyrex glass. Under higher powerful microscopes, many particles, which were similar to "tiny crystal" were observed. Their diameters were about 3~-10nm, which resulted in the un-homogenizing of chemistry and structure. It was suggested that fining agents had no direct influence on the microstructure of glass, as the "tiny crystals" were similar in all kinds of glasses.In this essay, effects of kinds of fining agents on comprehension properties such as density, U-V transmissivity and dielectric were furtherly researched. The densities of Pyrex glass were found between 2.32 and 2.35g/cnr1 and the visible transmissivities varied between 90.8% and 92%. That was to say, fining agents had less influence on them. But they had obvious effect on dielectric constant and dielectric loss of glass. The change of dielectric property had great relativity with the change of inner structure of glass, concentration of mobile ions, concentration of non-bridging oxygens and concentration of apt-to-polarization ion when kinds of fining agents were added.
由于高硼硅玻璃特殊的工艺特点(熔化温度高、澄清困难、硼挥发、易分层分相)难以满足浮法成形工艺,目前国际上能生产高硼硅平板玻璃的只有德国Schott公司,国内该领域尚属空白。高硼硅平板玻璃难于生产的主要原因之一是它的澄清非常困难。气泡的存在影响了玻璃的光学均匀性、机械强度等性能,对平板玻璃来说,属于严重的质量缺陷。因此,高硼硅平板玻璃的澄清研究具有十分重要的意义。
本论文从探索高硼硅玻璃的制备工艺出发,对实验室里用坩埚熔化高硼硅玻璃的特点进行了研究,确定了最佳的配方和合理的熔制制度。本论文主要针对高硼硅平板玻璃的澄清进行研究。选择在玻璃成分中加入少量的氯化钠、氧化铈、氧化镧、焦锑酸钾作澄清剂。通过比较几种澄清剂的澄清效果,找出了最佳的澄清剂种类及含量。研究表明,单一澄清剂无法达到高硼硅平板玻璃澄清的要求。用稀土氧化物配合氯化钠用作高硼硅玻璃的澄清剂,前者主要用于澄清玻璃中的灰泡,后者主要用于消除尺寸较大的气泡,澄清效果显著,玻璃外观质量和透明度明显提高。而焦锑酸钾不适宜作高硼硅玻璃的澄清剂。
为了深入研究高硼硅玻璃的结构,采用红外吸收光谱、透射电镜等分析手段,研究各种澄清剂对玻璃微观结构的影响。红外吸收光谱的研究发现,高硼硅玻璃中[SiO_4]、[AlO_4]、[BO_4]共同组成架状结构。由于[BO_4]本身带负电,需要不带电的[BO_3]进行隔离,因此在结构中存在少量硼酸盐基团。加入各种澄清剂没有造成玻璃结构明显的变化。这是因为无机玻璃的振动光谱主要取决于网络结构,而网络外离子的影响是次要的。残余的Cl~-和稀土离子处在结构网络空隙中;而Sb在结构中则形成了(Sb_3O_9)~(3-)环。另外,通过透射电镜观察到了高硼硅玻璃在局
Pyrex glass is a kind of borosilicate which contains above 78% SiO_2 and 13% B2O3. It was invented and granted patent by Sullivan in 1915, researcher of Corning Inc. America. Pyrex flat glass, produced based on floating technology, has a lot of advantages, such as high thermal shock resistance, good chemical resistance, excellent transmissivity, fine level surface, low thermal expansion coefficient and various thickness-standards, therefore it is widely used in plane display(for example LCD), biologic DNA CMOS chip, photoelectric cell, superior quality bulletproof glass and fireproof glass, etc.Pyrex glass is hard to satisfy float-shaping technics because of special technical characteristics (high melting temperature, hard to fining, boron volatilization, layering and phase separation). Now, only Schott Inc. of Germany can produce Pyrex flat glass, while it is a gap in our country. As Pyrex glass is hard to fining, there will be many bubbles in glass, which are considered as serious defects of flat glass and can induce negative effects on properties of glass, such as optical uniformity, mechanical strength, etc. Therefore, it is very important to research fining of Pyrex flat glass.In this essay, starting from preparation processes of Pyrex glass, the characteristics of melting Pyrex glass with crucible in lab were researched, and the optimal composition of glass and proper melting system were determined. The topic of this paper was about fining of Pyrex flat glass. Little NaCl, CeO_2, La_2O_3 and K_2H_2Sb_2O_7.4H_2O were chosen as fining agents. The optimal kind of fining agent and content were determined by comparison with the fining effects. The study suggested that using single fining agent couldn't satisfy the fining require of Pyrex flat glass. When rare earth oxide was compounded with NaCl used as fining agents, the fining effect, apparent quality and transmissivity could be greatly improved. This was because rare earth oxide was mainly used to eliminate fmeseeds while the function of NaCl was to remove bubbles. However, K_2H_2Sb_2O_7.4H_2O was found unfit for fining
of Pyrex glass.Furtherly, FTIR and TEM measurements were adopted to research the influence of fining agents on the microstructure of Pyrex glass. By FTIR, it was found that in Pyrex glass, [SiO4], [BO4] and [A1O4] formed the frame structure together. As [BO4] is negatively charged, it needs [BO3] to isolate and there were borate group in the structure of glass. The addition of fining agents didn't induce the change of glass structure. This is because FTIR of inorganic glass is mainly determined by the network-structure while not extra-network ions. The remaining Cl" and rare earth ions were located in the interstices of network, while antimony ions formed the (SbaOg) " rings in the structure. By TEM, a small amount of crystals were observed due to phase separation existed on the slight local area of Pyrex glass. Under higher powerful microscopes, many particles, which were similar to "tiny crystal" were observed. Their diameters were about 3~-10nm, which resulted in the un-homogenizing of chemistry and structure. It was suggested that fining agents had no direct influence on the microstructure of glass, as the "tiny crystals" were similar in all kinds of glasses.In this essay, effects of kinds of fining agents on comprehension properties such as density, U-V transmissivity and dielectric were furtherly researched. The densities of Pyrex glass were found between 2.32 and 2.35g/cnr1 and the visible transmissivities varied between 90.8% and 92%. That was to say, fining agents had less influence on them. But they had obvious effect on dielectric constant and dielectric loss of glass. The change of dielectric property had great relativity with the change of inner structure of glass, concentration of mobile ions, concentration of non-bridging oxygens and concentration of apt-to-polarization ion when kinds of fining agents were added.
引文
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