摘要
玻璃纤维是一种新型功能材料和结构材料,以其优良的性能广泛应用于电子、通讯、核能、航空、航天、兵器等高端领域,成为二十一世纪不可缺少的可持续发展的高新技术材料。目前生产的连续玻璃纤维90%以上是E玻璃,但是,在E玻璃熔制过程中硼、氟以氟硅酸、氢氟酸和氟硼酸盐的形式挥发,不但会影响玻璃成分的均一性、玻璃的使用性能,而且会污染环境。降低E玻璃纤维生产过程中硼、氟对环境造成的污染,成为人们关注的焦点。
本文在充分分析国内外研究现状的基础上,对无硼无氟玻璃系统结构、性能和工艺性能进行了系统研究。分别采用相同摩尔数的MgO、TiO_2、ZnO替代CaO,通过传统的熔融冷却法制备无硼无氟玻璃系统玻璃。运用红外光谱分析(IR)、核磁共振等方法分析了玻璃结构的变化,并对玻璃的密度、介电常数、化学稳定性、工艺性能进行了测试,讨论微观结构与性能之间的关系。在此基础上设计优化得到最优无硼无氟玻璃纤维的配方。
无硼无氟玻璃纤维基础体系引入碱土金属氧化物MgO。红外光谱和核磁共振研究结果表明:在基础玻璃体系中,Al~(3+)没有完全进入玻璃网络结构,部分Al~(3+)以[AlO_6]的形式存在于网络结构;1.5mol%MgO的引入有利于剩余的Al3+进入网络结构,玻璃的网络结构增强。随着MgO取代量的增加,玻璃的密度逐渐增加;介电常数和介电损耗值降低;化学稳定性增强;析晶上限温度先降低后升高;拉丝温度逐渐降低,其中MgO取代量为3mol%-6mol%时,符合玻璃纤维的拉丝工艺要求。
无硼无氟玻璃纤维基础体系分别引入过渡金属氧化物TiO_2和ZnO的研究。①红外光谱分析表明,TiO_2取代量为1.5mol%-3mol%时,Ti~(4+)以网络外体的形式存在;取代量4.5mol%时,Ti~(4+)以[TiO4]形式进入网络结构;取代量6mol%时,Ti4+反极化作用明显,玻璃的网络结构先增强后降低。随着TiO_2取代量的增加,玻璃的密度逐渐增加;介电常数和介电损耗值均表现出先降低后增大的趋势;化学稳定性提高;析晶上限温度先降低后升高;拉丝温度逐渐降低。TiO_2取代量为1.5-3mol%时,符合玻璃纤维的拉丝工艺要求。②红外光谱测试表明,ZnO取代量为7.5mol%时,Zn~(2+)仍以网络外体的形式存在,玻璃的网络结构逐渐增强。随着ZnO取代量的增加,密度增加;玻璃介电常数先降低后增加;介电损耗逐渐降低;化学稳定性提高;析晶上限温度先降低后升高;拉丝温度逐渐降低。ZnO取代量为1.5-4.5mol%时,符合玻璃纤维的拉丝工艺要求。
根据前面的实验结果,考察了MgO、ZnO、TiO_2共同作用对无硼无氟玻璃纤维性能的影响,并得到最佳无硼无氟玻璃纤维配方。
Fiberglass is one kind of new functional materials and the structural material,which has been applied in the electron, communication, nuclear power, aviation, astronautics, weapon and other high-end areas for a series of outstanding characteristics. Fiberglass becomes the essential high technology material for sustainable developments in 21st century. At present the produced continuous glass fibers above 90% is E glass. Boron and fluoride evaporate in the form of fluoride acid, hydrofluoric acid and fluorine borate in E glass-melting process, which not only affect the uniformity of glass composition and performance, but also pollute the environment. Now reducing boron-fluoride evaporation becomes the focus of attention.
Based on the analysis of the situation at home and abroad, structure,basic properties and processing properties of Boron-fluorine-free glass fibers was studied. In this thesis, series of Boron-fluorine-free glasses that CaO was replaced by MgO, TiO_2, ZnO respectively in the same moore number were prepared via a usual melting and quenching technique in the air medium. A number of studies differential infrared spectra (IR), nuclear magnetic resonance were used to analyze the structure of glass, chemical resistant, density, dielectric constant, glass fiber process have been carried out to explain the relation between glass structure and dielectric properties. Based on this, the study got optimal formula of boron-fluorine-free glass fiber by design optimization.
The study of boron-fluorine-free glassfiber based system for doping metal oxide MgO. IR spectra and NMR analysis showed that Al~(3+) isn’t fully into the glass network structure, part Al~(3+) exists in the network structure in the form of [AlO_6]. As 1.5mol % MgO introduced, the rest Al~(3+) enters the network structure.Glass network structure firstly increase then decrease, the glass density increase, the chemical durability improve ,dielectric constant and loss decrease after adding more MgO. Devitrification temperature and fiber-forming temperature firstly decreases then increases. The substituted amount of MgO increased from 3mol% to 6mol% is accord with glass fiber drawing technology requirements.
The study of boron-fluorine-free glass fiber based system for doping transition metal oxides TiO_2 and ZnO respectively.①IR spectra shows that when the substituted amount of TiO_2 increased from 1.5mol%-3mol%, Ti4+enters the glass network as a modifier; but for 4.5 mol%, Ti~(4+) enter the glass network in form of [TiO4].The extreme unstability of Ti~(4+) is significant when TiO_2 is increased at 6mol%. Glass network structure firstly increases then decreases by doping TiO_2; the glass density increases; dielectric constant and loss firstly decreases then increases; the glass chemical durability increases after more TiO_2was added. Devitrification temperature firstly decreases and then increases, however fiber-forming temperature gradually reduced. The substituted amount of TiO_2 increased from 1.5mol% to 3mol% is accord with glass fiber drawing technology requirements.②IR spectra shows that Zn~(2+) enters the glass network as a modifier when the substituted amount is7.5mol%. Glass network structure increases by doping ZnO; the glass density increases; dielectric constant firstly decreases then increases, however dielectric loss decreases; the glass chemical durability improves. Devitrification temperature firstly decreases and then increases, however fiber-forming temperature gradually reduced. The substituted amount of ZnO increased from 1.5mol% to 4.5mol% is accord with glass fiber drawing technology requirements.
From the experimental result above, the interaction of MgO, ZnO and TiO_2 to boron-fluorine-free glass fiber was investigated. The best formula was obtained.
引文
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