无氟环保乳浊玻璃的研究
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摘要
乳浊玻璃在建筑、瓶罐、器皿、艺术和装饰等方面已得到广泛的应用,常用的乳浊剂为氟化物,如萤石、氟硅酸钠、冰晶石、氟化铝、氟化钾等。但是在原料处理、玻璃熔制和成型过程中,氟化物的挥发会造成人类急性和慢性中毒,同时对周围环境产生严重污染;另外,氟化物在玻璃熔制过程中会与耐火材料发生反应从而很大程度上降低玻璃窑炉的使用寿命,使生产成本增加,因此无氟乳浊玻璃的开发已成为解决问题的关键。
本文以含磷硅酸盐系统玻璃为研究对象,系统地研究了玻璃组成和热处理制度对玻璃试样的影响。采用X射线衍射分析(XRD)、扫描电子显微镜(SEM)和其自带的能量色散谱分析(EDS)、差示扫描量热分析(DSC)等测试方法研究了玻璃试样微观结构和乳浊机理,并且测试了试样的白度、密度、三点抗弯强度、热膨胀系数、化学稳定性、硬度等理化性能,以判断其是否达到实用的要求。
实验结果表明:通过调整SiO2和P_2O_5两种网络形成体的组成,同时引入碱金属或碱土金属氧化物,可以获得乳浊效果显著的乳白玻璃。玻璃系统中用质量分数为3%的B_2O_3取代Al_2O_3的结果表明:取代前后玻璃试样都会因亚稳分相的不稳分解造成玻璃失透,玻璃试样的白度均达到80%以上;玻璃中出现少量的晶体,并且第二相的颗粒尺寸变得不均匀;玻璃的密度、三点抗弯强度减小,化学稳定性降低,热膨胀系数增加;玻璃的性能改变的原因是B在玻璃中以[BO3]三角体和[BO_4]四面体两种配位方式共存。
网络修饰体对玻璃微观结构和性能的影响研究表明:玻璃网络中只含有CaO和Na_2O时,玻璃仍然保持透明,玻璃中析出了NaCaPO_4晶体;MgO和Li_2O的引入不会改变析出晶体的种类,但是会促进玻璃的分相和析晶,改变玻璃的微观形貌,这是造成玻璃失透的主要原因;600℃或700℃热处理20h都会使晶体长大到10-30μm,玻璃乳浊程度明显增加;热处理(600℃,20h)后,玻璃的三点抗弯强度、硬度、韧性均有一定程度的增加。
P_2O_5的含量对玻璃粘度影响的研究表明:质量分数为2%的P_2O_5取代SiO_2后,玻璃的粘度会因网络中形成大的阴离子基团(PO_4~(3-))增加了原子移动所需的粘滞活化能而增加;Vogel-Fulcher- Tamman(VFT)、Adam & Gibbs(AG)、Avramov (AV)公式拟合粘度数据的方差都小于3.03×10~(-6),拟合质量的顺序为VFT>AG>AV;取代后玻璃化转变温度(Tg)减小,Tg时的构型熵(Sc(Tg))增加,脆性指数(CAV)减小。
Opal glass receives a wide range of applications in many fields such as construction, bottles, wares, art, decoration, and so on. Common emulsion agents are fluorides such as fluorite, sodium fluoride and cryolite, aluminum fluoride, potassium fluoride, and so on. However, during glass making such as raw materials processing, glass melting and molding process, the volatilization of fluorides will cause human’s acute and chronic poisoning as well as environmental pollution. In addition, fluorides can react with firebrick and shorten the lifetime of kiln, which increases the cost of glass making. Such the investigation of fluorine-free opal glass is the key factor to solve above problem.
In this work, influence of compositions and heat treatment of Phosphorus- containing silicate opal glass on structure and properties was systematically investigated. Microstructure and opaque mechanism was studied by using XRD, SEM, EDS and DSC method. Furthermore, to judge whether it can be applied practically or not, the physical and chemical properties such as whiteness, density, bending strength, thermal expansion behavior, chemical stability and micro hardness were measured.
The results show that the excellent opaque glasses can be obtained by adjusting the ratio of SiO_2 and P_2O_5, and by introducing proper content of alkali or/and alkaline oxides. Although the substitution of 3wt% B_2O_3 for Al_2O_3 has little effect on appearance, i.e. heavy opaque glass can be obtained in both composition due to unstable phase separation and the whiteness of both glasses is larger than 80%. However, the substitution produces great change in following aspects: first, small amounts of crystal are precipitated during cooling and the particle size becomes more inhomogeneous, second, the destiny and bending strength decrease and chemical stability also reduces, thermal expansion coefficient increases, which could attribute to coexistence of [BO_3] tetragonal and [BO_4] tetrahedral coordination.
The type and content of network modifiers has great influence on the microstructure and properties of opal glasses. The glass remain transparent when only Na_2O and CaO are introduced and NaCaPO_4 crystals were observed, whereas the glasses become opalescent when MgO and/or Li_2O are used, which implies addition of MgO and/or Li_2O enhance the phase-separation and crystalization. In addition, the heat treatment also has effect on morphology and properties. The size of hexagonal NaCaPO_4 increases to10-30μm after heat treatment at 600 oC/700 oC for 20h, leading to that all samples appear heavy opalescent, at the same time, bending strength, micro hardness, toughness increase obviously.
Viscosity measurement results show that viscosity increases with substituting P_2O_5 for SiO_2, and this is due to formation of biger anion groups (PO_43-)which enhances the activation enthalpy of viscous flow. A good quality of fitting of Vogel-Fulcher- Tamman (VFT), Adam & Gibbs(AG) and Avramov(AV) equations to the measured viscosity has been achieved, which is reflected by the less standard deviations than 3.03×10-6, and the order is VFT>AG>AV. In addition, the glass transition temperature(Tg) and fragility index decrease, and the configurational entropy increase with the addition of P_2O_5.
本文以含磷硅酸盐系统玻璃为研究对象,系统地研究了玻璃组成和热处理制度对玻璃试样的影响。采用X射线衍射分析(XRD)、扫描电子显微镜(SEM)和其自带的能量色散谱分析(EDS)、差示扫描量热分析(DSC)等测试方法研究了玻璃试样微观结构和乳浊机理,并且测试了试样的白度、密度、三点抗弯强度、热膨胀系数、化学稳定性、硬度等理化性能,以判断其是否达到实用的要求。
实验结果表明:通过调整SiO2和P_2O_5两种网络形成体的组成,同时引入碱金属或碱土金属氧化物,可以获得乳浊效果显著的乳白玻璃。玻璃系统中用质量分数为3%的B_2O_3取代Al_2O_3的结果表明:取代前后玻璃试样都会因亚稳分相的不稳分解造成玻璃失透,玻璃试样的白度均达到80%以上;玻璃中出现少量的晶体,并且第二相的颗粒尺寸变得不均匀;玻璃的密度、三点抗弯强度减小,化学稳定性降低,热膨胀系数增加;玻璃的性能改变的原因是B在玻璃中以[BO3]三角体和[BO_4]四面体两种配位方式共存。
网络修饰体对玻璃微观结构和性能的影响研究表明:玻璃网络中只含有CaO和Na_2O时,玻璃仍然保持透明,玻璃中析出了NaCaPO_4晶体;MgO和Li_2O的引入不会改变析出晶体的种类,但是会促进玻璃的分相和析晶,改变玻璃的微观形貌,这是造成玻璃失透的主要原因;600℃或700℃热处理20h都会使晶体长大到10-30μm,玻璃乳浊程度明显增加;热处理(600℃,20h)后,玻璃的三点抗弯强度、硬度、韧性均有一定程度的增加。
P_2O_5的含量对玻璃粘度影响的研究表明:质量分数为2%的P_2O_5取代SiO_2后,玻璃的粘度会因网络中形成大的阴离子基团(PO_4~(3-))增加了原子移动所需的粘滞活化能而增加;Vogel-Fulcher- Tamman(VFT)、Adam & Gibbs(AG)、Avramov (AV)公式拟合粘度数据的方差都小于3.03×10~(-6),拟合质量的顺序为VFT>AG>AV;取代后玻璃化转变温度(Tg)减小,Tg时的构型熵(Sc(Tg))增加,脆性指数(CAV)减小。
Opal glass receives a wide range of applications in many fields such as construction, bottles, wares, art, decoration, and so on. Common emulsion agents are fluorides such as fluorite, sodium fluoride and cryolite, aluminum fluoride, potassium fluoride, and so on. However, during glass making such as raw materials processing, glass melting and molding process, the volatilization of fluorides will cause human’s acute and chronic poisoning as well as environmental pollution. In addition, fluorides can react with firebrick and shorten the lifetime of kiln, which increases the cost of glass making. Such the investigation of fluorine-free opal glass is the key factor to solve above problem.
In this work, influence of compositions and heat treatment of Phosphorus- containing silicate opal glass on structure and properties was systematically investigated. Microstructure and opaque mechanism was studied by using XRD, SEM, EDS and DSC method. Furthermore, to judge whether it can be applied practically or not, the physical and chemical properties such as whiteness, density, bending strength, thermal expansion behavior, chemical stability and micro hardness were measured.
The results show that the excellent opaque glasses can be obtained by adjusting the ratio of SiO_2 and P_2O_5, and by introducing proper content of alkali or/and alkaline oxides. Although the substitution of 3wt% B_2O_3 for Al_2O_3 has little effect on appearance, i.e. heavy opaque glass can be obtained in both composition due to unstable phase separation and the whiteness of both glasses is larger than 80%. However, the substitution produces great change in following aspects: first, small amounts of crystal are precipitated during cooling and the particle size becomes more inhomogeneous, second, the destiny and bending strength decrease and chemical stability also reduces, thermal expansion coefficient increases, which could attribute to coexistence of [BO_3] tetragonal and [BO_4] tetrahedral coordination.
The type and content of network modifiers has great influence on the microstructure and properties of opal glasses. The glass remain transparent when only Na_2O and CaO are introduced and NaCaPO_4 crystals were observed, whereas the glasses become opalescent when MgO and/or Li_2O are used, which implies addition of MgO and/or Li_2O enhance the phase-separation and crystalization. In addition, the heat treatment also has effect on morphology and properties. The size of hexagonal NaCaPO_4 increases to10-30μm after heat treatment at 600 oC/700 oC for 20h, leading to that all samples appear heavy opalescent, at the same time, bending strength, micro hardness, toughness increase obviously.
Viscosity measurement results show that viscosity increases with substituting P_2O_5 for SiO_2, and this is due to formation of biger anion groups (PO_43-)which enhances the activation enthalpy of viscous flow. A good quality of fitting of Vogel-Fulcher- Tamman (VFT), Adam & Gibbs(AG) and Avramov(AV) equations to the measured viscosity has been achieved, which is reflected by the less standard deviations than 3.03×10-6, and the order is VFT>AG>AV. In addition, the glass transition temperature(Tg) and fragility index decrease, and the configurational entropy increase with the addition of P_2O_5.
引文
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