铝硼硅系低介电常数玻璃纤维结构及失透行为研究
发布时间：2018-08-27 13:52
【摘要】：当前我国电子信息产业的高速发展,对于通信设备提出了高速化、高频化和小型化的需求。印制电路板和雷达天线罩等是信号传输工具关键部分,低介电常数玻璃纤维又是这些部分不可缺少的增强材料,有着十分重要地位。本文主要研究对象为铝硼硅系低介电常数玻璃,其应用背景是低介电常数玻璃纤维拉丝生产中可能遇到的分相或析晶问题。固定玻璃中其他组分,分别改变各种二价氧化物和CaO的摩尔比,外掺不同量的TiO2,设kn(n=1、2、3、4)=(MO/(MO+CaO))(MO为MgO、SrO、BaO、ZnO)。使用(MAS)NMR、FTIR、DSC、梯温析晶炉、XRD和SEM等测试手段,对铝硼硅系低介电常数玻璃纤维结构和失透行为做出了系统的研究,得出以下结论:随着k1的增大,玻璃网络结构逐渐解聚,玻璃结构中[BO4]、[AlO4]和含四个桥氧的[Si O4](Q4)相对含量减少,[BO3]逐渐增多;玻璃热稳定性随之降低,失透温度范围和失透上线温度都逐渐增大,其失透主要是由于分相引起的;k1较小时,玻璃分相形貌为蜂窝状的连通相,其机理为为亚稳分相,随着成分和热处理变化,富碱土金属和富硼相集聚析出,形成直径约为1μm的液滴相,稳定分相。随着k2的增大,玻璃结构中[BO4]、[AlO4]和Q4含量略有增多,SrO对玻璃网络结构有一定的增强作用,但并不明显。失透温度范围和失透上线温度都随之减小,甚至不失透,其失透主要是由于分相引起的。随着k3增大,玻璃结构更加稳定,玻璃结构中出现“硼反常”现象[BO4]含量先增多后减少,[AlO4]和Q4含量和桥氧数逐渐增多。BaO对玻璃网络结构有一定的增强作用,并且相对于SrO增强作用更大。失透温度范围和失透上线温度都随之减小,其失透主要是由于分相引起的。随着k4增大,ZnO对玻璃网络结构破坏和解聚作用增大,玻璃结构中[BO4]、[AlO4]和Q4相对含量减少,玻璃网络中非桥氧增多,并且各结构的变化相对于Mg组变化更大;其密度逐渐增大,失透温度范围和失透上线温度都随之增大。当ZnO含量较低和热处理温度较小时,失透主要是由于分相引起的。但随着k4值的增大和热处理温度升高和保温时间的延长,失透是由析晶引起的,主晶相为铝氧化锌(Al2ZnO4),次晶相为硼酸铝(Al8B4O33)。TiO2有减弱玻璃结构,促进玻璃分相和析晶的作用。随着外掺TiO2量增加,玻璃中各四面体结构单元四配位硼[BO4]、四配位铝[AlO4]和含有四个桥氧的[SiO4](Q4)逐渐减少,三配位硼[BO3]增多,玻璃结构稳定性减弱。其玻璃密度增大,其失透温度范围大大增加,其更加容易分相和析晶。析出主晶相是长约1μm的板条状的金红石型氧化钛晶体,次晶相是呈颗粒状的硼酸铝(Al18B4O33)晶体。
[Abstract]:With the rapid development of electronic information industry in China, the demand of high speed, high frequency and miniaturization for communication equipment is put forward. Printed circuit board (PCB) and radar radome are the key parts of signal transmission tools. Low dielectric constant fiberglass is an indispensable reinforcement material in these parts, and has a very important position. The main research object of this paper is the low dielectric constant glass of aluminum-boron-silicon system. Its application background is the problem of phase separation or crystallization that may be encountered in the production of glass fiber with low dielectric constant. The molar ratios of various divalent oxides and CaO were changed respectively for the other components in the fixed glass. The TiO2, with different admixtures of kn (NX _ (1) O _ (2) O _ (3) O _ (4) = (MO/ (MO CaO) (MO = (MgO,SrO,BaO,ZnO) was used. The structure and devitrification behavior of glass fiber with low permittivity of Al-BB-Si system were systematically studied by means of (MAS) NMR,FTIR,DSC, and SEM. The following conclusions were drawn: with the increase of K1, the network structure of glass was gradually depolymerized. The relative contents of [BO4], [AlO4] and [Si O _ 4] (Q _ 4) in glass structure decrease, and [BO3] increase gradually. The morphology of glass phase is honeycomb, and its mechanism is metastable phase. With the change of composition and heat treatment, alkali rich earth metal and boron rich phase are precipitated, and liquid droplet phase with diameter about 1 渭 m is formed, and the phase separation is stabilized. With the increase of K2, the contents of [BO4], [AlO4] and Q4 in glass structure increase slightly. Both the range of the temperature and the temperature on the line of the loss decrease and even do not lose their transmittance, which is mainly caused by the separation of phases. With the increase of K3, the glass structure becomes more stable. The "boron anomaly" [BO4] content in the glass structure increases first and then decreases. The content of [AlO4] and Q4 and the number of bridge oxygen increase gradually. Bao has a certain enhancement effect on the glass network structure. And it is more effective than SrO. Both the range of the temperature and the temperature of the line are decreased, which is mainly caused by the phase separation. With the increase of k4, the destruction and depolymerization of glass network structure increases, the relative contents of [BO4], [AlO4] and Q4 in glass structure decrease, and the unbridged oxygen in glass network increases, and the change of each structure is larger than that of Mg group, and its density increases gradually. Both the temperature range and the line temperature increase. When the content of ZnO is low and the heat treatment temperature is small, the breakdown is mainly caused by phase separation. However, with the increase of K _ 4 value, heat treatment temperature and holding time, the breakdown is caused by crystallization. The main crystalline phase is Al2ZnO4, and the secondary phase is aluminum borate (Al8B4O33) .TiO _ 2 has the function of weakening glass structure and promoting glass phase separation and crystallization. With the increase of TiO2 content, tetrahedral boron [BO4], tetrahedral aluminum [AlO4] and [SiO4] (Q4) containing four bridged oxygen in glass gradually decrease, while tri-coordinated boron [BO3] increases, and the structural stability of glass decreases. With the increase of glass density, the temperature range of the glass is greatly increased, and it is easier to separate and crystallize. The main precipitated phase is a plate-shaped rutile titanium oxide crystal with a length of about 1 渭 m, while the secondary phase is a granular aluminum borate (Al18B4O33) crystal.
【学位授予单位】：重庆理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ171.771
本文编号：2207486
[Abstract]:With the rapid development of electronic information industry in China, the demand of high speed, high frequency and miniaturization for communication equipment is put forward. Printed circuit board (PCB) and radar radome are the key parts of signal transmission tools. Low dielectric constant fiberglass is an indispensable reinforcement material in these parts, and has a very important position. The main research object of this paper is the low dielectric constant glass of aluminum-boron-silicon system. Its application background is the problem of phase separation or crystallization that may be encountered in the production of glass fiber with low dielectric constant. The molar ratios of various divalent oxides and CaO were changed respectively for the other components in the fixed glass. The TiO2, with different admixtures of kn (NX _ (1) O _ (2) O _ (3) O _ (4) = (MO/ (MO CaO) (MO = (MgO,SrO,BaO,ZnO) was used. The structure and devitrification behavior of glass fiber with low permittivity of Al-BB-Si system were systematically studied by means of (MAS) NMR,FTIR,DSC, and SEM. The following conclusions were drawn: with the increase of K1, the network structure of glass was gradually depolymerized. The relative contents of [BO4], [AlO4] and [Si O _ 4] (Q _ 4) in glass structure decrease, and [BO3] increase gradually. The morphology of glass phase is honeycomb, and its mechanism is metastable phase. With the change of composition and heat treatment, alkali rich earth metal and boron rich phase are precipitated, and liquid droplet phase with diameter about 1 渭 m is formed, and the phase separation is stabilized. With the increase of K2, the contents of [BO4], [AlO4] and Q4 in glass structure increase slightly. Both the range of the temperature and the temperature on the line of the loss decrease and even do not lose their transmittance, which is mainly caused by the separation of phases. With the increase of K3, the glass structure becomes more stable. The "boron anomaly" [BO4] content in the glass structure increases first and then decreases. The content of [AlO4] and Q4 and the number of bridge oxygen increase gradually. Bao has a certain enhancement effect on the glass network structure. And it is more effective than SrO. Both the range of the temperature and the temperature of the line are decreased, which is mainly caused by the phase separation. With the increase of k4, the destruction and depolymerization of glass network structure increases, the relative contents of [BO4], [AlO4] and Q4 in glass structure decrease, and the unbridged oxygen in glass network increases, and the change of each structure is larger than that of Mg group, and its density increases gradually. Both the temperature range and the line temperature increase. When the content of ZnO is low and the heat treatment temperature is small, the breakdown is mainly caused by phase separation. However, with the increase of K _ 4 value, heat treatment temperature and holding time, the breakdown is caused by crystallization. The main crystalline phase is Al2ZnO4, and the secondary phase is aluminum borate (Al8B4O33) .TiO _ 2 has the function of weakening glass structure and promoting glass phase separation and crystallization. With the increase of TiO2 content, tetrahedral boron [BO4], tetrahedral aluminum [AlO4] and [SiO4] (Q4) containing four bridged oxygen in glass gradually decrease, while tri-coordinated boron [BO3] increases, and the structural stability of glass decreases. With the increase of glass density, the temperature range of the glass is greatly increased, and it is easier to separate and crystallize. The main precipitated phase is a plate-shaped rutile titanium oxide crystal with a length of about 1 渭 m, while the secondary phase is a granular aluminum borate (Al18B4O33) crystal.
【学位授予单位】：重庆理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ171.771
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2 刘新年;张红林;贺祯;田鹏;;玻璃纤维新的应用领域及发展[J];陕西科技大学学报(自然科学版);2009年05期
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