CN106915903A - 二氧化硅绝缘电缆连接用抗辐射微晶玻璃及制备方法 - Google Patents
二氧化硅绝缘电缆连接用抗辐射微晶玻璃及制备方法 Download PDFInfo
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- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
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- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
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- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
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Abstract
本发明涉及二氧化硅绝缘电缆连接用抗辐射微晶玻璃及制备方法。该材料以锂铝硅酸盐(LAS)为主的低膨胀微晶玻璃,其具有适应的热膨胀0.3‑1.2·10‑6 /K。该玻璃包括以下成分,按重量百分比计,Li2O2.5‑8.5,Al2O316.2‑26,SiO240‑71.8,TiO20.8‑4.6,ZrO20.6‑3.7,P2O51.3‑7,F‑0.7‑3.1,CeO20.7‑3.9,B2O31.8‑6.9,Na2O0.5‑3.5,K2O0.4‑3,MgO0.6‑4.5,CaO0.2‑5.2,SrO0‑3.7,BaO0‑3,ZnO1.9‑8.2,Cl‑0‑1.2,SO4 2‑0‑1.3。本发明的连接材料高强度、耐冷热冲击性能好、膨胀系数小、具有抗辐照稳定性,能够能应用于高辐射区域。
Description
技术领域
本发明涉及一种二氧化硅绝缘电缆连接用抗辐射微晶玻璃及制备方法。
背景技术
在超过300度的恶劣环境下,特别是还有高低温冲击、辐射、震动等共同作用的情况下,如果需要高可靠的传输信号,目前最高档的选择就是二氧化硅绝缘电缆,因为二氧化硅材料低损耗、电绝缘性良好等特性,完全消除了塑料绝缘在高温高辐射等情况下容易裂化损坏的致命缺点,被广泛应用与航空航天核电等高端信号传输领域。
但对于实际应用时(尤其是在核电站内应用),如果需要连接二氧化硅绝缘电缆,必须要求连接材料和连接件除了具有与二氧化硅热膨胀匹配性相同的要求外,还必须保证其具有较好的抗辐射性。目前相关研究欠缺。
发明内容
本发明是为了克服传统二氧化硅绝缘电缆连接存在的抗辐射性局限,发明了一种抗辐射低膨胀微晶玻璃作为连接材料或附件。
众所周知,要求连接材料尽可能地具有与二氧化硅类似的热膨胀性(0.5·10-6/K)、绝缘性,保障绝缘材料不影响正常工作。微晶玻璃是通过控制玻璃的结晶而得到的一类多晶材料,由于它同时具备了抗温度冲击,高频绝缘,高机械强度,高化学稳定性这四个方面的优良性能,所以能够应用于特殊领域,锂铝硅酸盐(LAS)玻璃材料,其具有β-石英固溶体或β-锂辉石固溶体微小晶相,具有良好的抗热震、耐高温、耐腐蚀及高机械强度等性能,导致其优异的耐温差性和耐温度变化性,并且还具有尺寸稳定性。
本发明的抗辐射微晶玻璃材料,含有以下主要成分:
Li2O2.5-8.5,Al2O316.2-26,SiO240-71.8,TiO20.8-4.6,ZrO20.6-3.7,P2O51.3-7,F-0.7-3.1,CeO20.7-3.9,B2O31.8-6.9,Na2O0.5-3.5,K2O0.4-3,MgO0.6-4.5,CaO0.2-5.2,SrO0-3.7,BaO0-3,ZnO1.9-8.2,Cl-0-1.2,SO4 2-0-1.3
其中,Li2O、B2O3、Na2O、K2O起到助熔作用,加速玻璃熔制和澄清。MgO、CaO、SrO、BaO、ZnO能够改善玻璃稳定性,降低玻璃的高温粘度,ZrO2、P2O5、F-、TiO2作为玻璃的晶核剂,促进玻璃微晶化,提高晶化质量,减少晶化时间,CeO2作为抗辐射剂,增强了该玻璃成品应对高能粒子、电子、质子等的强辐射,氯、硫酸根离子作为本发明组成玻璃的澄清剂,促进玻璃熔化时气泡的排除,减少玻璃缺陷的产生。
本发明中,Li2O用量2.5-8.5,含量低了玻璃在核化与晶化困难,含量高晶化时候晶体颗粒大,玻璃性能变差。Al2O3用量16.2-26,含量低晶体含量低,含量高了会造成玻璃熔化困难。SiO2用量40-71.8,含量低了玻璃网络结构疏松,含量高了会造成玻璃熔化困难。
本发明中,采用ZrO2、P2O5、F-、TiO2作为晶核剂,其中P2O5可促进TiO2的熔融,有利于形成空间相互连接结构。CeO2含量0.7-3.9,获得辐照稳定性:电子能量为1MeV,累计通量为1×1016 e/cm2,光谱在500nm-2000nm范围内,辐照前后光谱特性平均值的衰减值<0.1。
本发明的生产工艺中,通过将玻璃高温熔融、澄清,退火后经一定的热处理制度进行成核和晶化以获得晶粒细小、含量多、结构均匀的微晶玻璃材料。通过受控析晶而获得晶粒细小、含量多、结构均匀多晶材料,保证本发明的材料的各种性能满足使用要求。
具体实施例:
通过如下实施例示例本发明。
实施例1
Li2O8.5,Al2O326,SiO240,TiO24.6,ZrO20.6,P2O53,F-3.1,CeO23.9,B2O35.2,Na2O0.7,K2O0.6,MgO0.7,CaO0.4,SrO0.2,BaO0.3,ZnO2,Cl-0.1,SO4 2-0.1
实施例2
Li2O3,Al2O317.6,SiO241,TiO21.9,ZrO21.7,P2O51.5,F-1.5,CeO21.3,B2O36.9,Na2O3.5,K2O3,MgO4.5,CaO1.2,SrO3.7,BaO3,ZnO2.2,Cl-1.2,SO4 2-1.3
实施例3
Li2O 3.2,Al2O3 17,SiO2 40.7,TiO20.9,ZrO20.7,P2O57,F- 1.7,CeO2 1.7,B2O32.5,Na2O2,K2O1.7,MgO2.2,CaO5.2,SrO1.6,BaO1.9,ZnO8.2,Cl-0.8,SO4 2- 1
实施例4
Li2O 3,Al2O3 17,SiO2 45,TiO23,ZrO22.7,P2O56,F-2.5,CeO23,B2O34,Na2O 2,K2O2.5,MgO3.5,CaO1,SrO0.5,ZnO2.5,Cl- 0.8,SO4 2- 1
使用如下温度进行制备:(1)将玻璃料在1300℃温度下熔化并高温澄清;(2)将熔化好的玻璃液水淬并磨成粉;(3)将玻璃粉600℃热处理1小时;(4)700℃核化2h后,800℃晶化4小时;(5)降温冷却。在表1中显示实施例的基本物性。
表1:实施例基本物性表
Claims (3)
1.二氧化硅绝缘电缆连接用抗辐射微晶玻璃及制备方法,该材料以锂铝硅酸盐(LAS)为的抗辐射低膨胀微晶玻璃,其配合比按重量百分比的组合为:
Li2O2.5-8.5,Al2O316.2-26,SiO240-71.8,TiO20.8-4.6,ZrO20.6-3.7,P2O51.3-7,F-0.7-3.1,CeO20.7-3.9,B2O31.8-6.9,Na2O0.5-3.5,K2O0.4-3,MgO0.6-4.5,CaO0.2-5.2,SrO0-3.7,BaO0-3,ZnO1.9-8.2,Cl-0-1.2,SO4 2-0-1.3。
2.根据权利要求1所述的二氧化硅绝缘电缆连接用抗辐射微晶玻璃及制备方法,其具有适应的热膨胀0.3-1.2·10-6 /K。
3.根据权利要求1所述的二氧化硅绝缘电缆连接用抗辐射微晶玻璃及制备方法,其特征在于制造方法步骤如下:(1)将玻璃料在1200-1350℃温度下高温熔融并澄清;(2)将熔化好的玻璃液水淬并磨成粉;(3)将玻璃粉填充在二氧化硅绝缘电缆的连接部位,热处理温度为590-620℃,退火时间为1-1.5小时;(4)680-730℃核化处理1-5h;760-850℃晶化处理3-9h;(5)降温冷却。
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CN111072276A (zh) * | 2019-12-25 | 2020-04-28 | 温州市康尔微晶器皿有限公司 | 含复合澄清剂的锂铝硅微晶玻璃及其制备方法 |
CN116553833A (zh) * | 2023-03-23 | 2023-08-08 | 成都光明光电有限责任公司 | 一种低膨胀微晶玻璃及其制备方法 |
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CN105948516A (zh) * | 2016-06-03 | 2016-09-21 | 秦皇岛星箭特种玻璃有限公司 | 抗辐射锂铝硅系低膨胀视窗玻璃及其加工工艺 |
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CN105948516A (zh) * | 2016-06-03 | 2016-09-21 | 秦皇岛星箭特种玻璃有限公司 | 抗辐射锂铝硅系低膨胀视窗玻璃及其加工工艺 |
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CN111072276A (zh) * | 2019-12-25 | 2020-04-28 | 温州市康尔微晶器皿有限公司 | 含复合澄清剂的锂铝硅微晶玻璃及其制备方法 |
CN111072276B (zh) * | 2019-12-25 | 2022-05-03 | 温州市康尔微晶器皿有限公司 | 含复合澄清剂的锂铝硅微晶玻璃及其制备方法 |
CN116553833A (zh) * | 2023-03-23 | 2023-08-08 | 成都光明光电有限责任公司 | 一种低膨胀微晶玻璃及其制备方法 |
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