CN111635226B - 一种低介电常数陶瓷材料及其制备方法 - Google Patents

一种低介电常数陶瓷材料及其制备方法 Download PDF

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CN111635226B
CN111635226B CN202010598569.8A CN202010598569A CN111635226B CN 111635226 B CN111635226 B CN 111635226B CN 202010598569 A CN202010598569 A CN 202010598569A CN 111635226 B CN111635226 B CN 111635226B
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张军志
杨和成
罗昌宸
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XIAMEN SONGYUAN ELECTRONICS CO Ltd
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Abstract

本发明提供一种低介电常数陶瓷材料，涉及信息功能材料领域。该陶瓷材料包括主材与改性添加物。主材的化学式为ZnxSiO4·y(Al2O3·0.05TiO2)，其中1.2<x<2.5，0<y<0.25；所述主材在所述低介电常数陶瓷材料中所占的质量分数为97～99wt％；所述改性添加物在所述低介电常数陶瓷材料中所占的质量分数为1～3wt％。改性添加物选自BaCO3、SrCO3、Nb2O5、Ce2O3、NiO、Mg(OH)2、CaCO3、ZrO2和TiO2中的一种或几种。本发明的陶瓷材料是一种无铅环保型材料，采用固相合成方法合成主材成分，掺杂改性添加物，经过合理设计配方，优化合成工艺，制备出平均粒径为0.5‑1.0um粉体，利用该粉体制作电子陶瓷器件可在1240～1320℃的温度范围内烧结成瓷，其室温介电常数ε介于4.5～7之间，品质因数Qf值≥40000GHz，温度系数τf(‑40～85℃)：±20ppm/℃。

Description

一种低介电常数陶瓷材料及其制备方法
技术领域
本发明涉及信息功能材料领域，且特别涉及一种低介电常数陶瓷材料及其制备方法。
背景技术
微波介质陶瓷材料是近年来迅速发展起来的一类新型功能陶瓷材料。它具有低介电损耗、高介电常数ε及介电常数温度系数τf稳定等特点。它是介质谐振器、滤波器、振荡器、双工器、天线、介质基板等在内的新型微波电路和器件的核心基础材料，在现代微波通信和卫星导航系统和设备中有广泛的应用。随着移动通信和雷达技术的进步，微波电子元器件逐渐向高频方向发展，低介电常数的微波介质陶瓷材料越来越成为研究热点。但目前的微波介质陶瓷材料的介电常数均较高，或者介电常数较低但谐振频率温度系数却较高，性能不稳定。
发明内容
本发明的目的在于提供一种低介电常数陶瓷材料及其制备方法，以满足微波器件对其使用材料的低介电常数、低谐振频率温度系数的需求。
本发明采用以下方案来实现目的。
本发明提供一种低介电常数陶瓷材料，包括主材和改性添加物，所述主材的化学式为ZnxSiO4·y(Al2O3·0.05TiO2)，其中1.2<x<2.5，0<y<0.25；所述主材在所述低介电常数陶瓷材料中所占的质量分数为97～99wt％；所述改性添加物在所述低介电常数陶瓷材料中所占的质量分数为1～3wt％。
所述改性添加物选自BaCO3、SrCO3、Nb2O5、Ce2O3、NiO、Mg(OH)2、CaCO3、ZrO2和TiO2中的一种或几种。
进一步的，各个所述改性添加物在所述低介电常数陶瓷材料中所占的质量分数范围是：BaCO3为0～0.1％，SrCO3为0～0.3％，Nb2O5为0.3～1.5％，Ce2O3为0～0.2％，NiO为0～0.1％，Mg(OH)2为0～0.1％，CaCO3为0～0.8％，ZrO2为0～0.1％，TiO2为0.4～1.6％。
本发明还提供一种如上所述的低介电常数陶瓷材料的制备方法，包括以下步骤：
S1，固相法合成ZnxSiO4：将氧化锌、二氧化硅按配比置于球磨机中，加水混合均匀，进行湿法球磨，再在空气气氛中950℃～1150℃的温度范围煅烧2～4小时，得到ZnxSiO4；
S2，固相法合成Al2O3·0.05TiO2：将氧化铝及二氧化钛按配比置于球磨机中，加水混合均匀，进行湿法球磨，再在空气气氛中1250℃～1350℃的温度范围煅烧1～2小时，得到Al2O3·0.05TiO2；
S3，将步骤S1获得的ZnxSiO4、步骤S2获得的Al2O3·0.05TiO2以及改性添加物按配方要求一并置于球磨机中，加水进行湿法球磨，经过均匀化处理，然后把球磨好的物料进行干燥，获得粉末态的所述低介电常数陶瓷材料。
进一步的，步骤S3中，球磨后的物料粒径为0.5-1.0um。
进一步的，所述的制备方法，还包括以下步骤：
S4，在步骤S3得到的粉末态的所述低介电常数陶瓷材料中加入粘合剂、增塑剂、分散剂等，球磨1～2小时，获得浆料，再干燥后获得粉料，将粉料压制成生坯；
S5，排胶：将生坯置于500℃～650℃中，保温16～32小时，得到坯体；
S6，烧结：排胶后的坯体，在空气气氛中，1240～1320℃内保温3～5小时；
S7，退火：烧结后，在950℃～1050℃范围内，保温2～3小时，得到成型的低介电常数陶瓷材料。
进一步的，步骤S4中，所述粘合剂为聚乙烯醇，所述增塑剂为聚乙二醇，所述分散剂为羧酸铵盐。
进一步的，步骤S5的排胶过程，升温速度小于10℃/小时。
进一步的，步骤S6的烧结过程，升温速度为150℃～200℃/小时。
根据上述制备方法得到成型的低介电常数陶瓷材料，其室温介电常数介于4.5～7，温度系数τf(-40～85℃)：±20ppm/℃，Qf值≥40000GHz。
ZnxSiO4陶瓷在微波频段内具有优异的介电性能，其介电常数约为6.5，并随着SiO2量的增加而变小，Qf值约220000，但其谐振频率温度系数为-60ppm/℃，影响了它的实际应用。Al2O3·0.05TiO2陶瓷介电常数约为10，Qf值约为150000，将两者材料按一定比例进行混合，并添加一定量的辅助材料，可获得一种低介电常数，温度系数在±20ppm/℃以内的具有良好性能的低介电常数陶瓷材料。
本发明的有益效果是：将ZnxSiO4、Al2O3·0.05TiO2以及改性添加物结合，制备出材料均匀性好，满足微波器件要求的粉末态的低介电常数陶瓷材料，其化学式为ZnxSiO4·y(Al2O3·0.05TiO2)，其中1.2<x<2.5，0<y<0.25。该粉末态的低介电常数陶瓷材料在1240-1320℃温度中烧结后得到具有低介电常数的陶瓷材料。该陶瓷材料通过调整原材料合成的配比可形成室温介电常数介于4.5～7之间，Qf值≥40000GHz，温度系数τf(-40～85℃)：±20ppm/℃，满足微波器件的微波性能要求。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本发明提供一种低介电常数陶瓷材料，包括主材和改性添加物，所述主材的化学式为ZnxSiO4·y(Al2O3·0.05TiO2)，其中1.2<x<2.5，0<y<0.25；所述主材在所述低介电常数陶瓷材料中所占的质量分数为97～99wt％；所述改性添加物在所述低介电常数陶瓷材料中所占的质量分数为1～3wt％。
所述改性添加物选自BaCO3、SrCO3、Nb2O5、Ce2O3、NiO、Mg(OH)2、CaCO3、ZrO2和TiO2中的一种或几种。
优选地，各个所述改性添加物在所述低介电常数陶瓷材料中所占的质量分数范围是：BaCO3为0～0.1％，SrCO3为0～0.3％，Nb2O5为0.3～1.5％，Ce2O3为0～0.2％，NiO为0～0.1％，Mg(OH)2为0～0.1％，CaCO3为0～0.8％，ZrO2为0～0.1％，TiO2为0.4～1.6％。
本发明还提供一种如上所述的低介电常数陶瓷材料的制备方法，包括以下步骤：
①制备主材其中之一的ZnxSiO4粉末：其中1.2<x<2.5，按化合物中Zn和Si元素的比例，称量相应质量高纯、超细的ZnO和SiO2，置于球磨机中，按质量比为固体物料：水＝1：(1.0～2.0)的比例加入水进行球磨混合均匀，砂磨处理后，用喷雾干燥塔或其他方法进行干燥，在空气气氛炉中950℃～1150℃的温度范围煅烧2～4小时，最终得到ZnxSiO4粉末。
②制备主材中另一成分的Al2O3·0.05TiO2粉末：把高纯、超细的Al2O3及TiO2按1:0.05的摩尔比称量好，置于球磨机中，按质量比为固体物料：去离子水＝1：(1.0～2.0)的比例加入水进行球磨混合均匀，达到一定粒径后，用喷雾干燥塔或其他方法进行干燥，在空气气氛炉中1250℃～1350℃的温度范围煅烧1～2小时，最终得到Al2O3·0.05TiO2粉末。
③制备配方粉末：把①、②中获得的两种主材成分ZnxSiO4与Al2O3·0.05TiO2，以及各种改性添加物BaCO3、SrCO3、Nb2O5、Ce2O3、NiO、Mg(OH)2、CaCO3、ZrO2和TiO2中的一种或几种，按所述低介电常数陶瓷材料的组成来配方称重，置于球磨机中，按质量比为固体物料：水＝1：(0.6～1.0)的比例加入水进行湿法砂磨，要求物料混合均匀，使砂磨后的粉体用激光粒度仪测试平均颗粒径在0.50-1.0um。球磨完毕后用喷雾干燥塔或其他方法进行干燥，得到本发明粉末态的低介电常数陶瓷材料。
进一步地，本发明的低介电常数陶瓷材料的制备方法还包括以下步骤：
④在粉末态的低介电常数陶瓷材料中，加入适当的粘合剂、增塑剂、分散剂等，用氧化锆球为磨介在球磨罐中球磨1～2小时，获得浆料，进行离心喷雾干燥，获得流动性良好的球形颗粒粉料。所述粘合剂可选用聚乙烯醇，所述增塑剂可选用聚乙二醇，所述分散剂可选用羧酸铵盐。
⑤将球形颗粒粉料，压制成生坯器件。
⑥将生坯器件置于500℃～650℃的温度范围内，保温16～32小时，排除生坯片中的有机物，得到坯体，整个排胶过程的升温速度要求小于10℃/小时。
⑦烧结：将排胶好的坯体，在空气中进行烧结，以150℃～200℃/小时的升温速度升温到1240～1320℃，保温时间为3～5小时。烧结温度优选1280℃。烧结能使陶瓷坯体中的粉粒晶界移动，气孔逐步排除，坯体收缩成为具有一定强度的致密陶瓷体。
⑧退火处理：高温烧结后，炉温在950℃～1050℃范围内，保温2～3小时，得到成型的低介电常数陶瓷材料。退火可以减小坯体内部应力，细化晶粒，弥合微裂纹，改善材料的组织结构，提高陶瓷的力学性能。
⑨器件测试：采用安捷伦网分，在频率10-11GHz下进行微波性能测试。
根据测试结果：上述得到成型的低介电常数陶瓷材料，其温介电常数介于4.5～7，温度系数τf(-40～85℃)：±20ppm/℃，Qf值≥40000GHz。
实施例
本实施例提供一种低介电常数陶瓷材料及其制备方法，本发明的方案不局限于实施例。
(1)按照ZnxSiO4组成，其中1.2<x<2.5，如表1所示的原料配方，称取三组相应质量的ZnO和SiO2，依次置于球磨机中，按质量比为每组固体物料：去离子水＝1：1.5的比例加入去离子水进行湿法球磨，球磨后用喷雾干燥塔进行干燥，在空气炉中1100℃煅烧3小时。各组样品中：ZS1中，x＝1.3；ZS2中，x＝2；ZS3中，x＝2.4。
表1ZnxSiO4实施例配方
Figure BDA0002558303720000061
(2)按照Al2O3·0.05TiO2组成，将Al2O3及TiO2按1:0.05的摩尔比配置于球磨机中，按质量比为固体物料：去离子水＝1：1.5的比例加入去离子水进行湿法球磨，混合均匀，用喷雾干燥塔进行干燥，在空气炉中1300℃的温度煅烧1.5小时。
(3)按照ZnxSiO4·y(Al2O3·0.05TiO2)，其中1.2<x<2.5，0<y<0.25的组成，按表2的试样化学组成，称取(1)得到的ZnxSiO4、(2)得到的Al2O3·0.05TiO2以及各种改性添加物，分组置于球磨机中，每组试样按质量比为固体物料：去离子水＝1：0.8的比例加入去离子水进行湿法砂磨，要求物料混合均匀，使砂磨后的粉体用激光粒度仪测试平均颗粒径在0.50-1.0um。砂磨完毕后，加入分别占总质量0.5～3％的聚乙烯醇粘合剂、聚乙二醇增塑剂、羧酸铵盐分散剂，分散均匀后，用喷雾干燥塔进行干燥，干燥后粉体压制成圆柱型生坯圆片；然后设定温度曲线，先置于600℃中保温24小时以进行排胶，整个排胶过程的升温速度为10℃/小时；再以200℃/小时的升温速度升温至1240～1320℃保温3小时进行烧结；高温烧结后，在1000℃中保温2.5小时，得到成型的低介电常数陶瓷材料圆片。
表2低介电常数陶瓷材料试样化学组成
Figure BDA0002558303720000071
对成型的低介电常数陶瓷材料进行微波性能测试，测试结果列于表3中。表3的1～15号试样取自表2中的1～15号试样，且相同编号一一对应。
表3低介电常数陶瓷材料试样烧结制成圆片各项电性能测试结果
Figure BDA0002558303720000072
Figure BDA0002558303720000081
从表3可以看出，经过上述过程制成的陶瓷材料，可以在1240℃～1320℃的温度范围内。通过调整材料合成的配比可形成室温介电常数介于4.5～7，温度系数τf(-40～85℃)：±20ppm/℃，Qf值≥40000GHz，微波性能参数连续可调的系统陶瓷材料，可满足微波器件的低介电常数和窄波动范围的温度系数τf(-40～85℃)的应用要求。
以上所描述的实施例是本发明的一部分实施例，而不是全部的实施例。本发明的实施例的详细描述并非旨在限制要求保护的范围，而是仅仅表示本发明的选定实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。

Claims (5)

1.一种低介电常数陶瓷材料的制备方法，其特征在于，所述低介电常数陶瓷材料包括主材和改性添加物，所述主材的化学式为ZnxSiO4·y(Al2O3·0.05TiO2)，其中1.2<x<2.5，0<y<0.25；所述主材在所述低介电常数陶瓷材料中所占的质量分数为97～99wt％；所述改性添加物在所述低介电常数陶瓷材料中所占的质量分数为1～3wt％；
其中，所述改性添加物选自BaCO3、SrCO3、Nb2O5、Ce2O3、NiO、Mg(OH)2、CaCO3、ZrO2和TiO2中的一种或几种；
其中，各个所述改性添加物在所述低介电常数陶瓷材料中所占的质量分数范围是：BaCO3为0～0.1％，SrCO3为0～0.3％，Nb2O5为0.3～1.5％，Ce2O3为0～0.2％，NiO为0～0.1％，Mg(OH)2为0～0.1％，CaCO3为0～0.8％，ZrO2为0～0.1％，TiO2为0.4～1.6％；
其中，所述低介电常数陶瓷材料的制备包括以下步骤：
S1，固相法合成ZnxSiO4：将氧化锌、二氧化硅按配比置于球磨机中，加水混合均匀，进行湿法球磨，再在空气气氛中950℃～1150℃的温度范围煅烧2～4小时，得到ZnxSiO4；
S2，固相法合成Al2O3·0.05TiO2：将氧化铝及二氧化钛按配比置于球磨机中，加水混合均匀，进行湿法球磨，再在空气气氛中1250℃～1350℃的温度范围煅烧1～2小时，得到Al2O3·0.05TiO2；
S3，将步骤S1获得的ZnxSiO4、步骤S2获得的Al2O3·0.05TiO2以及改性添加物按配方要求一并置于球磨机中，加水进行湿法球磨，经过均匀化处理，然后把球磨好的物料进行干燥，获得粉末态的所述低介电常数陶瓷材料；
S4，在步骤S3得到的粉末态的所述低介电常数陶瓷材料中加入粘合剂、增塑剂、分散剂，球磨1～2小时，获得浆料，再干燥后获得粉料，将粉料压制成生坯；
S5，排胶：将生坯置于500℃～650℃中，保温16～32小时，得到坯体；
S6，烧结：排胶后的坯体，在空气气氛中，1240～1290℃内保温3～5小时；
S7，退火：烧结后，在950℃～1050℃范围内，保温2～3小时，得到成型的低介电常数陶瓷材料。
2.根据权利要求1所述的低介电常数陶瓷材料的制备方法，其特征在于，步骤S3中，球磨后的物料粒径为0.5-1.0um。
3.根据权利要求1所述的低介电常数陶瓷材料的制备方法，其特征在于，步骤S4中，所述粘合剂为聚乙烯醇，所述增塑剂为聚乙二醇，所述分散剂为羧酸铵盐。
4.根据权利要求1所述的低介电常数陶瓷材料的制备方法，其特征在于，步骤S5的排胶过程，升温速度小于10℃/小时。
5.根据权利要求1所述的低介电常数陶瓷材料的制备方法，其特征在于，步骤S6的烧结过程，升温速度为150℃～200℃/小时。
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