CN114394827A - 一种低介电常数硅酸盐微波介质陶瓷及其制备方法 - Google Patents

一种低介电常数硅酸盐微波介质陶瓷及其制备方法 Download PDF

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CN114394827A
CN114394827A CN202111621061.6A CN202111621061A CN114394827A CN 114394827 A CN114394827 A CN 114394827A CN 202111621061 A CN202111621061 A CN 202111621061A CN 114394827 A CN114394827 A CN 114394827A
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吕学鹏
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Abstract

本发明公开了一种低介电常数硅酸盐微波介质陶瓷及其制备方法，该陶瓷的化学表达式为Ca1‑x‑y/2AxMg1‑y/2B y Si3O9‑zBa5Si8O21，其中A=Sr、Ba；B=Zn、Co、Mn；0.02≤x≤0.10；0.10≤y≤0.50；0.30≤z≤0.50。该陶瓷材料制备工艺依次如下：合成Ca1‑x‑y/2AxMg1‑y/2B y Si3O9粉体、合成Ba5Si8O21粉体、复合粉末配制、球磨、DCS快速烧结成瓷。本发明一方面通过微量Sr离子取代提高CaMgSi3O9晶相的Qf值，另一方面通过Zn或Co获Mn离子共取代A、B位调控CaMgSi3O9结构的层状结构，进而调控其Qf值和τ f 值。此外，本发明制备所得Ca1‑x‑y/2AxMg1‑y/2B y Si3O9‑zBa5Si8O21陶瓷材料的介电常数为5.5~8.2，Qf值为28500~76450GHz，τ f 值在±15 ppm/℃以内，且制备工艺简单，制备周期短，工艺稳定好，抗还原特性好，可耐还原气氛烧结而使用贱金属内电极，适合制造温度补偿型MLCC电容器。

Description

一种低介电常数硅酸盐微波介质陶瓷及其制备方法
技术领域
本发明属于微波介质陶瓷领域，尤其涉及一种低介电常数硅酸盐微波介质陶瓷及其制备方法。
背景技术
随着通信技术逐渐向毫米波方向发展，MLCC对电介质材料的微波介电性能要求越来越高，要求其具有低的介电常数(εr<10)以提高器件的信息传输速率、较低的高频介电损耗(tanδ<0.001，f=10GHz)以增强其选频性和降低能耗、近零的谐振频率温度系数(τ f ~±10ppm/℃)来保证谐振与传输时信号的工作稳定性。目前，国内外低介电常数材料的研究工作主要集中在Al2O3、Mg2SiO4、AWO4（A=Ca, Sr, Ba）、磷酸盐和R2BaCuO5（R=Y, Sm, Yb）等材料体系。这些材料体系存在着烧结温度范围窄，微观组织不够致密，相控制困难，低介电常数、高品质因数、近零温度系数难以得到统一，抗还原性较差等各种问题，限制了其在高频元器件中的实际应用。考虑到环境友好和低成本等因素，低介电常数硅酸盐微波介质陶瓷在MLCC元器件制备方面具有重要的研究意义。
辉石结构硅酸盐化合物（ABSi2O6）具有低廉的原料成本、良好的生物相容性、良好的光致发光性能和优异的微波介电性能成为生物材料、稀土无机发光材料和电介质材料的研究热点。Zhang等（Sun H, Zhang Q, Yang H, et al. (Ca1−xMgx)SiO3: A low-permittivity microwave dielectric ceramic system. Materials Science andEngineering B, 2007, 138: 46-50.）研究发现辉石结构的CaMgSi2O6陶瓷经1290℃烧结后具有优异的微波介电性能：ε r = 7.46, Q×f = 59638 GHz, τ f = -46 ppm/℃，其晶体结构为单斜辉石结构，空间群为C2/c。CaMgSi2O6陶瓷具有低的介电常数和介电损耗，但其烧结温度范围窄，烧结成瓷较难，限制了其实际应用。虽然通过Co2+、Ni2+、Al3+等离子置换可以降低材料的介电损耗，但对其烧结特性的改善非常有限。我们前期研究发现CaMgSi3O9化合物同样具有层状辉石结构，且其烧结温度范围相对较宽，成瓷温度从1150℃到1300℃，可以极大地降低陶瓷的烧结难度，但其谐振频率温度系数负的较大，需要调节近零。基于上述背景，本发明提出了一种低介硅基微波介质陶瓷（Ca1-x-y/2AxMg1-y/2B y Si3O9-zBa5Si8O21）及其制备方法。
发明内容
本发明的目的在于克服辉石结构硅酸盐化合物烧结温度范围窄、成瓷较难、谐振频率温度系数负的较大的问题，提供一种低介电常数硅酸盐微波介质陶瓷及其制备方法，该金属陶瓷的主晶相为辉石结构Ca1-x-y/2AxMg1-y/2B y Si3O9固溶体相和Ba5Si8O21相，具有低成本、低介电常数、低介电损耗、温度稳定型好、优异的抗还原性，且烧结温度范围宽、制备工艺稳定。
为解决现有技术问题，本发明公开了一种低介电常数硅酸盐微波介质陶瓷，该陶瓷的化学表达式为Ca1-x-y/2AxMg1-y/2B y Si3O9-zBa5Si8O21，其中A=Sr、Ba；B=Zn、Co、Mn；0.02≤x≤0.10；0.10≤y ≤0.50；0.30≤ z ≤0.50。
本发明还公开了一种低介电常数硅酸盐微波介质陶瓷的制备方法，其特征在于包括如下步骤：
步骤一、合成Ca1-x-y/2AxMg1-y/2B y Si3O9粉体：以CaCO3、BaCO3、SrCO3、Mg(OH)2·4MgCO3·5H2O、ZnO、CoO、MnO和SiO2粉末为原料，按照化学表达式为Ca1-x-y/2AxMg1- y/2B y Si3O9（A=Sr、Ba；B=Zn、Co、Mn；0.02≤x ≤0.10；0.10≤y ≤0.50）进行称量配料形成混合粉末，湿法球磨12小时，干燥后置于氧化铝坩埚，在高温箱式电炉中1050~1150℃预烧2~6小时，得到Ca1-x-y/2AxMg1-y/2B y Si3O9粉体；
步骤二、合成Ba5Si8O21粉体：以BaCO3和SiO2粉末为原料，按照化学表达式为Ba5Si8O21进行称量配料形成混合粉末，湿法球磨12小时，干燥后置于氧化铝坩埚，在高温箱式电炉中1050~1150℃预烧3~5小时，得到Ba5Si8O21粉体；
步骤三、复合粉末配制：将上述合成制得的Ca1-x-y/2AxMg1- y/2B y Si3O9粉体和Ba5Si8O21粉体按照化学组成表达式Ca1-x-y/2AxMg1-y/2B y Si3O9-zBa5Si8O21（0.30≤ z ≤0.50）配制复合粉末；
步骤四、球磨：将配置好的复合粉末置于行星式球磨机中进行球磨，球磨介质为无水乙醇，磨球材质为二氧化锆，混合料、磨球与无水乙醇的质量比为1：5：1.2，球磨时间12~24小时，球磨机转速为250~350 rpm；
步骤五、DCS快速烧结：将球磨料浆烘干后置于石墨模具中，在DCS快速烧结炉中烧结成瓷，烧结温度1100~1200℃，保温时间5~15min，升温速率100~150℃/min。
本发明具有的有益效果：
（1）本发明中Sr离子微量取代可以调控CaMgSi3O9晶相的晶格畸变和原子堆积密度，提高其Qf值，进而保证电子元器件良好的信号选择性。
（2）本发明中Zn或Co获Mn离子取代时，该离子一方面取代Mg进入[MgO6]八面体的中心位置，另一方面取代Ca离子进入配位多面体的中心位置，进而对CaMgSi3O9结构中层状结构进行调控，进而调控其Qf值和τ f 值。
（3）本发明采用DCS快速烧结制备陶瓷材料，该方法制备工艺简单、制备周期短、工艺稳定好、烧结温度相对较低，且无需造粒、压制成型等工序，在MLCC叠层陶瓷的快速烧结方面具有较大的工业应用价值。
（4）本发明通过Ba5Si8O21调节Ca1-x-y/2AxMg1-y/2B y Si3O9陶瓷的谐振频率温度系数近零，一方面可以保证电子元器件的工作稳定性，另一方面可以保证陶瓷材料的抗还原特性，可耐还原气氛烧结而使用贱金属内电极，因而可降低MLCC电容器的制造成本。
（5）本发明制备所得Ca1-x-y/2AxMg1-y/2B y Si3O9-zBa5Si8O21陶瓷材料的介电常数为5.5~8.2，Qf值为28500~76450GHz，τ f 值在±15 ppm/℃以内，且不含铅、镉、 铋等有毒成分，适合制造温度补偿型MLCC电容器。
附图说明
图1是本发明实施例三制得Ca0.84Sr0.06Mg0.90Zn0.20Si3O9-zBa5Si8O21（0.30≤ z ≤0.50）陶瓷的XRD图谱。
图2是本发明实施例三制得Ca0.84Sr0.06Mg0.90Zn0.20Si3O9-zBa5Si8O21（0.30≤ z ≤0.50）陶瓷的SEM图。
具体实施方式
下面对本发明作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。
表1是4种成分配方的混合料末。采用不同的工艺参数将其制备成低介电常数硅酸盐微波介质陶瓷，并分别测定其微波介电性能。
表1 四种成分配方
Figure 561657DEST_PATH_IMAGE001
实施例一
步骤一、合成Ca1-x-y/2AxMg1-y/2B y Si3O9粉体：以CaCO3、BaCO3、SrCO3、Mg(OH)2·4MgCO3·5H2O、ZnO、CoO、MnO和SiO2粉末为原料，按照化学表达式为Ca1-x-y/2AxMg1- y/2B y Si3O9（A=Sr、Ba；B=Zn、Co、Mn；0.02≤x ≤0.10；0.10≤y ≤0.50）进行称量配料形成混合粉末，湿法球磨12小时，干燥后置于氧化铝坩埚，在高温箱式电炉中1050℃预烧2小时，得到Ca1-x-y/ 2AxMg1-y/2B y Si3O9粉体；
步骤二、合成Ba5Si8O21粉体：以BaCO3和SiO2粉末为原料，按照化学表达式为Ba5Si8O21进行称量配料形成混合粉末，湿法球磨12小时，干燥后置于氧化铝坩埚，在高温箱式电炉中1050℃预烧3小时，得到Ba5Si8O21粉体；
步骤三、复合粉末配制：将上述合成制得的Ca1-x-y/2AxMg1- y/2B y Si3O9粉体和Ba5Si8O21粉体按照化学组成表达式Ca1-x-y/2AxMg1-y/2B y Si3O9-zBa5Si8O21（0.30≤ z ≤0.50）配制复合粉末；
步骤四、球磨：将配置好的复合粉末置于行星式球磨机中进行球磨，球磨介质为无水乙醇，磨球材质为二氧化锆，混合料、磨球与无水乙醇的质量比为1：5：1.2，球磨时间12小时，球磨机转速为350 rpm；
步骤五、DCS快速烧结：将球磨料浆烘干后置于石墨模具中，在DCS快速烧结炉中烧结成瓷，烧结温度1100℃，保温时间15min，升温速率100℃/min。
对本实施例获得的材料进行性能检测，检测结果如表2所示。
表2 采用实施例一制备出陶瓷材料的介电性能
Figure 433798DEST_PATH_IMAGE002
实施例二
步骤一、合成Ca1-x-y/2AxMg1-y/2B y Si3O9粉体：以CaCO3、BaCO3、SrCO3、Mg(OH)2·4MgCO3·5H2O、ZnO、CoO、MnO和SiO2粉末为原料，按照化学表达式为Ca1-x-y/2AxMg1- y/2B y Si3O9（A=Sr、Ba；B=Zn、Co、Mn；0.02≤x ≤0.10；0.10≤y ≤0.50）进行称量配料形成混合粉末，湿法球磨12小时，干燥后置于氧化铝坩埚，在高温箱式电炉中11150℃预烧6小时，得到Ca1-x-y/2AxMg1-y/2B y Si3O9粉体；
步骤二、合成Ba5Si8O21粉体：以BaCO3和SiO2粉末为原料，按照化学表达式为Ba5Si8O21进行称量配料形成混合粉末，湿法球磨12小时，干燥后置于氧化铝坩埚，在高温箱式电炉中1150℃预烧5小时，得到Ba5Si8O21粉体；
步骤三、复合粉末配制：将上述合成制得的Ca1-x-y/2AxMg1- y/2B y Si3O9粉体和Ba5Si8O21粉体按照化学组成表达式Ca1-x-y/2AxMg1-y/2B y Si3O9-zBa5Si8O21（0.30≤ z ≤0.50）配制复合粉末；
步骤四、球磨：将配置好的复合粉末置于行星式球磨机中进行球磨，球磨介质为无水乙醇，磨球材质为二氧化锆，混合料、磨球与无水乙醇的质量比为1：5：1.2，球磨时间24小时，球磨机转速为350 rpm；
步骤五、DCS快速烧结：将球磨料浆烘干后置于石墨模具中，在DCS快速烧结炉中烧结成瓷，烧结温度1200℃，保温时间5min，升温速率150℃/min。
对本实施例获得的材料进行性能检测，检测结果如表3所示。
表3 采用实施例二制备出陶瓷材料的介电性能
Figure 896004DEST_PATH_IMAGE004
实施例三
步骤一、合成Ca1-x-y/2AxMg1-y/2B y Si3O9粉体：以CaCO3、BaCO3、SrCO3、Mg(OH)2·4MgCO3·5H2O、ZnO、CoO、MnO和SiO2粉末为原料，按照化学表达式为Ca1-x-y/2AxMg1- y/2B y Si3O9（A=Sr、Ba；B=Zn、Co、Mn；0.02≤x ≤0.10；0.10≤y ≤0.50）进行称量配料形成混合粉末，湿法球磨12小时，干燥后置于氧化铝坩埚，在高温箱式电炉中1100℃预烧4小时，得到Ca1-x-y/ 2AxMg1-y/2B y Si3O9粉体；
步骤二、合成Ba5Si8O21粉体：以BaCO3和SiO2粉末为原料，按照化学表达式为Ba5Si8O21进行称量配料形成混合粉末，湿法球磨12小时，干燥后置于氧化铝坩埚，在高温箱式电炉中110℃预烧4小时，得到Ba5Si8O21粉体；
步骤三、复合粉末配制：将上述合成制得的Ca1-x-y/2AxMg1- y/2B y Si3O9粉体和Ba5Si8O21粉体按照化学组成表达式Ca1-x-y/2AxMg1-y/2B y Si3O9-zBa5Si8O21（0.30≤ z ≤0.50）配制复合粉末；
步骤四、球磨：将配置好的复合粉末置于行星式球磨机中进行球磨，球磨介质为无水乙醇，磨球材质为二氧化锆，混合料、磨球与无水乙醇的质量比为1：5：1.2，球磨时间20小时，球磨机转速为300rpm；
步骤五、DCS快速烧结：将球磨料浆烘干后置于石墨模具中，在DCS快速烧结炉中烧结成瓷，烧结温度1150℃，保温时间10min，升温速率125℃/min。
对本实施例获得的材料进行性能检测，检测结果如表4所示。
表4 采用实施例三制备出陶瓷材料的介电性能
Figure 853596DEST_PATH_IMAGE006
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变形，这些改进和变形也应视为本发明的保护范围。

Claims (6)

1.一种低介电常数硅酸盐微波介质陶瓷，其特征在于，该陶瓷的化学表达式为Ca1-x-y/ 2AxMg1-y/2B y Si3O9-zBa5Si8O21，其中A=Sr、Ba；B=Zn、Co、Mn；0.02≤x ≤0.10；0.10≤y ≤0.50；0.30≤ z ≤0.50。
2.一种低介电常数硅酸盐微波介质陶瓷的制备方法，其特征在于包括如下步骤：
步骤一、合成Ca1-x-y/2AxMg1-y/2B y Si3O9粉体：以CaCO3、BaCO3、SrCO3、Mg(OH)2·4MgCO3·5H2O、ZnO、CoO、MnO和SiO2粉末为原料，按照化学表达式为Ca1-x-y/2AxMg1- y/2B y Si3O9（A=Sr、Ba；B=Zn、Co、Mn；0.02≤x ≤0.10；0.10≤y ≤0.50）进行称量配料形成混合粉末，湿法球磨12小时，干燥后置于氧化铝坩埚，在高温箱式电炉中预烧得到Ca1-x-y/2AxMg1-y/2B y Si3O9粉体；
步骤二、合成Ba5Si8O21粉体：以BaCO3和SiO2粉末为原料，按照化学表达式为Ba5Si8O21进行称量配料形成混合粉末，湿法球磨12小时，干燥后置于氧化铝坩埚，在高温箱式电炉中预烧得到Ba5Si8O21粉体；
步骤三、复合粉末配制：将上述合成制得的Ca1-x-y/2AxMg1- y/2B y Si3O9粉体和Ba5Si8O21粉体按照化学组成表达式Ca1-x-y/2AxMg1-y/2B y Si3O9-zBa5Si8O21（0.30≤ z ≤0.50）配制复合粉末；
步骤四、球磨：将配置好的复合粉末置于行星式球磨机中进行球磨，球磨介质为无水乙醇，磨球材质为二氧化锆，混合料、磨球与无水乙醇的质量比为1：5：1.2，球磨时间12~24小时，球磨机转速为250~350 rpm；
步骤五、DCS快速烧结：将球磨料浆烘干后置于石墨模具中，在DCS快速烧结炉中烧结成瓷，烧结温度1100~1200℃，保温时间5~15min，升温速率100~150℃/min。
3.根据权利要求2所述的一种低介电常数硅酸盐微波介质陶瓷的制备方法，其特征在于步骤一中CaCO3、BaCO3、SrCO3、Mg(OH)2·4MgCO3·5H2O、ZnO、CoO、MnO和SiO2粉末的粒度为2~5μm，纯度≥99.5%。
4.根据权利要求2所述的一种低介电常数硅酸盐微波介质陶瓷的制备方法，其特征在于步骤一中Ca1-x-y/2AxMg1-y/2B y Si3O9粉体的预烧工艺为1050~1150℃保温2~6小时，升温速率为5℃/min。
5.根据权利要求2所述的一种低介电常数硅酸盐微波介质陶瓷的制备方法，其特征在于步骤二中BaCO3和SiO2粉末的粒度为2~5μm，纯度≥99.5%。
6.根据权利要求2所述的一种低介电常数硅酸盐微波介质陶瓷的制备方法，其特征在于步骤二中Ba5Si8O21粉体的预烧工艺为1050~1150℃保温3~5小时，升温速率为5℃/min。
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