CN112919894B - 一种频率稳定型低介微波介质陶瓷材料及其制备方法 - Google Patents

一种频率稳定型低介微波介质陶瓷材料及其制备方法 Download PDF

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CN112919894B
CN112919894B CN202110260060.7A CN202110260060A CN112919894B CN 112919894 B CN112919894 B CN 112919894B CN 202110260060 A CN202110260060 A CN 202110260060A CN 112919894 B CN112919894 B CN 112919894B
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ceramic material
deionized water
grinding
mixture
frequency
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CN112919894A (zh
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刘顺国
童建喜
刘强
黄丹
胥金华
史雪斌
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Jiaxing Glead Electronics Co ltd
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Jiaxing Glead Electronics Co ltd
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Priority to CN202110260060.7A priority Critical patent/CN112919894B/zh
Priority to JP2022536683A priority patent/JP7381761B2/ja
Priority to US17/779,133 priority patent/US20230416155A1/en
Priority to PCT/CN2021/084472 priority patent/WO2022188219A1/zh
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Abstract

本发明涉及一种频率稳定型低介微波介质陶瓷材料及其制备方法，所述材料由质量百分比为70％～90％的主相陶瓷材料A、10％～30％的副相陶瓷材料B和0～1.0％的氧化物助烧剂C组成。其中主相陶瓷材料A为MgxMeySiO2+x+y，副相陶瓷材料B组成为aRO‑bRe2O3‑cTiO2，R为Ca或Sr中的至少一种，Re2O3为Sm2O3、Nd2O3、Y2O3、Al2O3和La2O3中的至少两种，氧化物助烧剂C为MnO2、WO3和CeO2中的至少一种。本发明制备的微波介质陶瓷材料介电常数9.5～13.6，频率温度系数τf在‑16ppm/℃～13ppm/℃连续可调，具有较好的频率稳定性，适用于新一代移动通信和高频网络通讯等领域。

Description

一种频率稳定型低介微波介质陶瓷材料及其制备方法
技术领域
本发明属于材料科学技术领域，尤其涉及一种频率稳定型低介微波介质陶瓷材料及其制备方法。
背景技术
微波介质陶瓷是应用于微波频段电路中实现一种或多种功能的功能陶瓷材料，在现代通讯技术应用中起着重要作用，是制备介质谐振器、介质滤波器和介质波导滤波器等器件的关键材料。随着新一代移动通信和高频网络通讯对信号传输的低时延和可靠性要求越来越高，低介电常数且温度系数稳定性优良的微波介质陶瓷材料受到越来越多的关注。典型应用如5G基站中的滤波器，通常要求其-40℃～110℃的频率温度系数均在±5ppm/℃以内，从而保证器件在温差变化较大的环境中有较高的频率稳定性。
Mg2SiO4是一种性能优异的频率稳定型低介微波介质陶瓷材料，其εr＝6.8，Q×f＝270,000GHz，但是其τf为-70ppm/℃，通常需要通过掺杂或引入正τf的材料如CaTiO3来调节τf至近0方可应用于微波元器件制备。专利CN101863655公开了通过Ca取代Mg制备的Mg2SiO4和MgCaSiO4陶瓷，τf近0且可调，但Q×f值太低，仅为20000GHz左右。另一方面，Mg2SiO4陶瓷还有较高的热膨胀系数(～10ppm/℃左右)，可降低器件在温度变化环境中的开裂风险，提高了产品的可靠性，而同为低介材料的堇青石陶瓷热膨胀系数仅为2ppm/℃左右。
Ling Liu等在《Journal of Materials Science:Materials in Electronics》在2014年26卷1316-1321页发表的“Microstructures and microwave dielectricproperties of Mg2SiO4–Ca0.9Sr0.1TiO3 ceramics”一文中通过Sr2+取代Ca2+的Ca0.9Sr0.1TiO3将Mg2SiO4的τf调整至-3.62ppm/℃，同时获得较高的Q×f值。但实际应用中，由于简单钙钛矿结构的CaTiO3、SrTiO3或Ca 1-xSrxTiO3的温度系数线性度较差，相应产品在全温度范围(如-40℃～110℃)内频率温度系数难以同时满足τf≤±5ppm/℃的要求，相关器件频率稳定性较差，这限制了其在移动基站中的使用。
另一方面，由于烧结过程中Mg2+的Si4+扩散速度存在较大差异，极容易形成第二相MgSiO3或未完全反应的SiO2。由于MgSiO3的损耗远大于Mg2SiO4相，这严重恶化了Mg2SiO4陶瓷的介电性能。而过量的SiO2则容易在烧结过程中形成液相，导致晶粒异常长大，同样会恶化材料的介电性能和机械强度。专利CN101429015中公布了调整Mg/Si比例消除第二相的方法，但是烧结温度较高且未将τf调节至近0，材料应用易受限制。
发明内容
为了解决上述技术问题，本发明的第一个目的在于提供一种频率稳定型低介微波介质陶瓷材料，该材料具有较高的Q×f值，在较宽温度范围内具有较小的频率温度系数；本发明的第二个目的在于提供一种频率稳定型低介微波介质陶瓷材料的制备方法，该制备方法烧结工艺简单，可重复性好。
为了实现上述第一个发明的目的，本发明采用以下技术方案：
一种频率稳定型低介微波介质陶瓷材料，由质量百分比为70％～90％的主相陶瓷材料A、10％～30％的副相陶瓷材料B和0～1.0％的氧化物助烧剂C组成，且主相陶瓷材料A、副相陶瓷材料B和氧化物助烧剂C的质量百分比和为100％；其中主相陶瓷材料A符合化学式MgxMeySiO2+x+y，其中Me为Co或者Zn，副相陶瓷材料B组成符合aRO-bRe2O3-cTiO2，其中R为Ca或Sr中的至少一种，Re2O3为Sm2O3、Nd2O3、Y2O3、Al2O3和La2O3中的至少两种，氧化物助烧剂C为MnO2，MnCO3、WO3和CeO2中的至少一种。
作为优选方案：2.00≤x+y≤2.20，1.80≤x≤2.15，0≤y≤0.40。
作为优选方案：1.0≤a≤2.0，0.05≤b≤0.50，1.0≤c≤1.5。
作为进一步的优选方案：2.00≤x+y≤2.10，1.80≤x≤2.05，0.05≤y≤0.25。
作为进一步的优选方案：1.0≤a≤1.5，0.05≤b≤0.30，1.0≤c≤1.2。
作为优选方案：所述副相陶瓷材料B的化学式中的Re2O3为Al2O3和Sm2O3，或者Al2O3和Nd2O3，或者Al2O3和Y2O3，或者Al2O3和La2O3。
为了实现上述第二个发明的目的，本发明采用以下技术方案：
一种制备如上所述的频率稳定型低介微波介质陶瓷的制备方法，包括以下步骤：
1)主相陶瓷材料A合成：
按化学式MgxMeySiO2+x+y计量比称量原材料MgO、SiO2、ZnO、CoO进行混合，以去离子水为溶剂，球磨混合16～24h后烘干；将烘干后的混合料过40目筛网，装入氧化铝坩埚于1150℃～1300℃下煅烧2～4h合成主相粉料A，研磨并过40目筛网备用；
2)副相陶瓷材料B合成：
按化学式aRO-bRe2O3-cTiO2组成称量原材料CaCO3、SrCO3、Sm2O3、Nd2O3、Y2O3、Al2O3和La2O3进行混合，以去离子水为溶剂，球磨混合16～24h后烘干；然后过40目筛网，装入氧化铝坩埚于1100℃～1300℃下煅烧2～4h合成副相粉料B，研磨并过40目筛网备用；
3)按一定配比称量制备好的主相陶瓷材料A、副相陶瓷材料B和氧化物助烧剂C进行混合，以ZrO2球为磨介，按混合料与去离子水的重量比1：1.5～2加入去离子水，采用湿法混料12～18h后于120℃烘干，加入重量含量为1％～3％的聚乙烯醇粘合剂研磨造粒，过40目筛网后在80～120MPa压力下压制成直径20mm，厚度10mm的坯体，在空气气氛中于1300℃～1450℃烧结2～4h，即得到所述频率稳定型低介微波介质陶瓷材料。
对比现有技术，本发明具有如下优点：
1、通过对简单钙钛矿结构CaTiO3和SrTiO3进行改进处理，并调整陶瓷各组分的配比，优化了陶瓷材料全温度范围内的频率温度系数，从而保证器件在温差变化较大的环境中有较高的频率稳定性。
2、本发明通过Mg2SiO4的非化学计量比设计和A位Mg2+的取代消除了第二相MgSiO3以及SiO2相残余的问题，抑制晶粒的异常长大，具有较宽的烧结温度范围，氧化物助烧剂的引入则进一步降低了材料的烧结温度。本发明制备工艺简单，工艺可操作性和再现性好，微波介电性能佳，可用于新一代移动通信以及高频网络通讯中的介质滤波器、介质双工器等器件的制备。
附图说明
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的限定。
图1中的(a)为对照例1，(b)为对照例2，(c)实施例3，(d)为实施例6制备的微波介质陶瓷材料扫描电镜图；
图2为对照例1、2与实施例5和8不同温度下的频率温度系数对比图。
具体实施方式
下面结合具体实施方式对本发明进行说明：
实施例1
1)主相陶瓷材料A合成：
按化学式Mg2.00Co0.10SiO4.10计量比称量原材料MgO、SiO2和CoO，按混合料与去离子水比例1：3加入去离子水，混合研磨20h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1250℃下煅烧3h，得到主相预烧粉料A。
2)副相陶瓷材料B合成：
按照化学组成0.99CaO·0.11SrO-0.06La2O3·0.05Al2O3-1.00TiO2称量原材料CaCO3、SrCO3、La2O3、Al2O3和TiO2进行混合，按混合料与去离子水比例1：2加入去离子水，混合研磨16h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1200℃下煅烧3h，得到副相预烧粉料B。
3)将82.3wt％的主相陶瓷材料A、16.7wt％的副相陶瓷材料B进行混合、0.25wt％的CeO2以及0.75％的MnO2进行混合，以ZrO2球为磨介，按混合料：氧化锆球：去离子水的重量比1：5:1.8加入去离子水，采用湿法混料15h后于120℃烘干，加入2wt％聚乙烯醇(PVA粘结剂)研磨造粒并过40目筛网。然后将造粒粉料在100MPa压力下压制成直径20mm，高度为10mm的圆柱状坯体，在1300℃下保温3h，得到频率稳定型低介陶瓷材料并测试介电性能。
实施例2
1)主相陶瓷材料A合成：
按化学式Mg2.02Zn0.05SiO4.07计量比称量原材料MgO、SiO2和ZnO，按混合料与去离子水比例1：3加入去离子水，混合研磨16h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1200℃下煅烧3h，得到主相预烧粉料A。
2)副相陶瓷材料B合成：
按照化学组成1.05CaO·0.12SrO-0.08Nd2O3·0.06Al2O3-1.05TiO2称量原材料CaCO3、SrCO3、Nd2O3、Al2O3和TiO2进行混合，按混合料与去离子水比例1：2加入去离子水，混合研磨20h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1200℃下煅烧3h，得到副相预烧粉料B。
3)将81.8wt％的主相陶瓷材料A、17.7wt％的副相陶瓷材料B、0.2wt％的WO3以及0.3wt％的MnO2进行混合，以ZrO2球为磨介，按混合料：氧化锆球：去离子水的重量比1：5：1.8加入去离子水，采用湿法混料12h后于120℃烘干，加入2wt％聚乙烯醇(PVA粘结剂)研磨造粒并过40目筛网。然后将造粒粉料在100MPa压力下压制成直径20mm，高度为10mm的圆柱状坯体，在1350℃下保温3h，得到频率稳定型低介陶瓷材料并测试介电性能。
实施例3
1)主相陶瓷材料A合成：
按化学式Mg1.95Co0.10SiO4.05计量比称量原材料MgO、SiO2和CoO，按混合料与去离子水比例1：3加入去离子水，混合研磨20h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1150℃下煅烧4h，得到主相预烧粉料A。
2)副相陶瓷材料B合成：
按照化学组成1.25CaO·0.20SrO-0.15La2O3·0.12Al2O3-1.20TiO2称量原材料CaCO3、SrCO3、La2O3、Al2O3和TiO2进行混合，按混合料与去离子水比例1：2加入去离子水，混合研磨16h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1250℃下煅烧2h，得到副相预烧粉料B。
3)将79.5wt％的主相陶瓷材料A、20.1wt％的副相陶瓷材料B、0.3％的CeO2以及0.1％的WO3进行混合，以ZrO2球为磨介，按混合料：氧化锆球：去离子水的重量比1：5：1.8加入去离子水，采用湿法混料15h后于120℃烘干，加入2wt％聚乙烯醇(PVA粘结剂)研磨造粒并过40目筛网。然后将造粒粉料在100MPa压力下压制成直径20mm，高度为10mm的圆柱状坯体，在1300℃下保温3h，得到频率稳定型低介陶瓷材料并测试介电性能。
实施例4
1)主相陶瓷材料A合成：
按化学式Mg2.00Co0.05SiO4.05计量比称量原材料MgO、SiO2和CoO，按混合料与去离子水比例1：3加入去离子水，混合研磨20h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1200℃下煅烧3h，得到主相预烧粉料A。
2)副相陶瓷材料B合成：
按照化学组成0.85CaO·0.45SrO-0.15Sm2O3·0.10Al2O3-1.10TiO2称量原材料CaCO3、SrCO3、Sm2O3、Al2O3和TiO2进行混合，按混合料与去离子水比例1：2加入去离子水，混合研磨20h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1150℃下煅烧4h，得到副相预烧粉料B。
3)将84.6wt％的主相陶瓷材料A、14.9wt％的副相陶瓷材料B以及0.5wt％的MnO2进行混合，以ZrO2球为磨介，按混合料：氧化锆球：去离子水的重量比1：5:1.8加入去离子水，采用湿法混料18h后于120℃烘干，加入2wt％聚乙烯醇(PVA粘结剂)研磨造粒并过40目筛网。然后将造粒粉料在100MPa压力下压制成直径20mm，高度为10mm的圆柱状坯体，在1400℃下保温2h，得到频率稳定型低介陶瓷材料并测试介电性能。
实施例5
1)主相陶瓷材料A合成：
按化学式Mg1.90Zn0.20SiO4.10计量比称量原材料MgO、SiO2和ZnO，按混合料与去离子水比例1：3加入去离子水，混合研磨16h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1150℃下煅烧2h，得到主相预烧粉料A。
2)副相陶瓷材料B合成：
按照化学组成0.95CaO·0.15SrO-0.10Y2O3·0.08Al2O3-1.05TiO2称量原材料CaCO3、SrCO3、Nd2O3、Al2O3和TiO2进行混合，按混合料与去离子水比例1：2加入去离子水，混合研磨24h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1100℃下煅烧3h，得到副相预烧粉料B。
3)将80.6wt％的主相陶瓷材料A、18.4wt％的副相陶瓷材料B、0.5wt％的CeO2、以及0.5wt％的MnO2进行混合，以ZrO2球为磨介，按混合料：氧化锆球：去离子水的重量比1：5:1.8加入去离子水，采用湿法混料12h后于120℃烘干，加入2wt％聚乙烯醇(PVA粘结剂)研磨造粒并过40目筛网。然后将造粒粉料在100MPa压力下压制成直径20mm，高度为10mm的圆柱状坯体，在1300℃下保温4h，得到频率稳定型低介陶瓷材料并测试介电性能。
实施例6
1)主相陶瓷材料A合成：
按化学式Mg2.00Zn0.03SiO4.10计量比称量原材料MgO、SiO2和ZnO，按混合料与去离子水比例1：3加入去离子水，混合研磨16h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1200℃下煅烧3h，得到主相预烧粉料A。
2)副相陶瓷材料B合成：
按照化学组成1.10CaO·0.20SrO-0.18Nd2O3·0.12Al2O3-1.20TiO2称量原材料CaCO3、SrCO3、Nd2O3、Al2O3和TiO2进行混合，按混合料与去离子水比例1：2加入去离子水，混合研磨20h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1250℃下煅烧2h，得到副相预烧粉料B。
3)将79.5wt％的主相陶瓷材料A、19.9wt％的副相陶瓷材料B、0.1wt％的WO3以及0.5wt％的MnO2进行混合，以ZrO2球为磨介，按混合料：氧化锆球：去离子水的重量比1：5:1.8加入去离子水，采用湿法混料18h后于120℃烘干，加入2wt％聚乙烯醇(PVA粘结剂)研磨造粒并过40目筛网。然后将造粒粉料在100MPa压力下压制成直径20mm，高度为10mm的圆柱状坯体，在1350℃下保温3h，得到频率稳定型低介陶瓷材料并测试介电性能。
实施例7
1)主相陶瓷材料A合成：
按化学式Mg1.85Co0.25SiO4.10计量比称量原材料MgO、SiO2和CoO，按混合料与去离子水比例1：3加入去离子水，混合研磨20h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1250℃下煅烧2h，得到主相预烧粉料A。
2)副相陶瓷材料B合成：
按照化学组成1.20CaO·0.25SrO3-0.20La2O3·0.10Al2O3-1.18TiO2称量原材料CaCO3、SrCO3、La2O3、Al2O3和TiO2进行混合，按混合料与去离子水比例1：2加入去离子水，混合研磨16h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1300℃下煅烧4h，得到副相预烧粉料B。
3)将76.8wt％的主相陶瓷材料A、22.9wt％的副相陶瓷材料B以及0.3wt％的CeO2进行混合，以ZrO2球为磨介，按混合料：氧化锆球：去离子水的重量比1：5：1.8加入去离子水，采用湿法混料15h后于120℃烘干，加入2wt％聚乙烯醇(PVA粘结剂)研磨造粒并过40目筛网。然后将造粒粉料在100MPa压力下压制成直径20mm，高度为10mm的圆柱状坯体，在1400℃下保温3h，得到频率稳定型低介陶瓷材料并测试介电性能。
实施例8
1)主相陶瓷材料A合成：
按化学式Mg2.02Zn0.05SiO4.07计量比称量原材料MgO、SiO2和ZnO，按混合料与去离子水比例1：3加入去离子水，混合研磨16h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1200℃下煅烧3h，得到主相预烧粉料A。
2)副相陶瓷材料B合成：
按照化学组成1.15CaO·0.10SrO-0.10Sm2O3·0.15Al2O3-1.10TiO2称量原材料CaCO3、SrCO3、Sm2O3、Al2O3和TiO2进行混合，按混合料与去离子水比例1：2加入去离子水，混合研磨20h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1200℃下煅烧3h，得到副相预烧粉料B。
3)将79.3wt％的主相陶瓷材料A、20.2wt％的副相陶瓷材料B、0.2wt％的CeO2以及0.3wt％的MnO2进行混合，并加入占主相A和副相B总质量0.5％的CeO2和0.3％的MnO2，以ZrO2球为磨介，按混合料：氧化锆球：去离子水的重量比1：5：1.8加入去离子水，采用湿法混料15h后于120℃烘干，加入2wt％聚乙烯醇(PVA粘结剂)研磨造粒并过40目筛网。然后将造粒粉料在100MPa压力下压制成直径20mm，高度为10mm的圆柱状坯体，在1370℃下保温3h，得到频率稳定型低介陶瓷材料并测试介电性能。
实施例9
1)主相陶瓷材料A合成：
按化学式Mg1.90Co0.10SiO4.00计量比称量原材料MgO、SiO2和CoO，按混合料与去离子水比例1：3加入去离子水，混合研磨20h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1250℃下煅烧2h，得到主相预烧粉料A。
2)副相陶瓷材料B合成：
按照化学组成1.25CaO·0.25SrO-0.15Y2O3·0.15Al2O3-1.08TiO2称量原材料CaCO3、SrCO3、La2O3、Al2O3和TiO2进行混合，按混合料与去离子水比例1：2加入去离子水，混合研磨20h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1300℃下煅烧3h，得到副相预烧粉料B。
3)将75.7wt％的主相陶瓷材料A、24.0wt％的副相陶瓷材料B以及0.3wt％的WO3进行混合，以ZrO2球为磨介，按混合料：氧化锆球：去离子水的重量比1：5：1.8加入去离子水，采用湿法混料18h后于120℃烘干，加入2wt％聚乙烯醇(PVA粘结剂)研磨造粒并过40目筛网。然后将造粒粉料在100MPa压力下压制成直径20mm，高度为10mm的圆柱状坯体，在1350℃下保温4h，得到频率稳定型低介陶瓷材料并测试介电性能。
对照例1
1)主相陶瓷材料A合成：
按化学式Mg2.00SiO4.00计量比称量原材料MgO和SiO2，按混合料与去离子水比例1：3加入去离子水，混合研磨24h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1300℃下煅烧3h，得到主相预烧粉料A。
2)副相陶瓷材料B合成：
按化学式CaTiO3组成称量原材料CaCO3和TiO2进行混合，按混合料与去离子水比例1：2加入去离子水，混合研磨16h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1100℃下煅烧3h，得到副相预烧粉料B。
3)将85wt％的主相陶瓷材料A和15wt％的副相陶瓷材料B进行混合，以ZrO2球为磨介，按混合料：氧化锆球：去离子水的重量比1：5：1.8加入去离子水，采用湿法混料18h后于120℃烘干，加入2wt％聚乙烯醇(PVA粘结剂)研磨造粒并过40目筛网。然后将造粒粉料在100MPa压力下压制成直径20mm，高度为10mm的圆柱状坯体，在1420℃下保温3h，得到对照例微波介质陶瓷并测试介电性能。
对照例2
1)主相陶瓷材料A合成：
按化学式Mg2.05SiO4.00计量比称量原材料MgO和SiO2，按混合料与去离子水比例1：3加入去离子水，混合研磨24h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1300℃下煅烧3h，得到主相预烧粉料A。
2)副相陶瓷材料B合成：
按照化学组成CaTiO3称量原材料CaCO3 TiO2进行混合，按混合料与去离子水比例1：2加入去离子水，混合研磨16h后在120℃烘箱中烘干，用石英研钵研磨后过40目筛网，然后将粉末装入氧化铝坩埚在1300℃下煅烧4h，得到副相预烧粉料B。
3)将82.4wt％的主相陶瓷材料A、17.3wt％的副相陶瓷材料B以及0.3wt％的CeO2进行混合，以ZrO2球为磨介，按混合料：氧化锆球：去离子水的重量比1：5：1.8加入去离子水，采用湿法混料18h后于120℃烘干，加入2wt％聚乙烯醇(PVA粘结剂)研磨造粒并过40目筛网。然后将造粒粉料在100MPa压力下压制成直径20mm，高度为10mm的圆柱状坯体，在1370℃下保温3h，得到对照例微波介质陶瓷并测试介电性能。
表1是对照例与实施例1～9对应的介电性能。其中，介电性能采用Agilent 8719ET网络分析仪，根据Hakki-Coleman谐振腔法测试介电常数εr和Q×f值，频率温度系数τf＝(f80-f25)/(f25×55)计算确定，其中f80和f25分别为样品在80℃和25℃下的中心频率。
表1各实施例的微波介电性能
编号 ε<sub>r</sub> Q×f(GHz) τ<sub>f</sub>(ppm/℃)
1 9.80 63000 -8
2 10.59 58000 -1.79
3 11.25 53500 9.6
4 9.50 68000 -16
5 10.48 59000 -1.8
6 10.75 55360 2.75
7 12.36 51090 11.6
8 11.98 56900 4.8
9 13.60 45000 13
对照例1 10.30 40000 -2.5
对照例2 10.85 49700 0.50
上表列出的各实施例Q×f值较对照例有明显提升，且烧结温度较低，可见通过本发明方法制备的材料有较高的Q×f值，且显著降低烧结温度。附图1(a)、(b)、(c)和(d)分别为对照例1、对照例2、实施例3和实施例6的扫描电镜照片，可以看出通过本发明制备的介质陶瓷晶粒尺寸均匀，致密性良好，且不存在异常长大现象。附图2为对照例1、对照例2、实施例5和实施例8的-40℃～110℃温度系数对照图，结合对照例1和对照例2，可见在CaTiO3未进行掺杂改性的情况下，只能将全温区范围的单边(即-40℃或110℃)温度系数调整至<±5ppm/℃。对比对照例与实施例5和8，可见通过本发明方法对副相陶瓷B进行改性后，可显著改善材料的全温区范围的温度系数至<±5ppm/℃以内。
需要说明的是，在本发明的描述中，术语“包括”、“包含”等意在涵盖非排他性的包含，还包括一些没有明确列出的其他要素的过程、方法和原物料等。“实施例”或某个“具体实施例”等意指结合该实施例描述的具体特征、结构、材料或特点包含于本发明的至少一个实施例中。因此，尽管上文已经应用了具体实施例对发明进行阐述，可以理解的是，上述实施例是用于理解本发明的方法及核心事项，不能理解为对本发明的限制。本领域的普通技术人员在不脱离本发明的原理和宗旨的情况下在本发明的范围内可以对上述实施例进行变化、修改、替换和变型，凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均应视为本发明的保护范围。

Claims (5)

1.一种频率稳定型低介微波介质陶瓷材料，其特征在于：由质量百分比为70%～90%的主相陶瓷材料A、10%～30%的副相陶瓷材料B和0～1.0%的氧化物助烧剂C组成，且主相陶瓷材料A、副相陶瓷材料B和氧化物助烧剂C的质量百分比和为100%；其中主相陶瓷材料A符合化学式Mg x Me y SiO 2+x+y ，其中Me为Co或者Zn，副相陶瓷材料B组成符合aRO-bRe 2 O 3 -cTiO 2 ，其中R为Ca或Sr中的至少一种，Re2O3为Sm2O3、Nd2O3、Y2O3、Al2O3和La2O3中的至少两种，氧化物助烧剂C为MnO2，MnCO3、WO3和CeO2中的至少一种， 2.00≤x+y≤2.20，1.80≤x≤2.15，0＜y≤0.40，1.0≤a≤2.0，0.05≤b≤0.50，1.0≤c≤1.5。
2.根据权利要求1所述的一种频率稳定型低介微波介质陶瓷材料，其特征在于：2.00≤x+y≤2.10，1.80≤x≤2.05，0.05≤y≤0.25。
3.根据权利要求1所述的一种频率稳定型低介微波介质陶瓷材料，其特征在于：1.0≤a≤1.5，0.05≤b≤0.30，1.0≤c≤1.2。
4.根据权利要求1-3中任意一项所述的一种频率稳定型低介微波介质陶瓷材料，其特征在于：所述副相陶瓷材料B的化学式中的Re2O3为Al2O3和Sm2O3，或者Al2O3和Nd2O3，或者Al2O3和Y2O3 ，或者Al2O3和La2O3。
5.一种如权利要求1-3所述的频率稳定型低介微波介质陶瓷材料的制备方法，其特征在于，包括以下步骤：
1）主相陶瓷材料A合成：
按化学式Mg x Me y SiO 2+x+y 计量比称量原材料MgO、SiO2、ZnO、CoO进行混合，以去离子水为溶剂，球磨混合16~24h后烘干；将烘干后的混合料过40目筛网，装入氧化铝坩埚于1150℃~1300℃下煅烧2~4h合成主相粉料A，研磨并过40目筛网备用；
2）副相陶瓷材料B合成：
按化学式aRO-bRe 2 O 3 -cTiO 2 组成称量原材料CaCO3、SrCO3、Sm2O3、Nd2O3、Y2O3、Al2O3和La2O3进行混合，以去离子水为溶剂，球磨混合16~24h后烘干；然后过40目筛网，装入氧化铝坩埚于1100℃~1300℃下煅烧2~4h合成副相粉料B，研磨并过40目筛网备用；
3）按一定配比称量制备好的主相陶瓷材料A、副相陶瓷材料B和氧化物助烧剂C进行混合，以ZrO2球为磨介，按混合料与去离子水的重量比1：1.5~2加入去离子水，采用湿法混料12~18h后于120℃烘干，加入重量含量为1%~3%的聚乙烯醇粘合剂研磨造粒，过40目筛网后在80~120MPa压力下压制成直径20mm，厚度10mm的坯体，在空气气氛中于1300℃~1450℃烧结2~4h，即得到所述频率稳定型低介微波介质陶瓷材料。
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