CN110229004B - 一种低温烧结微波介质陶瓷材料及其制备方法 - Google Patents

一种低温烧结微波介质陶瓷材料及其制备方法 Download PDF

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CN110229004B
CN110229004B CN201910603226.3A CN201910603226A CN110229004B CN 110229004 B CN110229004 B CN 110229004B CN 201910603226 A CN201910603226 A CN 201910603226A CN 110229004 B CN110229004 B CN 110229004B
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ceramic material
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dielectric ceramic
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CN110229004A (zh
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李恩竹
杨鸿程
孙成礼
钟朝位
张树人
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University of Electronic Science and Technology of China
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Abstract

本发明属于电子陶瓷及其制造领域，涉及一种低温烧结微波介质陶瓷材料及其制备方法，主要用于通讯系统的介质滤波器。本发明材料为BaWO4基微波介质陶瓷材料，烧结温度850℃～900℃，介电常数5.8～9.0，损耗低至3.70×10‑4，频率温度系数‑30～‑10ppm/℃；其化学通式为BaWO4‑xM2CO3‑yBaO‑zB2O3‑wSiO2，其中M为Li+、K+或Na+碱金属离子，且x、y、z、w不能同时为零。当y＝0时，在850℃～900℃下烧结后均为BaWO4相；当y不等于0时，主晶相为BaWO4相，次晶相为BaSi2O5相。制备时，直接将原料按照所需化学式配料，通过固相烧结法制得；最终获得烧结温度低至850℃，保温时间0.5～2h，介电性能5.8～9.0满足高频介质滤波器的BaWO4基的LTCC微波介质陶瓷材料，可应用在LTCC领域。

Description

一种低温烧结微波介质陶瓷材料及其制备方法
技术领域
本发明属于电子陶瓷及其制造领域，涉及一种低温烧结微波介质陶瓷材料及其制备方法，主要用于通讯系统的介质滤波器。
背景技术
在20世纪70年代，介质滤波器就被用于微波通信领域，80年代以后，随着蜂窝电话的出现，介质滤波器也被用于移动通信系统。随着移动通信业务和内容的不断拓展，我国的移动通信频段由早期的900MHz和1800MHz频段于2013年底正式拓展到4G。如今，5G技术的发展也方兴未艾，而用于该波段的微波介质陶瓷需有低介电常数(εr<10)，因此，开发出能满足5G技术发展的微波介质陶瓷具有重要的工业应用价值。
同时，低温共烧技术(LTCC)是电子元器件制造工艺的主流趋势，该技术能够实现电子元器件的集成化、模块化，且生产成本较低。对于应用于LTCC的陶瓷材料，需要其能在低于银电极熔点(961℃)的温度下烧结成瓷。目前，刚玉瓷Al2O3是介电常数在10左右的主要微波介质陶瓷，但其较高的烧结温度(1600℃～1800℃)难以满足工厂批量化生产的要求，所以寻求具有较低烧结温度的低介电常数材料是科研人员将微波介质陶瓷用于5G技术中不断探索的目标。
低介电常数微波介质陶瓷中具有四方相白钨矿结构的A2+W6+O4(A＝Ca，Sr，Ba)陶瓷因其较好的烧结特性和微波介电性能而被关注，尤其是针对CaWO4陶瓷的改性和降烧研究极为广泛。其中，BaWO4陶瓷能在1100℃烧结致密且介电性能为：εr＝9.0，Q×f＝32200GHz，但其相对较高的烧结温度及较长的保温时间，限制了其在LTCC中的应用。然而迄今为止，对BaWO4基陶瓷的烧结性能的研究仅限于加入Ba3(VO4)2后能够在925℃保温4h烧结致密并获得较好性能或者利用BaWO4的中温烧结特性来降低高温烧结陶瓷材料的温度，而对BaWO4微波介质陶瓷的低温烧结的系统研究及LTCC应用并未报道。
发明内容
针对上述存在问题或不足，为改善BaWO4陶瓷的烧结特性，使其能够应用在LTCC领域，并且保持良好的介电性能，本发明提供了一种低温烧结微波介质陶瓷材料及其制备方法，在低至850℃下保温0.5～2h烧结成瓷，使BaWO4陶瓷材料能够在LTCC领域应用。
该低温烧结微波介质陶瓷材料为BaWO4基微波介质陶瓷材料，烧结温度850℃～900℃，介电常数5.8～9.0，损耗低至3.70×10-4，频率温度系数-30～-10ppm/℃，应用在LTCC领域；其化学通式为BaWO4-xM2CO3-yBaO-zB2O3-wSiO2，x＝0～0.2mol，y＝0～0.05mol，z＝0～0.2mol，w＝0～0.1mol，其中M为Li+、K+或Na+碱金属离子，且x、y、z、w不能同时为零，通过固相烧结法制得。
该BaWO4基LTCC材料，当y＝0时，在850℃～900℃下烧结后均为BaWO4相；当y不等于0时，主晶相为BaWO4相，次晶相为BaSi2O5相。
上述低温烧结微波介质陶瓷材料的制备方法，包括以下步骤：
步骤1：将原料BaCO3，WO3，M2CO3，B2O3和SiO2按照化学通式BaWO4-xM2CO3-yBaO-zB2O3-wSiO2，x＝0～0.2mol，y＝0～0.05mol，z＝0～0.2mol，w＝0～0.1mol进行配料，其中M为碱金属离子Li+、K+或Na+；且x，y，z，w不能同时为零。
步骤2：将步骤1配好的粉体装入尼龙球磨罐，研磨介质为锆球和去离子水，按照粉料：锆球：去离子水质量比为1:5:1～1:5:2进行球磨，行星球磨4～7小时，取出后在80～120℃烘箱中烘干，以40～60目筛网过筛，后在600～800℃大气气氛中预烧2～4小时。
步骤3：将步骤2预烧后的粉体，再次按照粉体：锆球：去离子水质量比为1:5:1～1:5:2进行球磨，行星球磨混合3～6小时，取出烘干后，向得到的粉体中添加粘结剂造粒(丙烯酸溶液)。
步骤4：将步骤3制得产物压制成型，在400～500℃排胶后在850℃～900℃大气气氛中烧结0.5～2小时，即可制得BaWO4基的低温烧结微波介质陶瓷材料。
综上所述，本发明不同于在二次球磨时添加助烧剂对基体陶瓷进行降烧，直接将原料按照所需化学式配料，且最终制得烧结温度低至850℃，保温时间0.5～2h，介电性能5.8～9.0满足用于高频介质滤波器的BaWO4基的LTCC微波介质陶瓷材料，解决了BaWO4低介陶瓷在LTCC技术上的应用需求。
附图说明
图1为实施例12、13、14、15号的XRD衍射图谱。
具体实施方式
下面结合附图和实施例对本发明做进一步的详细说明。
本发明材料组成按化学式BaWO4-xM2CO3-yBaO-zB2O3-wSiO2，x＝0～0.2mol,y＝0～0.05mol，z＝0～0.2mol，w＝0～0.1mol其中M为碱金属离子Li+，K+，Na+，且x，y，z，w不能同时为零，由固相反应即可制得本发明材料。
该BaWO4基的低温烧结微波介质陶瓷材料的制造原料为:BaCO3，WO3，Li2CO3，K2CO3，Na2CO3，B2O3和SiO2。通过固相反应法即可获得本材料，具体步骤同上述步骤一样。
具体实施例的成分和微波介电性能如下
Figure BDA0002119883230000031
Figure BDA0002119883230000041
Figure BDA0002119883230000042
Figure BDA0002119883230000051
上表格数据囊括了在化学通式范围内的实施例配料结果及烧熟样品性能，从表中可以看出，在烧结温度为850℃～900℃保温0.5小时，所有的样品微波介电性能优异，说明在该温度下该微波介质材料成瓷良好，能够满足于LTCC工艺要求。
图1展示了本发明陶瓷材料在900℃保温0.5小时后的XRD衍射图谱，分别对应实施例样品12、13、14和15号。从图1可以看出，对y＝0的陶瓷样品，在该烧结温度下，样品均呈现出单一的纯相白钨矿BaWO4(JCPDS#01-072-0746)；而15号样品生成的主晶相为BaWO4(JCPDS#01-072-0746)和次晶相为BaSi2O5(JCPDS#00-011-0170)。

Claims (3)

1.一种低温烧结微波介质陶瓷材料，其特征在于：
为BaWO4基微波介质陶瓷材料，烧结温度850℃～900℃，应用在LTCC领域；介电常数5.8～9.0，损耗低至3.70×10-4，频率温度系数-30～-10ppm/℃；
该低温烧结微波介质陶瓷材料的化学通式为BaWO4-xM2CO3-yBaO-zB2O3-wSiO2，0<x≤0.2mol，0≤y≤0.05mol，0<z≤0.2mol，0<w≤0.1mol，其中M为Li+、K+或Na+碱金属离子，通过固相烧结法制得；
该BaWO4基微波介质陶瓷材料，当y＝0时，在850℃～900℃下烧结后均为BaWO4相；当y不等于0时，主晶相为BaWO4相，次晶相为BaSi2O5相。
2.如权利要求1所述低温烧结微波介质陶瓷材料的制备方法，步骤如下：
步骤1：将原料BaCO3，WO3，M2CO3，B2O3和SiO2按照化学通式BaWO4-xM2CO3-yBaO-zB2O3-wSiO2，0<x≤0.2mol，0≤y≤0.05mol，0<z≤0.2mol，0<w≤0.1mol进行配料，其中M为碱金属离子Li+，K+或Na+；
步骤2：将步骤1配好的粉体装入尼龙球磨罐，研磨介质为锆球和去离子水，按照粉料：锆球：去离子水质量比为1:5:1～1:5:2进行球磨，行星球磨4～7小时，取出后在80～120℃烘箱中烘干，以40～60目筛网过筛，后在600～800℃大气气氛中预烧2～4小时；
步骤3：将步骤2预烧后的粉体，再次按照粉体：锆球：去离子水质量比为1:5:1～1:5:2进行球磨，行星球磨混合3～6小时，取出烘干后，向得到的粉体中添加粘结剂造粒；
步骤4：将步骤3制得产物压制成型，在400～500℃排胶后在850℃～900℃大气气氛中烧结0.5～2小时，即可制得BaWO4基的烧结微波介质陶瓷材料。
3.如权利要求2所述低温烧结微波介质陶瓷材料的制备方法，其特征在于：所述步骤3采用的粘结剂为丙烯酸溶液。
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