CN107986774B - 低温烧结高介电常数微波介质陶瓷材料及其制备方法 - Google Patents

低温烧结高介电常数微波介质陶瓷材料及其制备方法 Download PDF

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CN107986774B
CN107986774B CN201711224893.8A CN201711224893A CN107986774B CN 107986774 B CN107986774 B CN 107986774B CN 201711224893 A CN201711224893 A CN 201711224893A CN 107986774 B CN107986774 B CN 107986774B
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张树人
方梓烜
唐斌
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University of Electronic Science and Technology of China
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Abstract

本发明提供一种低温烧结高介电常数微波介质陶瓷材料及制备方法，由质量百分比为87％～95％的Ca0.35Li0.25Nd0.35TiO3、质量百分比为2％～6％的低温相A、以及质量百分比为3％～7％的降烧剂B组成，材料化学通式为：Ca0.35Li0.25Nd0.35TiO3+xA+yB，x＝2wt％‑6wt％，y＝3wt％‑7wt％；其中，低温相A为BaCu(B2O5)或Ca5Co4V5.95O24；降烧剂B由氟化锂、碳酸锂、二氧化硅、硼酸、氧化锌、添加物组成，本发明制备的陶瓷材料可低温烧结，体系致密，具有高介电常数，高品质因数，较小的频率温度系数，本发明材料不与银浆发生反应，能够在LTCC工艺中与银良好共烧，工艺简单，易于工业化生产且材料性能稳定，适合用于低温共烧陶瓷系统LTCC、多层介质谐振器、微波天线、滤波器等微波器件的制造。

Description

低温烧结高介电常数微波介质陶瓷材料及其制备方法
技术领域
本发明属于电子信息功能材料制备技术领域，涉及一种基于Ca-Li-Nd-Ti系高介电常数微波介质陶瓷材料，尤其是一种低温烧结高介电常数微波介质陶瓷材料及其制备方法。
背景技术
微波介质陶瓷是指应用于微波(300MHz到300GHz)频段电路中作为介质材料并完成一种或多种功能的陶瓷，是现代通信技术中的关键基础材料，被广泛应用于介质谐振器、滤波器、介质基片、介质波导回路、微波电容、双工器、天线等微波元器件。
随着电子信息技术不断向高频化和数字化方向发展，对元器件的小型化，集成化以至模块化的要求也越来越迫切。低温共烧陶瓷LTCC(Low Temperature Co-firedCeramics)以其优异的电学、机械、热学及工艺特性，已经成为电子器件模块化的主要技术之一。
应用于微波频段的介电陶瓷，应满足要求：(1)高的介电常数以利于器件的小型化(介质元器件的尺寸与介电常数εr的平方根成反比)；(2)高的品质因数Qf值和低的损耗(其中Q～1/tanδ，f是谐振频率)；(3)近零可调的谐振频率温度系数；(4)与银或铜有良好的共烧性。
在众多高介电常数的体系中，CaO-Nd2O3-Li2O-TiO2体系中的Ca0.35Li0.25Nd0.35TiO3具有良好的微波介电性能：εr＝134，Q×f＝2000GHz，τf＞+60ppm/℃，但其极高的烧结温度(1200℃)，不能直接与Ag、Cu等低熔点金属共烧。降低烧结温度的方法有：添加低熔点氧化物或低熔点玻璃烧结助剂，引入化学合成方法，以及超细粉体作原料等。化学方法合成和超细粉体作原料可导致工艺过程复杂，制造成本和周期会上升。相比较而言，添加低熔点氧化物或低熔点玻璃烧结助剂的工艺相对简单，易于批量生产。传统的方法一种为掺入低熔点氧化物，如B2O3及V2O5，然而游离的B2O3及V2O5在后期流延过程中易导致浆料粘度过大而不稳定，限制了其实际应用。传统的方法一种为掺入低熔点氧化物，如B2O3及V2O5，然而游离的B2O3及V2O5在后期流延过程中易导致浆料粘度过大而不稳定，限制了其实际应用。并且Ca0.35Li0.25Nd0.35TiO3极大的谐振频率温度系数(τf)也限制了其在LTCC工艺中的应用，降低频率温度系数通常是以两相复合的方式来实现，但加入过量的第二相会严重恶化综合微波性能。
发明内容
本发明的发明目的在于克服上述存在的问题，提供一种低温烧结高介电常数微波介质陶瓷材料及其制备方法：
为实现上述发明目的，本发明技术方案如下：
一种低温烧结高介电常数微波介质陶瓷材料，由质量百分比为87％～95％的Ca0.35Li0.25Nd0.35TiO3、质量百分比为2％～6％的低温相A、以及质量百分比为3％～7％的降烧剂B组成，材料化学通式为：Ca0.35Li0.25Nd0.35TiO3+xA+yB，x＝2wt％-6wt％，y＝3wt％-7wt％；
其中，低温相A为BaCu(B2O5)或Ca5Co4V5.95O24；
降烧剂B由分别占降烧剂B总质量30％～46.8％的氟化锂、10.12％～20％碳酸锂、6.49％～10.76％的二氧化硅、35.59％～39.24％的硼酸、0％～4％的氧化锌、以及0.05％～0.1％的添加物组成，所述添加物为质量比为1:3碳酸锰和氧化亚钴。
作为优选方式，所述材料的介电常数εr在98～105之间，品质因数Q×f在600GHz～4000GHz之间，频率温度系数τf在11ppm/℃～+56ppm/℃之间。
为实现上述发明目的，本发明还提供一种上述的低温烧结高介电常数微波介质陶瓷材料的制备方法，将微波陶瓷材料各组分按所述化学通式配料，经过第一次球磨混合后，再经过第二次球磨混合，在850～900℃下进行气氛控制烧结制成。
作为优选方式，所述制备方法进一步包括以下步骤：
步骤1：将碳酸钡、碳酸锂、氧化钕、二氧化钛的粉末按Ca0.35Li0.25Nd0.35TiO3组成配料；将碳酸钡、氧化铜、氧化硼的粉末按BaCu(B2O5)组成配料；碳酸钡、氧化钴、氧化钒的粉末按Ca5Co4V5.95O24组成配料；
步骤2：将步骤1配好的粉体混合均匀，Ca0.35Li0.25Nd0.35TiO3以粉体和无水酒精质量比为1:1.4向粉体中加入无水酒精，以无水酒精为溶剂，行星球磨混合5～7小时，取出后在60℃下烘干，以80目筛网过筛，后在900℃～1100℃大气气氛中预烧3～4小时合成Ca0.35Li0.25Nd0.35TiO3晶相；
低温相B的合成：BaCu(B2O5)以粉体和去离子水质量比为1:4向粉体中加入去离子水，以去离子水为溶剂，行星球磨混合5～7小时，取出后在60℃下烘干，以70目筛网过筛，后在500℃～700℃大气气氛中预烧1～2小时合成BaCu(B2O5)晶相；Ca5Co4V5.95O24以粉体和去离子水质量比为1:1.1向粉体中加入去离子水，以去离子水为溶剂，行星球磨混合5～7小时，取出后在60℃下烘干，以70目筛网过筛，后在600℃～800℃大气气氛中预烧1～2小时合成Ca5Co4V5.95O24晶相；
步骤3：按配比将LiF、Li2CO3、SiO2、H3BO3、ZnO、MnCO3,CoO配料，球磨3～7小时，烘干过筛，500℃～700℃保温2～8小时预烧，然后在1200℃～1500℃保温2～6小时熔融玻璃渣，将制备的玻璃渣再破碎球磨成粉备用；
步骤4：在步骤2中预烧后的Ca0.35Li0.25Nd0.35TiO3粉体中加入占总质量百分比为2％～6％的低温相A，然后加入占总质量比为3％～7％的降烧剂B，得到混合粉体，以得到的混合粉体和去离子水质量比为1:1向混合粉体中加入去离子水，以去离子水为溶剂，行星球磨混合3～5小时，取出后在100℃下烘干，烘干后添加剂量占烘干料总质量的2～5％的丙烯酸溶液作为粘结剂造粒，压制成型，最后在850℃-900℃大气气氛中烧结8～10小时，制成微波介质陶瓷材料。
本发明的有益效果为：本发明制备的陶瓷材料可低温烧结(≤900℃)，体系致密，具有高介电常数(εr≥98)，高品质因数(Q×f≥2000GHz)，较小的频率温度系数(τf在11ppm/℃～+56ppm/℃之间)，本发明材料不与银浆发生反应，能够在LTCC工艺中与银良好共烧，工艺简单，易于工业化生产且材料性能稳定，适合用于低温共烧陶瓷系统(LTCC)、多层介质谐振器、微波天线、滤波器等微波器件的制造。
附图说明
图1是本发明实施例3制备的微波陶瓷介质材料的收缩率曲线分析结果。
图2是本发明实施例3制备的微波陶瓷介质材料XRD图。
图3是本发明实施例3制备的微波陶瓷介质材料的SEM图
图4是本发明实施例3制备的微波陶瓷介质材料与Ag在875℃共烧SEM图
具体实施方式
实施例
一种低温烧结高介电常数微波介质陶瓷材料，由质量百分比为87％～95％的Ca0.35Li0.25Nd0.35TiO3,质量百分比为2％～6％的低温相A，以及质量百分比为3％～7％的降烧剂B组成，材料的化学通式为Ca0.35Li0.25Nd0.35TiO3+xA+yB(x＝0wt％-9wt％,y＝3wt％-7wt％)。其中低温相A为BaCu(B2O5),Ca5Co4V5.95O24中的一种，降烧剂B由分别占降烧剂B总质量30％～46.8％的氟化锂、10.12％～20％碳酸锂、6.49％～10.76％的二氧化硅、35.59％～39.24％的硼酸、0％～4％的氧化锌、以及0.05％～0.1％的添加物组成，所述添加物为质量比为1:3碳酸锰和氧化亚钴。
将微波陶瓷材料各组分按所述化学通式配料，经过第一次球磨混合后，再经过第二次球磨混合，在850～900℃下进行气氛控制烧结制成。
以下各实施例具体包括以下步骤：
步骤1：将碳酸钡、碳酸锂、氧化钕、二氧化钛的粉末按Ca0.35Li0.25Nd0.35TiO3组成配料；将碳酸钡、氧化铜、氧化硼的粉末按BaCu(B2O5)组成配料；碳酸钡、氧化钴、氧化钒的粉末按Ca5Co4V5.95O24组成配料；
步骤2：将步骤1配好的粉体混合均匀，Ca0.35Li0.25Nd0.35TiO3以粉体和无水酒精质量比为1:1.4向粉体中加入无水酒精，以无水酒精为溶剂，行星球磨混合5～7小时，取出后在60℃下烘干，以80目筛网过筛，后在900℃～1100℃大气气氛中预烧3～4小时合成正交钙钛矿相的Ca0.35Li0.25Nd0.35TiO3晶相；
低温相B的合成：BaCu(B2O5)以粉体和去离子水质量比为1:4向粉体中加入去离子水，以去离子水为溶剂，行星球磨混合5～7小时，取出后在60℃下烘干，以70目筛网过筛，后在500℃～700℃大气气氛中预烧1～2小时合成BaCu(B2O5)晶相；Ca5Co4V5.95O24以粉体和去离子水质量比为1:1.1向粉体中加入去离子水，以去离子水为溶剂，行星球磨混合5～7小时，取出后在60℃下烘干，以70目筛网过筛，后在600℃～800℃大气气氛中预烧1～2小时合成Ca5Co4V5.95O24晶相；
步骤3：按配比将LiF、Li2CO3、SiO2、H3BO3、ZnO、MnCO3,CoO配料，球磨3～7小时，烘干过筛，500℃～700℃保温2～8小时预烧，然后在1200℃～1500℃保温2～6小时熔融玻璃渣，将制备的玻璃渣再破碎球磨成粉备用；
步骤4：在步骤2中预烧后的Ca0.35Li0.25Nd0.35TiO3粉体中加入占总质量百分比为2％～6％的低温相A，然后加入占总质量比为3％～7％的降烧剂B，得到混合粉体，以得到的混合粉体和去离子水质量比为1:1向混合粉体中加入去离子水，以去离子水为溶剂，行星球磨混合3～5小时，取出后在100℃下烘干，烘干后添加剂量占烘干料总质量的2～5％的丙烯酸溶液作为粘结剂造粒，压制成型，最后在850℃-900℃大气气氛中烧结8～10小时，制成微波介质陶瓷材料。
对比例1-8的配方、工艺参数见表1。
实施例1-实施例20为各实施例的具体配方、工艺参数、及性能数据，详见表2-表6：
表1对比例
Figure BDA0001487080630000061
表2具体实施例
Figure BDA0001487080630000062
Figure BDA0001487080630000071
表3具体实施例
Figure BDA0001487080630000072
表4对比例的微波介电性能
Figure BDA0001487080630000081
表5各实施例的微波介电性能
Figure BDA0001487080630000082
Figure BDA0001487080630000091
表6各实施例的微波介电性能
Figure BDA0001487080630000092
从上表可以看出，通过降烧剂的加入，使得体系能够在低温下烧结致密并获得高介电常数和优良的微波介电性能。并且通过对比未加入BaCu(B2O5)或Ca5Co4V5.95O24的体系(对比例1-8)和加入BaCu(B2O5)或Ca5Co4V5.95O24的体系(实施例1-20)，可以看出，适量BaCu(B2O5)或Ca5Co4V5.95O24的加入，有助于调节获得更稳定的谐振频率温度系数和高的品质因数。
通过烧结收缩曲线(附图1)可以进一步看出降烧剂能够在低温下有效促进烧结，使得体系致密。对比未加入降烧剂和加入降烧剂的样品可以看出，纯的Ca0.35Li0.25Nd0.35TiO3(a)在1040℃附近开始收缩，而加入低温相和降烧剂的Ca0.35Li0.25Nd0.35TiO3(b)收缩温度在790℃附近，明显低于纯的Ca0.35Li0.25Nd0.35TiO3。通过XRD图(附图2)可以看出，950℃预烧后可获得正交钙钛矿相(Ca0.35Li0.25Nd0.35TiO3相)和BaCu(B2O5)相，可以看出在加入低烧相和降烧剂并没有产生其他杂相。从SEM图(附图3)可以看出，在875℃烧结时，因为降烧剂的加入，结构致密，晶粒均匀分布，说明降烧剂对烧结致密有促进作用，从SEM图(附图4)可以看出，在875℃烧结时，Ag与本发明微波介质材料界面清晰没有发生反应，说明本材料完全满足LTCC工艺的需求。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (4)

1.一种低温烧结高介电常数微波介质陶瓷材料，其特征在于：由质量百分比为87％～95％的Ca0.35Li0.25Nd0.35TiO3、质量百分比为2％～6％的低温相A、以及质量百分比为3％～7％的降烧剂B组成，材料化学通式为：Ca0.35Li0.25Nd0.35TiO3+xA+yB，x＝2wt％-6wt％，y＝3wt％-7wt％；
其中，低温相A为Ca5Co4V5.95O24；
降烧剂B由分别占降烧剂B总质量30％～46.8％的氟化锂、10.12％～20％碳酸锂、6.49％～10.76％的二氧化硅、35.59％～39.24％的硼酸、0％～4％的氧化锌、以及0.05％～0.1％的添加物组成，所述添加物为质量比为1:3碳酸锰和氧化亚钴。
2.根据权利要求1所述的低温烧结高介电常数微波介质陶瓷材料，其特征在于：所述材料的介电常数εr在98～105之间，品质因数Q×f在600GHz～4000GHz之间，频率温度系数τf在11ppm/℃～+56ppm/℃之间。
3.权利要求1或2所述的低温烧结高介电常数微波介质陶瓷材料的制备方法，其特征在于：将微波陶瓷材料各组分按所述化学通式配料，经过第一次球磨混合后，再经过第二次球磨混合，在850～900℃下进行气氛控制烧结制成。
4.权利要求1或2所述的低温烧结高介电常数微波介质陶瓷材料的制备方法，其特征在于包括以下步骤：
步骤1：将碳酸钡、碳酸锂、氧化钕、二氧化钛的粉末按Ca0.35Li0.25Nd0.35TiO3组成配料；将碳酸钡、氧化钴、氧化钒的粉末按Ca5Co4V5.95O24组成配料；
步骤2：将步骤1配好的粉体混合均匀，Ca0.35Li0.25Nd0.35TiO3以粉体和无水酒精质量比为1:1.4向粉体中加入无水酒精，以无水酒精为溶剂，行星球磨混合5～7小时，取出后在60℃下烘干，以80目筛网过筛，后在900℃～1100℃大气气氛中预烧3～4小时合成正交钙钛矿相的Ca0.35Li0.25Nd0.35TiO3晶相；
低温相A的合成：Ca5Co4V5.95O24以粉体和去离子水质量比为1:1.1向粉体中加入去离子水，以去离子水为溶剂，行星球磨混合5～7小时，取出后在60℃下烘干，以70目筛网过筛，后在600℃～800℃大气气氛中预烧1～2小时合成Ca5Co4V5.95O24晶相，
步骤3：按配比将LiF、Li2CO3、SiO2、H3BO3、ZnO、MnCO3,CoO配料，球磨3～7小时，烘干过筛，500℃～700℃保温2～8小时预烧，然后在1200℃～1500℃保温2～6小时熔融玻璃渣，将制备的玻璃渣再破碎球磨成粉备用；
步骤4：在步骤2中预烧后的Ca0.35Li0.25Nd0.35TiO3粉体中加入占总质量百分比为2％～6％的低温相A，然后加入占总质量比为3％～7％的降烧剂B，得到混合粉体，以得到的混合粉体和去离子水质量比为1:1向混合粉体中加入去离子水，以去离子水为溶剂，行星球磨混合3～5小时，取出后在100℃下烘干，烘干后添加剂量占烘干料总质量的2～5％的丙烯酸溶液作为粘结剂造粒，压制成型，最后在850℃-900℃大气气氛中烧结8～10小时，制成微波介质陶瓷材料。
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