CN116693288A - 一种促进复合钙钛矿结构Ba(B′1/3B″2/3)O3微波介质陶瓷B位阳离子有序化的方法 - Google Patents
一种促进复合钙钛矿结构Ba(B′1/3B″2/3)O3微波介质陶瓷B位阳离子有序化的方法 Download PDFInfo
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Abstract
本发明公开了一种促进复合钙钛矿结构Ba(B′1/3B″2/3)O3微波介质陶瓷B位阳离子有序化的方法，所述方法为，采用CuO掺杂微波介质陶瓷，所述微波介质陶瓷为存在B位阳离子有序的复合钙钛矿结构Ba(B′1/3B″2/3)O3基陶瓷，其中B'选自Mg、Zn、Co、Mn、Ni中的至少一种或多种，所述B″选自Ta,Nb中的至少一种，通过掺入CuO可以促使Ba(B′1/3B″2/3)O3微波介质陶瓷B位阳离子有序化，从而提升微波介质陶瓷的品质因数Q。
Description
技术领域
本发明属于微波介质陶瓷制备技术领域，具体涉及一种促进复合钙钛矿结构Ba(B′1/3B″2/3)O3微波介质陶瓷B位阳离子有序化的方法。
背景技术
微波介质陶瓷是近几十年来发展起来的一种新型的功能介质陶瓷，是应用于微波频率电路中作为传输介质完成一种或多种功能的介质材料，在5G及毫米波通讯被用作谐振器、滤波器、介质基片和介电天线等。复合钙钛矿结构Ba(B′1/3B″2/3)O3微波介质陶瓷(其中B'＝Mg,Zn,Co,Ni等，B″＝Ta,Nb等，B'和B″位能由多种元素占据)具有适中的介电常数和高的品质因数Q并且已经获得了商业化的应用，通常认为Ba(B′1/3B″2/3)O3微波介质陶瓷品质因数Q与其晶体结构中B位阳离子1:2有序正相关。为了获得高有序的Ba(B′1/3B″2/3)O3微波介质陶瓷，需要对Ba(B′1/3B″2/3)O3微波介质陶瓷在制备过程中进行高温烧结和长时间的退火处理来促进其有序化。高温烧结和长时间的退火处理不仅造成Ba(B′1/3B″2/3)O3微波介质陶瓷制备周期较长，而且烧结和退火过程中容易造成Ba(B′1/3B″2/3)O3微波介质陶瓷中Zn和Co等元素的挥发，在陶瓷中形成点缺陷影响其微波介电性能。
发明内容
针对现有技术的不足，本发明的目的在于提供一种促进复合钙钛矿结构Ba(B′1/ 3B″2/3)O3微波介质陶瓷B位阳离子有序化的方法。
为了实现上述目的，本发明采用如下技术方案：
本发明一种促进复合钙钛矿结构Ba(B′1/3B″2/3)O3微波介质陶瓷B位阳离子有序化的方法，所述方法为，采用CuO掺杂微波介质陶瓷，所述微波介质陶瓷为存在B位阳离子有序的复合钙钛矿结构Ba(B′1/3B″2/3)O3基陶瓷，其中B'选自Mg、Zn、Co、Mn、Ni中的至少一种或多种，所述B″选自Ta,Nb中的至少一种或多种。
通常Ba(B′1/3B″2/3)O3微波介质陶瓷品质因数Q与其晶体结构中B位阳离子1:2有序正相关。发明人发现，通过掺入CuO可以促使Ba(B′1/3B″2/3)O3微波介质陶瓷有序化，从而提升微波介质陶瓷的品质因数Q。
B位阳离子1:2有序化是指当B位阳离子1:2有序时，二价B′位离子(Co2+、Zn2+、Mg2+、Mn2+和Ni2+等)和五价B″位离子(Nb5+和Ta5+等)沿[111]方向重复排列为1层B′和2层B″的{…B′-B″-B″-B′-B″-B″-B′-B″-B″…}有序结构。有序度:表征B位阳离子1:2有序化的程度。
优选的方案，所述CuO掺杂微波介质陶瓷，CuO的掺杂量为0.05～0.4wt％，优选为0.1～0.4wt％，进一步优选为0.2～0.3wt％。
将CuO的掺杂量控制在上述范围内，最终材料的性能最优。
优选的方案，所述B'选自Zn和/或Co，所述B″选自Nb。
优选的方案，所述CuO掺杂微波介质陶瓷的过程为：将Ba(B′1/3B″2/3)O3预烧粉、纳米CuO粉末、粘结剂、润滑剂球磨获得球磨料，球磨料干燥、造粒后，进行压制成型获得生坯，生坯于1300-1600℃，优选为1300℃烧结即得。
Ba(B′1/3B″2/3)O3微波介质陶瓷有序化过程受物质传输过程影响，在固相烧结过程中为基于空位扩散进行物质传输的体积扩散和晶界扩散，本发明通过添加低熔点纳米氧化物CuO在烧结初期形成晶界共晶液相，固相反应烧结转变为基于粘性流动的液相烧结极大加快了Ba(B′1/3B″2/3)O3微波介质陶瓷的物质传输过程，使得Ba(B′1/3B″2/3)O3微波介质陶瓷在低温快速实现致密化和有序化，避免了长时间退火处理工艺，减少了Ba(B′1/3B″2/3)O3微波介质陶瓷制备周期。CuO促进Ba(B′1/3B″2/3)O3微波介质陶瓷致密化和有序化机制如图1所示，在烧结初期，当烧结温度超过1040℃时纳米CuO颗粒逐渐分解并形成液态薄膜富集于晶界处，陶瓷烧结过程转变为黏性流动的液相烧结，显著促进了物质传输过程，在低温快速实现致密化和B位阳离子1:2有序化。而在烧结后期晶界处液态富Cu薄膜又固溶于基体中，不存在导致介电损耗明显增大的晶界第二相或者非晶相。CuO的加入能明显的降低了Ba(B′1/ 3B″2/3)O3微波介质陶瓷烧结温度和退火时间，提高了Ba(B′1/3B″2/3)O3微波介质陶瓷的品质因数Q值。
优选的方案，所述纳米CuO粉末的粒径≤100nm。
优选的方案，所述纳米CuO粉末的加入量为Ba(B′1/3B″2/3)O3预烧粉质量的0.05～0.4wt％，优选为0.1～0.4wt％，进一步优选为0.2～0.3wt％。
优选的方案，所述粘结剂为石蜡，润滑剂为硬脂酸，其中石蜡的加入量为Ba(B′1/ 3B″2/3)O3预烧粉质量的5-10wt％，硬脂酸的加入量为Ba(B′1/3B″2/3)O3预烧粉质量的2-4wt.％。
优选的方案，压制成型的压力为1000-2000kg/cm3，压制成型的时间为1-3min。
优选的方案，所述烧结的过程为：先以1℃/min的升温速率升温至400℃保温1h，然后以1℃/min升温速率升温至600℃保温1h，然后再以5℃/min升温速率升温至1300℃烧结10h，最后以1℃/min的降温速率降温至1000℃后随炉冷。
原理与优势
Ba(B′1/3B″2/3)O3微波介质陶瓷在制备过程中通常需要进行高温烧结(大于1400℃)和长时间的退火处理(通常为20-60小时)来促进其有序化。高温烧结和长时间的退火处理不仅造成Ba(B′1/3B″2/3)O3微波介质陶瓷制备周期较长，而且烧结和退火过程中容易造成Ba(B′1/3B″2/3)O3微波介质陶瓷中Zn和Co等元素的挥发，在陶瓷中形成点缺陷影响其微波介电性能。
本发明通过添加低熔点纳米氧化物CuO在烧结初期形成晶界共晶液相，固相反应烧结转变为基于粘性流动的液相烧结极大加快了Ba(B′1/3B″2/3)O3微波介质陶瓷的物质传输过程，使得Ba(B′1/3B″2/3)O3微波介质陶瓷在低温快速实现致密化和高有序化，避免了长时间退火处理工艺，减少了Ba(B′1/3B″2/3)O3微波介质陶瓷制备周期。CuO促进Ba(B′1/3B″2/3)O3微波介质陶瓷致密化和有序化机制如图1所示，在烧结初期，当烧结温度超过1040℃时纳米CuO颗粒逐渐分解并形成液态薄膜富集于晶界处，陶瓷烧结过程转变为黏性流动的液相烧结，显著促进了物质传输过程，在低温快速实现致密化和B位阳离子1:2有序化。而在烧结后期晶界液态富Cu薄膜又固溶于基体中，不存在导致介电损耗明显增大的晶界第二相或者非晶相。CuO的加入能明显的降低了Ba(B′1/3B″2/3)O3微波介质陶瓷烧结温度和退火时间，提高了Ba(B′1/3B″2/3)O3微波介质陶瓷的品质因数Q值。
附图说明
图1CuO促进陶瓷致密化和有序化机理。
图2 0.05-0.4wt％CuO掺杂BCZN微波陶瓷在1300℃烧结10h的相对密度图。
图3在1300℃烧结不同CuO掺杂量BCZN陶瓷的相对密度、有序度、介电性能与烧结温度的关系。
具体实施方式
实施例1
1.CuO掺杂Ba(Co,Zn)1/3Nb2/3O3陶瓷粉末制备:
将BaCoO3、ZnO、Co3O4和Nb2O5高纯粉末按Ba(Co,Zn)1/3Nb2/3O3陶瓷化学计量比称量，称量误差不超过±0.001g；将精确称量的原材料放入尼龙球磨罐中，以直径5mm和10mm二氧化锆球为球磨介质，酒精为溶剂，酒精、大小氧化锆球与原材料质量比为2:1:1:1。在行星球磨机中进行湿混球磨，转速设定为300r/min，运行1h停10min，运行总时长为24h。将湿混后的粉末浆料与二氧化锆磨球分离，放入烧杯中于鼓风干燥箱内进行干燥，由于溶剂为酒精，为防止酒精爆沸，设定鼓风干燥箱温度为75℃进行干燥。将干燥后的粉末放入刚玉坩埚中，在节能快速升温电阻炉中在1150℃预烧合成了Ba(Co,Zn)1/3Nb2/3O3单相。将预烧好的粉末分别加入0.05-0.4wt％的纳米CuO粉末，5wt％的石蜡和3wt％的硬脂酸进行湿混球磨和造粒。造粒后粉末采用压制成型的方法，压制压力为1500kg/cm3保压3min，得到CuO掺杂Ba(Co,Zn)1/3Nb2/3O3陶瓷生胚。
2.CuO掺杂Ba(Co,Zn)1/3Nb2/3O3陶瓷烧结工艺:采用热脱脂工艺，以1℃/min速率升温至400℃保温1h，然后以1℃/min速率升温至600℃保温1h完成排胶工艺。Ba(Co,Zn)1/ 3Nb2/3O3陶瓷排胶后样品以5℃/min升温至1300℃烧结10h，以1℃/min降温至1000℃后随炉冷。
3.CuO掺杂Ba(Co,Zn)1/3Nb2/3O3陶瓷性能测试:
如图2所示，随着CuO添加量的增加，CuO掺杂BCZN微波陶瓷的相对密度明显提高，1300℃烧结0.2wt％和0.4wt％掺杂CuO样品的相对密度分别为96.5％和97.1％，而1300℃烧结未掺杂样品的相对密度仅为87.1％；如图3所示，CuO添加量为0，0.05wt％，0.1wt％，0.2wt％，0.4wt％的Ba(Co,Zn)1/3Nb2/3O3陶瓷的有序度分别为38.6％，47.1％，61.4％，69.2％，70.6％。说明CuO的加入Ba(Co,Zn)1/3Nb2/3O3陶瓷有序化程度和致密化程度明显提升。CuO添加量为0.2wt％时，由于致密度和有序度的提升，Ba(Co,Zn)1/3Nb2/3O3陶瓷在1300℃烧结10小时的Q×f值(f为测试中心频率，为7GHz)从21,200GHz增加到69,300GHz。当CuO添加量增大为0.4wt％时，Ba(Co,Zn)1/3Nb2/3O3陶瓷Q×f值略微下降。
Claims (5)
1.一种促进复合钙钛矿结构Ba(B′1/3B″2/3)O3微波介质陶瓷B位阳离子有序化的方法，其特征在于：所述方法为，采用CuO掺杂微波介质陶瓷，所述微波介质陶瓷为存在B位阳离子有序的复合钙钛矿结构Ba(B′1/3B″2/3)O3基陶瓷，其中B'选自Mg、Zn、Co、Mn、Ni中的至少一种或多种，所述B″选自Ta,Nb中的至少一种或多种。
2.根据权利要求1所述的一种促进复合钙钛矿结构Ba(B′1/3B″2/3)O3微波介质陶瓷B位阳离子有序化的方法，其特征在于：所述CuO掺杂微波介质陶瓷，CuO的掺杂量为0.05～0.4wt％。
3.根据权利要求1或2所述的一种促进复合钙钛矿结构Ba(B′1/3B″2/3)O3微波介质陶瓷B位阳离子有序化的方法，其特征在于：所述CuO掺杂微波介质陶瓷的过程为：将Ba(B′1/3B″2/3)O3预烧粉、纳米CuO粉末、粘结剂、润滑剂球磨获得球磨料、球磨料干燥、造粒后，进行压制成型获得生坯，生坯于1300-1600℃烧结即得。
4.根据权利要求1或2所述的一种促进复合钙钛矿结构Ba(B′1/3B″2/3)O3微波介质陶瓷B位阳离子有序化的方法，其特征在于：所述纳米CuO粉末的粒径≤100nm。
5.根据权利要求4所述的一种促进复合钙钛矿结构Ba(B′1/3B″2/3)O3微波介质陶瓷B位阳离子有序化的方法，其特征在于：所述纳米CuO粉末的加入量为Ba(B′1/3B″2/3)O3预烧粉质量的0.05～0.4wt％。
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