CN114436647A - 低温共烧钛酸铋钠基介质陶瓷的制备方法 - Google Patents
低温共烧钛酸铋钠基介质陶瓷的制备方法 Download PDFInfo
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Abstract
本发明公开的低温共烧钛酸铋钠基介质陶瓷的制备方法,通过钽酸钠掺杂含有过量铋的钛酸铋钠陶瓷的制备以及对应最佳组分掺入烧结助剂的制备,通过将Bi2O3、Na2CO3、TiO2、和Ta2O5按照化学计量比称量混合、球磨干燥,以及Bi2O3、CuO、Li2CO3、ZnO和B2O3与80Bi0.51Na0.5TiO3‑20NaTaO3按照质量百分比称量混合、球磨干燥,然后将不同组分的混合粉末通过等静压技术挤压成片,最后在不同温度烧结即得。本发明解决了现有技术中陶瓷电容器在‑55℃~300℃的温度范围内介电损耗高,温度稳定性差,且内电极成本昂贵的问题。
Description
技术领域
本发明属于铁电陶瓷制备技术领域,具体涉及低温共烧钛酸铋钠基介质陶瓷的制备方法。
背景技术
钛酸铋钠(Bi0.5Na0.5TiO3)由于优异的绝缘性和高的居里温度,以其为材料制作的电容器介电性能的关注逐渐增多,通过掺杂改性,提高在100℃~300℃高温段稳定性,但这与现有商用多层陶瓷电容器(MLCC)在-55℃~300℃使用温度范围不兼容;另一方面,由于钛酸铋钠基陶瓷烧结温度普遍高于1100℃,导致只能与价格昂贵的银钯合金内电极共烧制备多层陶瓷电容器,成本大大提高。
现有的文献“Temperature-stable dielectric and energy properties of (1-x)(0.94Bi0.5Na0.5TiO3-0.09BiAlO3)-xSrTiO3 ceramics.Journal of Alloys andcompounds.807(2019)151676”中公开了一种高温介电陶瓷的制备方法,BiAlO3的掺杂抑制了氧化物离子的导电,显著降低了高温下介电损耗,SrTiO3的掺杂提高了介电性能温度稳定性,在132.8℃~391.8℃的温度范围内介电损耗小于0.02,介电常数的温度稳定性(Δε'/ε'200℃)不超过±15%,但与现有的商用陶瓷电容器-55℃~200℃的温度范围相比,低温温度限过高,具有明显的差异;并且烧结温度在1150℃以上,对应的MLCC只能以价格昂贵的银钯合金作为内电极,大大提高了成本。
发明内容
本发明的目的是提供低温共烧钛酸铋钠基介质陶瓷的制备方法,解决了现有技术中现有商用陶瓷电容器的温度范围窄,温区范围内介电损耗高,温度稳定性差的问题。
本发明所采用的技术方案是,低温共烧钛酸铋钠基介质陶瓷的制备方法,具体按照以下步骤进行实施:
步骤1,按照化学计量比(1-x)Bi0.51Na0.5TiO3-xNaTaO3,x=0.2~0.35,称量Bi2O3、Na2CO3、TiO2和Ta2O5,将Bi0.51Na0.5TiO3记为B0.51NT,B0.51NT与NaTaO3的摩尔比为80:20~65:35;
步骤2,在球磨机中用酒精为介质,球磨干燥并在800℃~900℃煅烧2h得到掺杂NaTaO3的Bi0.51Na0.5TiO3粉体;
步骤3,将步骤2得到的粉体在冷等静压机中,压力成型成圆片,将成型后的圆片烧结成瓷,将烧结后的陶瓷片打磨、抛光后用无水乙醇洗涤,通过银极测试陶瓷的介电性能,确定步骤1中具有最佳介电性能的组分x;
本发明的特点还在于,
根据步骤3得到介电性能组分x取值,通过以下操作确定步骤1中具有最佳介电性能的组分x;
步骤3.1,通过步骤3确定步骤1中组分x取值,称量步骤2中所得到的陶瓷粉体10~20g,再分别称取Bi2O3、CuO、Li2CO3、ZnO和B2O3作为助烧剂加入陶瓷粉体中,得到混合粉体;
步骤3.2,在球磨机中用酒精为介质,球磨干燥得到陶瓷/助烧剂混合粉体;
步骤3.3,将步骤3.2得到的粉体在冷等静压机中,压力成型成圆片;将成型后的圆片烧结成瓷;将烧结后的陶瓷片打磨、抛光后用无水乙醇洗涤,即得。
在步骤3中冷等静压机用200MPa的压力压5min,成为直径10mm,厚度1mm的圆片,烧结1100℃~1200℃下保温1~5h。
使用银极测试时,银电极烧成在850℃~950℃下保温20~60min,得到介电性能组分x取值。
步骤3.1中助烧剂Bi2O3、CuO、Li2CO3、ZnO和B2O3占混合粉体的质量百分比分别为0.2%、0.2%、0.15%、0.4%和0.07%。
步骤3.3中冷等静压机用200MPa的压力压5min,成为直径10mm,厚度1mm的圆片;烧结900℃~950℃下保温1~5h。
步骤2和步骤3.2中采用行星球磨机,均以250~400r/min的转速球磨12~24h。
步骤1中的Bi2O3、Na2CO3、TiO2、和Ta2O5纯度均不小于98.5%。
步骤3.1中Bi2O3、CuO、Li2CO3、ZnO和B2O3纯度均不小于98.5%。
本发明的有益效果是:本发明以氧化铋、碳酸锂、氧化锌、三氧化二硼和氧化铜,它们按一定比例混合作为烧结助剂掺杂钛酸铋钠-钽酸钠陶瓷制备,通过选取最优组分,通过烧结结助剂的加入来降低钛酸铋钠-钽酸钠陶瓷的烧结温度,从而使以其为材料制备的多层陶瓷电容器,用银作为内电极的制备方法,解决了钛酸铋钠基多层陶瓷电容器使用银钯合金作为内电极成本高的问题。钛酸铋钠陶瓷电容器介电常数提高,具有低介电损耗和宽的温度稳定性,降低烧结温度,使其MLCC可以与银作为内电极共烧。
附图说明
图1是本发明实施例1-4分别制备的(1-x)B0.51NT-xNaTaO3陶瓷的X射线衍射图谱;
图2是本发明实施例1-4分别所制陶瓷的介电温谱图;
图3是本发明实施例5中所制陶瓷的介电温谱图。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明通过钽酸钠掺杂含有过量铋的钛酸铋钠陶瓷以及烧结助剂掺入对应最佳组分的陶瓷制备,将Bi2O3、Na2CO3、TiO2、Ta2O5按照化学计量比称重、混合球磨干燥,然后将不同组分的混合粉末通过等静压技术挤压成片,最后在不同温度烧结即可。
本发明提供低温共烧钛酸铋钠基介质陶瓷的制备方法,具体按照以下步骤进行实施:
步骤1,按照化学计量比(1-x)Bi0.51Na0.5TiO3-xNaTaO3,x=0.2~0.35,称量Bi2O3、Na2CO3、TiO2和Ta2O5,将Bi0.51Na0.5TiO3记为B0.51NT,B0.51NT与NaTaO3的摩尔比为80:20~65:35;步骤1中的Bi2O3、Na2CO3、TiO2、和Ta2O5纯度均不小于98.5%。
步骤2,在球磨机中用酒精为介质,球磨干燥并在800℃~900℃煅烧2h得到掺杂NaTaO3的Bi0.51Na0.5TiO3粉体;步骤2中采用行星球磨机,以250~400r/min的转速球磨12~24h。
步骤3,将步骤2得到的粉体在冷等静压机中,压力成型成圆片,将成型后的圆片烧结成瓷,将烧结后的陶瓷片打磨、抛光后用无水乙醇洗涤,通过银极测试陶瓷的介电性能,确定步骤1中介电性能的组分x,即得。
在步骤3中冷等静压机用200MPa的压力压5min,成为直径10mm,厚度1mm的圆片,烧结1100℃~1200℃下保温1~5h。
使用银极测试时,银电极烧成在850℃~950℃下保温20~60min,得到介电性能组分x取值,通过以下操作确定步骤1中具有最佳介电性能的组分x;
步骤3.1,通过银极测试确定步骤1中组分x取值,称量步骤2中所得到的陶瓷粉体10~20g,再分别称取Bi2O3、CuO、Li2CO3、ZnO和B2O3作为助烧剂加入陶瓷粉体中,得到混合粉体;助烧剂Bi2O3、CuO、Li2CO3、ZnO和B2O3占混合粉体的质量百分比分别为0.2%、0.2%、0.15%、0.4%和0.07%;Bi2O3、CuO、Li2CO3、ZnO和B2O3纯度均不小于98.5%。
步骤3.2,在球磨机中用酒精为介质,球磨干燥得到陶瓷/助烧剂混合粉体;采用行星球磨机,以250~400r/min的转速球磨12~24h。
步骤3.3,将步骤3.2得到的粉体在冷等静压机中,压力成型成圆片;将成型后的圆片烧结成瓷;将烧结后的陶瓷片打磨、抛光后用无水乙醇洗涤,即得。冷等静压机用200MPa的压力压5min,成为直径10mm,厚度1mm的圆片;烧结900℃~950℃下保温1~5h。
本发明低温共烧钛酸铋钠基介质陶瓷的制备方法,通过将Bi2O3、Na2CO3、TiO2、和Ta2O5按照化学计量比称量混合、球磨干燥,以及Bi2O3、CuO、Li2CO3、ZnO和B2O3与80Bi0.51Na0.5TiO3-20NaTaO3按照质量百分比称量混合、球磨干燥,然后将不同组分的混合粉末通过等静压技术挤压成片,最后在不同温度烧结即得,获得了介电性能温度稳定性好,介电损耗低,温度兼容性好,烧结温度低的钛酸铋钠基陶瓷,在宽温及低成本内电极电容器领域的实际应用方面提供了一个很好的参考。
实施例1
步骤1,称取纯度为99%的Bi2O38.67161g、纯度为99.8%的Na2CO32.8775g、纯度为98.5%的TiO25.88798g和纯度为99.99%的Ta2O53.982914g,使得B0.51NT与Ta2O5的摩尔比为80:20;
步骤2,在行星球磨机中用80ml酒精为介质,以250r/min的转速球磨12h,粉体干燥后在800℃煅烧2h得到掺杂NaTaO3的Bi0.51Na0.5TiO3粉体;
步骤3,将粉体在冷等静压机中,用200MPa的压力压5min成为直径10mm,厚度1mm的圆片;将成型后的圆片在1140℃下保温2h烧结成瓷;将烧结后的陶瓷片打磨、抛光后用无水乙醇洗涤,然后被银极测试其介电性能,测得的组分80Bi0.51Na0.5TiO3-20NaTaO3陶瓷具有室温介电常数为877,以及-93~398℃同时满足温度范围内介电损耗低(tanδ≤0.02)和介电常数温度稳定(Δε'/ε'200°≤±15%)的优异介电性能,因而被选为掺杂烧结助剂的组分。
图1中(a)为实施例1中陶瓷粉体的X射线衍射图谱,从图1中(a)可看出,样品呈单一的钙钛矿相,无第二相出现。如图2所示,本实施例1中陶瓷在频率为1kHz下的介电常数曲线图,本实施例1中陶瓷室温下具有最高的介电常数(ε'25℃=877)和优异的温度稳定性(-93~398℃)同时满足介电损耗低(tanδ≤0.02)和介电常数温度稳定(Δε'/ε'200°≤±15%)。
实施例2
步骤1,称取纯度为99%的Bi2O38.06131g、纯度为99.8%的Na2CO32.972207g、纯度为98.5%的TiO25.47359g和纯度为99.99%的Ta2O54.936803g,使得B0.51NT与Ta2O5的摩尔比为75:25;
步骤2,在行星球磨机中用80ml酒精为介质,以250r/min的转速球磨12h,粉体干燥后在850℃煅烧2h得到掺杂NaTaO3的Bi0.51Na0.5TiO3粉体;
步骤3,将粉体在冷等静压机中,用200MPa的压力压5min成为直径10mm,厚度1mm的圆片;将成型后的圆片在1140℃下保温2h烧结成瓷;将烧结后的陶瓷片打磨、抛光后用无水乙醇洗涤,然后被银极测试其介电性能。
图1中(b)是实施例2中陶瓷粉体的X射线衍射图谱,从图中可以看出,样品呈单一的钙钛矿相,无第二相出现。如图2所示,本实施例2中陶瓷在频率为1kHz下的介电常数曲线图,本实施例2中陶瓷室温下具有介电常数(ε'25℃=711)和优异的温度稳定性(-100~400℃)同时满足介电损耗低(tanδ≤0.02)和介电常数温度稳定(Δε'/ε'200°≤±15%)。
实施例3
步骤1,称取纯度为99%的Bi2O37.46119g、纯度为99.8%的Na2CO33.06533g、纯度为98.5%的TiO25.066112g和纯度为99.99%的Ta2O55.87479g,使得B0.51NT与Ta2O5的摩尔比为70:30;
步骤2,在行星球磨机中用80ml酒精为介质,以250r/min的转速球磨12h,粉体干燥后在900℃煅烧2h得到掺杂NaTaO3的Bi0.51Na0.5TiO3粉体;
步骤3,将粉体在冷等静压机中,用200MPa的压力压5min成为直径10mm,厚度1mm的圆片;将成型后的圆片在1140℃下保温2h烧结成瓷;将烧结后的陶瓷片打磨、抛光后用无水乙醇洗涤,然后被银极测试其介电性能。
图1中(c)是实施例3中陶瓷粉体的X射线衍射图谱,从图中可以看出,样品呈单一的钙钛矿相,无第二相出现。如图2所示,本实施例3中陶瓷在频率为1kHz下的介电常数曲线图,本实施例3中陶瓷室温下具有介电常数(ε'25℃=648)和优异的温度稳定性(-100~400℃)同时满足介电损耗低(tanδ≤0.02)和介电常数温度稳定(Δε'/ε'200°≤±15%)。
实施例4
步骤1,称取纯度为99%的Bi2O36.87098g、纯度为99.8%的Na2CO33.15692g、纯度为98.5%的TiO24.665365g和纯度为99.99%的Ta2O56.7972736g,使得B0.51NT与Ta2O5的摩尔比为65:35;
步骤2,在行星球磨机中用80ml酒精为介质,以250r/min的转速球磨12h,粉体干燥后在900℃煅烧2h得到掺杂NaTaO3的Bi0.51Na0.5TiO3粉体;
步骤3,将粉体在冷等静压机中,用200MPa的压力压5min成为直径10mm,厚度1mm的圆片;将成型后的圆片在1140℃下保温2h烧结成瓷;将烧结后的陶瓷片打磨、抛光后用无水乙醇洗涤,然后被银极测试其介电性能。
图1中(d)是实施例4中陶瓷粉体的X射线衍射图谱,从图中可以看出,样品呈单一的钙钛矿相,无第二相出现。如图2所示,本实施例4中陶瓷在频率为1kHz下的介电常数曲线图,本实施例4中陶瓷室温下具有介电常数(ε'25℃=502)和优异的温度稳定性(-100~400℃)同时满足介电损耗低(tanδ≤0.02)和介电常数温度稳定(Δε'/ε'200°≤±15%)。
实施例5
步骤1,称取纯度为99%的Bi2O38.67161g、纯度为99.8%的Na2CO32.8775g、纯度为98.5%的TiO25.88798g和纯度为99.99%的Ta2O53.982914g,使得B0.51NT与Ta2O5的摩尔比为80:20;
步骤2,在行星球磨机中用80ml酒精为介质,以250r/min的转速球磨12h,粉体干燥后在800℃煅烧2h得到80Bi0.51Na0.5TiO3-20NaTaO3粉体;
步骤3,称取80Bi0.51Na0.5TiO3-20NaTaO3粉体15g,以此质量为基准,称取纯度为99%的Bi2O30.03g、CuO0.03g、Li2CO30.0225g、ZnO0.06g和B2O30.0105g,使得Bi2O3、CuO、Li2CO3、ZnO和B2O3占80Bi0.51Na0.5TiO3-20NaTaO3的质量百分比为分别为0.2%、0.2%、0.15%、0.4%和0.07%;
将上述粉体加入行星球磨机中,用80ml酒精为介质,以250r/min的转速球磨12h,干燥得到掺Bi2O3、CuO、Li2CO3、ZnO和B2O3的80Bi0.51Na0.5TiO3-20NaTaO3粉体;
将干燥粉体在冷等静压机中,用200MPa的压力压5min成为直径10mm,厚度1mm的圆片;将成型后的圆片在910℃下保温2h烧结成瓷;将烧结后的陶瓷片打磨、抛光后用无水乙醇洗涤,然后被银极测试其介电性能。
图3是本实施例5中掺杂烧结助剂陶瓷的介电温谱曲线图,可看出在910℃烧结陶瓷片的情况下,实施例5中的陶瓷仍然具有优异的介电性能,在-86~337℃温度范围内仍然同时满足介电损耗低(tanδ≤0.02)和介电常数温度稳定(Δε'/ε'200°≤±15%)。
本发明制备出的B0.51NT与NaTaO3的摩尔比为80:20的陶瓷以及其掺入了烧结助剂的陶瓷,即实施例1的最高的介电常数(ε'25℃=877),优异的温度温度稳定性,-93~398℃温度范围内同时满足介电损耗低(tanδ≤0.02)和介电常数温度稳定(Δε'/ε'200°≤±15%);加入了烧结助剂后,低的烧结温度910℃,以及此温度下陶瓷片优异的介电温度稳定性,-86~337℃温度范围内仍然同时满足介电损耗低(tanδ≤0.02)和介电常数温度稳定(Δε'/ε'200°≤±15%)。
本发明通过掺杂钽酸钠拓宽了含有过量铋的钛酸铋钠介电陶瓷的温度范围,从而满足其在-55℃~300℃的温度范围内介电损耗低(tanδ≤0.02)、介电常数温度稳定性好(Δε'/ε'200°≤±15%)的性能要求;其次又通过向最佳陶瓷组分中加入烧结助剂,将最佳组分陶瓷的烧结温度降到了纯银的熔点以下,并且仍然满足在-55℃~300℃的温度范围内介电损耗低(tanδ≤0.02)、介电常数温度稳定性好(Δε'/ε'200°≤±15%)的性能要求,使其可以用银作为内电极制作MLCC。本发明方法制备的含有过量铋的钽酸钠-钛酸铋钠陶瓷温度稳定性能好、介电损耗低、温度兼容性强,通过引入烧结助剂,使得BNT陶瓷的烧结机理发生了变化,降低了陶瓷烧结温度。该方法成本低、方法简单、可重复性好,所得材料介电性能优异。
Claims (9)
1.低温共烧钛酸铋钠基介质陶瓷的制备方法,其特征在于,具体按照以下步骤进行实施:
步骤1,按照化学计量比(1-x)Bi0.51Na0.5TiO3-xNaTaO3,x=0.2~0.35,称量Bi2O3、Na2CO3、TiO2和Ta2O5,将Bi0.51Na0.5TiO3记为B0.51NT,B0.51NT与NaTaO3的摩尔比为80:20~65:35;
步骤2,在球磨机中用酒精为介质,球磨干燥并在800℃~900℃煅烧2h得到掺杂NaTaO3的Bi0.51Na0.5TiO3粉体;
步骤3,将步骤2得到的粉体在冷等静压机中,压力成型成圆片,将成型后的圆片烧结成瓷,将烧结后的陶瓷片打磨、抛光后用无水乙醇洗涤,通过银极测试陶瓷的介电性能,通过银极测试陶瓷的介电性能,确定步骤1中具有最佳介电性能的组分x,即得。
2.根据权利要求1所述的低温共烧钛酸铋钠基介质陶瓷的制备方法,其特征在于,根据所述步骤3得到介电性能组分x取值,通过以下操作确定步骤1中具有最佳介电性能的组分x;
步骤3.1,通过步骤3确定步骤1中组分x取值,称量步骤2中所得到的陶瓷粉体10~20g,再分别称取Bi2O3、CuO、Li2CO3、ZnO和B2O3作为助烧剂加入陶瓷粉体中,得到混合粉体;
步骤3.2,在球磨机中用酒精为介质,球磨干燥得到陶瓷/助烧剂混合粉体;
步骤3.3,将步骤3.2得到的粉体在冷等静压机中,压力成型成圆片;将成型后的圆片烧结成瓷;将烧结后的陶瓷片打磨、抛光后用无水乙醇洗涤,即得。
3.根据权利要求1所述的低温共烧钛酸铋钠基介质陶瓷的制备方法,其特征在于,在所述步骤3中冷等静压机用200MPa的压力压5min,成为直径10mm,厚度1mm的圆片,烧结1100℃~1200℃下保温1~5h。
4.根据权利要求1所述的低温共烧钛酸铋钠基介质陶瓷的制备方法,其特征在于,使用银极测试时,银电极烧成在850℃~950℃下保温20~60min,得到介电性能组分x取值。
5.根据权利要求2所述的低温共烧钛酸铋钠基介质陶瓷的制备方法,其特征在于,所述步骤3.1中助烧剂Bi2O3、CuO、Li2CO3、ZnO和B2O3占混合粉体的质量百分比分别为0.2%、0.2%、0.15%、0.4%和0.07%。
6.根据权利要求2所述的低温共烧钛酸铋钠基介质陶瓷的制备方法,其特征在于,步骤3.3中冷等静压机用200MPa的压力压5min,成为直径10mm,厚度1mm的圆片;烧结900℃~950℃下保温1~5h。
7.根据权利要求2所述的低温共烧钛酸铋钠基介质陶瓷的制备方法,其特征在于,步骤2和步骤3.2中采用行星球磨机,均以250~400r/min的转速球磨12~24h。
8.根据权利要求1所述的低温共烧钛酸铋钠基介质陶瓷的制备方法,其特征在于,步骤1中的Bi2O3、Na2CO3、TiO2、和Ta2O5纯度均不小于98.5%。
9.根据权利要求2所述的低温共烧钛酸铋钠基介质陶瓷的制备方法,其特征在于,步骤3.1中Bi2O3、CuO、Li2CO3、ZnO和B2O3纯度均不小于98.5%。
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