CN117263679A - 一种Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料及其制备方法 - Google Patents

一种Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料及其制备方法 Download PDF

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CN117263679A
CN117263679A CN202311186211.4A CN202311186211A CN117263679A CN 117263679 A CN117263679 A CN 117263679A CN 202311186211 A CN202311186211 A CN 202311186211A CN 117263679 A CN117263679 A CN 117263679A
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王竹梅
骆雯琴
沈宗洋
李月明
左建林
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Jingdezhen Ceramic Institute
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Abstract

本发明公开了一种Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料及其制备方法，针对CaBi4Ti4O15陶瓷材料A位的Ca2+离子，采用具有12配位的高价Ce4+离子进行掺杂取代，针对B位的Ti4+离子，采用复合高价离子[Ga1/3Mo2/3]5+进行掺杂取代，通过上述复合掺杂改性，在不降低居里温度的同时，提高其压电性能和高温电阻率，从而提供了一种新型的、综合电性能优良的、环境友好型压电陶瓷材料，该材料具有良好的高温稳定性，在高温领域具有广阔的应用前景。本发明制备方法采用先进的陶瓷制备工艺，烧成温度低，制备成本低，工艺简单易操作，影响因素易控制，适合于大批量工业化生产，有助于推广和应用。

Description

一种Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料及其制 备方法
技术领域
本发明涉及压电陶瓷材料技术领域，尤其涉及一种铋层状结构钛酸铋钙高温压电陶瓷材料及其制备方法。
背景技术
目前，应用最广的压电陶瓷材料主要是钙钛矿结构的PZT基压电陶瓷，但是这类压电陶瓷的居里温度一般在400℃以下，由于压电材料退极化现象的存在，压电材料在居里温度以上无法正常工作。随着航空航天、地质勘探等工作的飞速发展和顺应人类社会可持续发展的需求，因此有必要寻求一种居里温度高、压电性能优异的环境友好型压电材料。
铋层状结构陶瓷具有居里温度高、耐疲劳性能好等优点，是适用在高温环境下的候选材料。铋层状结构陶瓷材料是由(Bi2O2)2+层和钙钛矿结构晶格层相互交替叠加而成，其化学通式为(Bi2O2)2+(Am-1BmO3m+1)2-，其中，CaBi4Ti4O15(CBT)是一种典型的铋层状结构铁电材料，A为12配位的Ca2+和Bi3+，B为6配位的Ti4+，m＝4，该材料具有高居里温度(TC≈790℃)、高压电电压系数、低电导率等优点，但其压电活性低、谐振频率温度系数较大，这些因素都制约着它在高温领域的应用。因此，如何在不降低居里温度的同时，提升压电活性，获得综合电性能优良的CBT压电陶瓷材料，成为了高温压电陶瓷材料领域研究的一个重要课题。
发明内容
本发明的目的在于克服现有技术的不足，提供一种Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料，针对CaBi4Ti4O15陶瓷材料A位的Ca2+离子，采用具有12配位的高价Ce4+离子进行掺杂取代，针对B位的Ti4+离子，采用复合高价离子[Ga1/3Mo2/3]5+进行掺杂取代，以便通过上述复合掺杂改性，在不降低居里温度的同时，提高其压电性能和高温电阻率，从而提供一种新型的、综合电性能优良的、环境友好型压电陶瓷材料。本发明的另一目的在于提供上述Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法。
本发明的目的通过以下技术方案予以实现：
本发明提供的一种Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料，以具有12配位的高价Ce4+离子掺杂取代CaBi4Ti4O15中A位的Ca2+离子，以复合高价离子[Ga1/3Mo2/3]5+掺杂取代CaBi4Ti4O15中B位的Ti4+离子，形成的化学通式为Ca1-xCexBi4Ti4-y[Ga1/3Mo2/3]yO15，其中0.045≤x≤0.075，0.05≤y≤0.075。
上述方案中，本发明所述压电陶瓷材料的d33≥28pC/N，TC≥775℃；500℃时电阻率(ρ)≥3.5×107Ω@cm，介电损耗(tanδ)≤0.35％；600℃退火后的d33≥24pC/N。
本发明的另一目的通过以下技术方案予以实现：
本发明提供的上述Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法，包括以下步骤：
(1)预合成前驱体粉料的制备
以CaCO3、CeO2、Bi2O3、TiO2、Ga2O3、MoO3作为与所述化学通式中Ca、Ce、Bi、Ti、Ga、Mo对应的原料，将各原料按照化学通式中的化学计量进行配料，然后以无水乙醇为球磨介质进行一次球磨处理，得到的物料经烘干、过筛、压制成型后置于密封的坩埚内进行煅烧处理；然后将煅烧处理后的物料经研磨、过筛后，进行二次球磨处理，得到的物料经烘干、研磨、过筛，即制得预合成前驱体粉料；
(2)高温压电陶瓷材料的制备
将所述预合成前驱体粉料装入石墨模具中，置于放电等离子烧结炉内进行一次煅烧处理，得到含碳烧制品；然后将所述含碳烧制品置于普通高温炉内进行二次煅烧处理以进行脱碳，得到脱碳烧制品；最后将所述脱碳烧制品进行极化处理，即制得高温压电陶瓷材料。
进一步地，本发明制备方法所述步骤(1)中各原料的纯度不低于99.9％。压制成型的压力为4～6Mpa；煅烧处理为以5℃/min升温至800～850℃。
进一步地，本发明制备方法所述步骤(2)中一次煅烧处理为，放电等离子烧结炉压力为25～30MPa、直流脉冲电流为500～550A，以100℃/min升温至800～850℃，保温5～8min后，停止直流脉冲电流，然后释放压力，随炉冷却至室温。二次煅烧处理为，5℃/min升至600～650℃，保温3～4h，随炉冷却至室温。
进一步地，本发明制备方法所述步骤(2)中极化处理为，先将所述脱碳烧制品的表面进行抛光处理；然后进行涂电极处理，即在抛光后脱碳烧制品的上下表面被上银电极；之后以5℃/min升至650～680℃进行煅烧，保温40～60min，随炉冷却至室温；最后在180～200℃的高温硅油中，加以5～10kV/mm的直流电压进行极化，极化时间为20～30min。
利用上述Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法制得的产品。
本发明具有以下有益效果：
(1)在制备CaBi4Ti4O15压电陶瓷材料的过程中，在高温下由于铋的挥发，必然形成铋空位从而产生空位缺陷。针对此现象，本发明采用价态比A位Ca2+离子高的Ce4+离子对其进行掺杂取代，同时亦采用价态比B位Ti4+离子高的复合离子[Ga1/3Mo2/3]5+对其进行掺杂取代，使A、B位均由于缺陷而使类钙钛矿层(Am-1BmO3m+1)2-产生电子，从而增强了铋氧层(Bi2O2)2+和类钙钛矿层(Am-1BmO3m+1)2-之间的相互作用，进而改变了晶粒的生长行为，最终获得了性能优异的CaBi4Ti4O15高温压电陶瓷材料。
(2)本发明采用先进的放电等离子烧结技术，该烧结技术所需烧结温度低、时间短，因而能耗低，且烧结后材料致密度高，可获得性能优异的CaBi4Ti4O15高温压电陶瓷材料。
(3)本发明Ce、Ga、Mo共掺杂型CaBi4Ti4O15压电陶瓷材料，居里温度≥775℃，压电常数d33≥28pC/N，600℃退火后的d33≥24pC/N；500℃时电阻率≥3.5×107Ω·cm，介电损耗≤0.35％。该材料具有良好的高温稳定性，在高温领域具有广阔的应用前景。
(4)本发明制备方法采用先进的陶瓷制备工艺，烧成温度低，制备成本低，工艺简单易操作，影响因素易控制，适合于大批量工业化生产，有助于推广和应用。
附图说明
下面将结合实施例和附图对本发明作进一步的详细描述：
图1是本发明实施例制备的Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷、以及对比例压电陶瓷材料的XRD图；
图2是本发明实施例制备的Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷的介电常数随温度变化曲线。
具体实施方式
实施例一：
本实施例一种Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法，其步骤如下：
(1)预合成前驱体粉料的制备
以纯度为99.9％的CaCO3、CeO2、Bi2O3、TiO2、Ga2O3、MoO3作为与化学通式Ce0.06Bi4Ti3.94[Ga1/3Mo2/3]0.06O15中Ca、Ce、Bi、Ti、Ga、Mo对应的原料，将各原料按照该化学通式中的化学计量进行配料，然后以无水乙醇为球磨介质，按照球∶料∶无水乙醇＝4∶1∶3，以转速400r/min在行星球磨机上进行一次球磨处理24h，得到的物料经烘干、过80目筛，在4Mpa下压制成型后置于密封的坩埚内，以5℃/min升温至800℃在氧化气氛下进行煅烧处理，保温时间为2h；将煅烧处理后的物料经研磨、过80目筛后，采用与一次球磨处理相同的工艺进行二次球磨处理后，得到的物料经烘干、研磨、过80目筛，即制得预合成前驱体粉料；
(2)高温压电陶瓷材料的制备
(2-1)取0.8g上述预合成前驱体粉料装入直径为20mm的圆柱形石墨模具中，置于放电等离子烧结炉内，设置压力为25MPa、直流脉冲电流为500A，以100℃/min升温至800℃进行一次煅烧处理，保温5min后，停止直流脉冲电流，然后释放压力，随炉冷却至室温，得到含碳烧制品；
(2-2)将上述含碳烧制品置于普通高温炉内，以5℃/min升至600℃进行二次煅烧处理而进行脱碳，保温3h，随炉冷却至室温，得到脱碳烧制品；
(2-3)将上述脱碳烧制品进行以下极化处理，先将上述脱碳烧制品的表面进行抛光处理；然后进行涂电极处理，即在抛光后脱碳烧制品的上下表面被上银电极；之后以5℃/min升至650℃进行煅烧，保温40min，随炉冷却至室温；最后在180℃的高温硅油中，加以5～10kV/mm的直流电压进行极化，极化时间为20min，即制得高温压电陶瓷材料。
实施例二：
本实施例一种Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法，与实施例一不同之处在于：
1、本实施例化学通式为Ca0.95Ce0.05Bi4Ti3.945[Ga1/3Mo2/3]0.055O15。
2、步骤(1)中的煅烧温度为820℃；步骤(2-1)中煅烧温度为820℃。
实施例三：
本实施例一种Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法，与实施例一不同之处在于：
1、本实施例化学通式为Ca0.93Ce0.07Bi4Ti3.93[Ga1/3Mo2/3]0.07O15。
2、步骤(1)中的煅烧温度为820℃；步骤(2-1)中煅烧温度为820℃。
对比例：
以未掺杂的、化学通式为CaBi4Ti4O15的高温压电陶瓷材料作为对比例，其制备步骤同实施例一。
本发明实施例和对比例压电陶瓷材料的XRD晶相图谱如图1所示，从图1中可以看出，各实施例和对比例制得的压电陶瓷材料的各衍射峰与标准图谱PDF 00-052-1640完全吻合，说明所得材料为单一晶相的CaBi4Ti4O15材料。
本发明实施例制备的Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷的介电常数随温度变化曲线如图2所示。本发明实施例和对比例压电陶瓷材料的性能测试结果如表1所示。
表1本发明实施例和对比例陶瓷材料的性能

Claims (9)

1.一种Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料，其特征在于：以具有12配位的高价Ce4+离子掺杂取代CaBi4Ti4O15中A位的Ca2+离子，以复合高价离子[Ga1/3Mo2/3]5+掺杂取代CaBi4Ti4O15中B位的Ti4+离子，形成的化学通式为Ca1-xCexBi4Ti4-y[Ga1/3Mo2/3]yO15，其中0.045≤x≤0.075，0.05≤y≤0.075。
2.根据权利要求1所述的Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料，其特征在于：所述压电陶瓷材料的d33≥28pC/N，TC≥775℃；500℃时电阻率(ρ)≥3.5×107Ω@cm，介电损耗(tanδ)≤0.35％；600℃退火后的d33≥24pC/N。
3.权利要求1或2所述Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法，其特征在于包括以下步骤：
(1)预合成前驱体粉料的制备
以CaCO3、CeO2、Bi2O3、TiO2、Ga2O3、MoO3作为与所述化学通式中Ca、Ce、Bi、Ti、Ga、Mo对应的原料，将各原料按照化学通式中的化学计量进行配料，然后以无水乙醇为球磨介质进行一次球磨处理，得到的物料经烘干、过筛、压制成型后置于密封的坩埚内进行煅烧处理；然后将煅烧处理后的物料经研磨、过筛后，进行二次球磨处理，得到的物料经烘干、研磨、过筛，即制得预合成前驱体粉料；
(2)高温压电陶瓷材料的制备
将所述预合成前驱体粉料装入石墨模具中，置于放电等离子烧结炉内进行一次煅烧处理，得到含碳烧制品；然后将所述含碳烧制品置于普通高温炉内进行二次煅烧处理以进行脱碳，得到脱碳烧制品；最后将所述脱碳烧制品进行极化处理，即制得高温压电陶瓷材料。
4.根据权利要求3所述Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法，其特征在于：所述步骤(1)中各原料的纯度不低于99.9％。
5.根据权利要求3所述Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法，其特征在于：所述步骤(1)中压制成型的压力为4～6Mpa；煅烧处理为以5℃/min升温至800～850℃。
6.根据权利要求3所述Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法，其特征在于：所述步骤(2)中一次煅烧处理为，放电等离子烧结炉压力为25～30MPa、直流脉冲电流为500～550A，以100℃/min升温至800～850℃，保温5～8min后，停止直流脉冲电流，然后释放压力，随炉冷却至室温。
7.根据权利要求3所述Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法，其特征在于：所述步骤(2)中二次煅烧处理为，5℃/min升至600～650℃，保温3～4h，随炉冷却至室温。
8.根据权利要求3所述Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法，其特征在于：所述步骤(2)中极化处理为，先将所述脱碳烧制品的表面进行抛光处理；然后进行涂电极处理，即在抛光后脱碳烧制品的上下表面被上银电极；之后以5℃/min升至650～680℃进行煅烧，保温40～60min，随炉冷却至室温；最后在180～200℃的高温硅油中，加以5～10kV/mm的直流电压进行极化，极化时间为20～30min。
9.利用权利要求3-8之一所述Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料的制备方法制得的产品。
CN202311186211.4A 2023-09-14 2023-09-14 一种Ce、Ga、Mo共掺杂型CaBi4Ti4O15高温压电陶瓷材料及其制备方法 Pending CN117263679A (zh)

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