CN114804872A - 一种高居里温度高稳定性偏铌酸铅基压电陶瓷材料及其制备方法 - Google Patents
一种高居里温度高稳定性偏铌酸铅基压电陶瓷材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种高居里温度高稳定性偏铌酸铅基压电陶瓷材料及其制备方法，偏铌酸铅基压电陶瓷，用通式Pb(1+δ‑x‑y)BaxCay[Nb(1‑z)Mnz]206表示材料组成，式中x、y、z表示组成元素的摩尔数，δ表示A位Pb过量的摩尔数，其中，0≤x≤0.1,0≤y≤0.1,0≤x+y≤0.1,0≤z≤0.1,0≤δ≤0.05。其制备方法包括混料、预烧、造粒、成型及排塑、烧结、被银、极化工艺步骤。本发明制备的偏铌酸铅基压电陶瓷其变温压电应变系数d* 33在室温～350℃温度范围内至少为75pC/N以上，优选为80pC/N以上，在高端声波石油测井等高温作业环境，显示出良好的应用前景。
Description
技术领域
本发明涉及压电陶瓷领域，主要是一种高居里温度高稳定性偏铌酸铅基压电陶瓷材料及其制备方法。
背景技术
随着我国成为世界第二大经济体，我国的能源需求逐渐增加，根据中国石油和化学工业联合会数据，2020年我国国内石油产量1.95亿吨，同比增长1.6％；原油表观消费量7.36亿吨，同比增长5.6％,原油对外依存度达到73.5％,且对外依存度不断上升，而同比新增探明油气地质储量降至10年来最低点，保障能源安全成为当务之急。随着高品质常规油气资源储量的减小，我国油气资源开发日益转向超深油气、页岩油气、深水油气、煤层气等领域。我国油气勘探开发区域中复杂和隐蔽岩性油气藏占整个油气资源的60％，勘探深度越来越深，难度越来越大，而这些资源的开采都迫切需要能在350℃稳定工作的压电陶瓷。
常用PZT压电陶瓷的居里温度一般在320℃～360℃的范围，其工作温度上限一般是在居里温度的1/2处；因而，目前国内多极子阵列声波测井仪器一般只能用到150℃左右的环境温度，远远不能满足深部(大于5000米)油气勘探的需要。长期以来，我国的高端声波测井仪器一直依赖进口，价格高昂且常常受制于人(如进口一套多极子阵列声波测井仪高达1300万人民币)，因此，研究制备具有高居里温度的压电陶瓷具有重要意义。
偏铌酸铅(PbNb206)是最早发现的钨青铜结构的铁电体，该体系具有压电系数各向异性大，品质因数低，且在较高的居里温度(Tc＝570℃)下不易退极化的特点，因此特别适合用于制造耐高温耐高静水压的换能器。但是纯的偏铌酸铅存在着压电活性差，机电耦合系数低，以及不易烧结等缺点。掺杂改性可以改善偏铌酸铅压电陶瓷的烧结性能和压电特性,Kunihiro等通过在PbNb206中固溶大量的Ba2+和La3+离子制备了(Pb0.62Ba0.38)0.94La0.04Nb206陶瓷材料，其具有较高的压电常数d33＝180pC/N,但同时居里温度会急剧下降，使其并不适合在高温下使用；周静等人通过Cr203、Y203、Sm203、Nd203和Ce02等氧化物进行掺杂改性，改善了材料的烧结性能，但是其居里温度下降到420℃左右[2]；专利CN 1064941C提供了一种铌酸铅压电陶瓷组合物，但其居里温度也只是高于400℃，相比纯偏铌酸铅居里温度降低很多，并且上述研究均没有给出高温条件下偏铌酸铅压电陶瓷的性能变化情况，鉴于上述情况，因而有必要继续进行掺杂改性研究，以期寻找到新的高居里温度高稳定性压电陶瓷材料。
发明内容
本发明的目的在于克服现有技术存在的不足，而提供一种高居里温度高稳定性偏铌酸铅基压电陶瓷材料及其制备方法，主要应用于高端声波石油测井等高温作业环境。
本发明的目的是通过如下技术方案来完成的。一种高居里温度高稳定性偏铌酸铅基压电陶瓷材料，用通式Pb(1+δ-x-y)BaxCay[Nb(1-z)Mnz]206表示的材料组成，式中x、y、z表示组成元素的摩尔数，δ表示A位Pb过量的摩尔数，其中，0≤x≤0.1,0≤y≤0.1,0≤x+y≤0.1,0≤z≤0.1,0≤δ≤0.05。
用通式Pb(1+δ-x-y)BaxCay[Nb(1-z)Mnz]206表示的材料组成，式中x、y、z表示组成元素的摩尔数，δ表示A位Pb过量的摩尔数，其较优的取值范围为0.01≤x≤0.08,0.01≤y≤0.08,0.02≤x+y≤0.1,0≤z≤0.08,0.02≤δ≤0.04。
较佳的，在A位采用Ba2+、Ca2+同时复合取代及Pb2+过量的形式，从而实现偏铌酸铅基压电陶瓷材料压电性能稳定性的提升。
较佳的，所述偏铌酸铅基压电陶瓷材料的居里温度为550℃以上。
较佳的，所述偏铌酸铅基压电陶瓷材料，其变温压电应变系数d* 33在室温～350℃温度范围内至少为75pC/N以上，优选为80pC/N以上。
本发明同时公开了一种制备上述高居里温度高稳定性偏铌酸铅基压电陶瓷材料的方法，包括下述步骤：
1)混料：根据高居里温度高稳定性偏铌酸铅基压电陶瓷材料的组成通式Pb(1+δ-x-y)BaxCay[Nb(1-z)Mnz]206，以Pb304、BaC03、CaC03、Nb205、Mn02为原料，按照化学计量比进行称量后，加入到滚筒磨中湿法混料18～20小时，充分混合均匀后出浆；
2)预烧：将混合好的料浆烘干，压块后置于氧化铝坩埚中，然后在800～900℃，保温2小时预烧合成；
3)造粒：预烧后的料块粉碎，然后置于搅拌磨中进行搅拌细磨，搅拌时按重量比，预烧料：锆球：纯净水＝1：2：0.7比例进行，搅拌3小时后加入聚乙烯醇粘结剂，然后在喷雾塔中进行造粒；
4)成型：通过干压法成型制得坯体；
5)排塑：坯体在700～750℃保温2小时排塑；
6)烧结：排塑后坯体在Al203坩埚中密封，于1250～1300℃保温2-3小时烧结；
7)被银：烧结后瓷体经研磨、清洗后被银，于780℃烧银；
8)极化：在170℃硅油中，施加4.0～5.0kv/mm直流电场极化，制得高居里温度高稳定性偏铌酸铅基压电陶瓷材料。
本发明的烧结工艺步骤6)中，排塑后坯体在Al203坩埚中密封，优选于1270～1290℃保温2-3小时烧结。
本发明的有益效果为：提供了一种居里温度高、稳定性好的偏铌酸铅基高温压电陶瓷，通过在A位采用Ba2+、Ca2+同时复合取代及Pb2+过量的形式，采用一次合成、一次烧结的制备方法，实现了偏铌酸铅基压电陶瓷材料的简单、快速制备及压电性能稳定性的提升；本发明制备的偏铌酸铅基压电陶瓷材料其变温压电应变系数d* 33在室温～350℃温度范围内至少为75pC/N以上，优选为80pC/N以上，在高端声波石油测井等高温作业环境方面，显示出良好的应用前景。
附图说明
图1是本发明实施例1～3的压电陶瓷的介电常数温谱图；
图2是本发明实施例1～3的压电陶瓷的介电损耗温谱图；
图3是本发明实施例1的压电陶瓷变温压电应变系数图；
图4是本发明实施例1的压电陶瓷断面显微形貌图。
具体实施方式
下面将结合附图和实施例对本发明做详细的介绍：
实施例1：
1)混料：根据高居里温度高稳定性偏铌酸铅基压电陶瓷材料的组成式Pb0.97Ba0.03Ca0.03[Nb0.97Mn0.03]206，以Pb304、BaC03、CaC03、Nb205、Mn02为原料，按照化学计量比进行称量后，加入到滚筒磨中湿法混料18～20小时，充分混合均匀后出浆；
2)预烧：将混合好的料浆烘干，压块后置于氧化铝坩埚中，然后在880℃，保温2小时预烧合成；
3)造粒：预烧后的料块粉碎，然后置于搅拌磨中进行搅拌细磨，搅拌时按重量比，预烧料：锆球：纯净水＝1：2：0.7比例进行，搅拌3小时后加入聚乙烯醇粘结剂，然后在喷雾塔中进行造粒；
4)成型：通过干压法成型制得坯体；
5)排塑：坯体在740℃保温2小时排塑；
6)烧结：排塑后坯体在Al203坩埚中密封，于1280℃保温3小时烧结；
7)被银：烧结后瓷体经研磨、清洗后被银，于780℃烧银；
8)极化：在170℃硅油中，施加4.0～5.0kv/mm直流电场极化，制得高居里温度高稳定性偏铌酸铅基压电陶瓷材料。
实施例2：
1)混料：根据高居里温度高稳定性偏铌酸铅基压电陶瓷材料的组成式Pb0.97Ba0.03Ca0.03[Nb0.95Mn0.05]206，以Pb304、BaC03、CaC03、Nb205、Mn02为原料，按照化学计量比进行称量后，加入到滚筒磨中湿法混料18～20小时，充分混合均匀后出浆；
步骤2)—8)与实施例1相同。
实施例3：
1)混料：根据高居里温度高稳定性偏铌酸铅基压电陶瓷材料的组成式Pb0.97Ba0.03Ca0.03[Nb0.92Mn0.08]206，以Pb304、BaC03、CaC03、Nb205、Mn02为原料，按照化学计量比进行称量后，加入到滚筒磨中湿法混料18～20小时，充分混合均匀后出浆；
步骤2)—8)与实施例1相同。
将实施例1—3制备出的压电陶瓷样品进行测试，结果如下表1所示：
1)采用阿基米德排水法，测试样品的体积密度ρ；
2)采用阻抗分析仪，测试样品在1KHz下的介电常数εT 33和介电损耗tgδ，观察样品的异常介电峰温度，确定居里温度Tc；
3)采用准静态d33测量仪，测试样品在室温条件下的压电应变系数d33；
4)采用高温d33测试系统，测试样品在变温条件下的压电应变系数d* 33；
5)采用扫描电子显微镜，对样品断面进行表征；
表1本发明各实施例压电陶瓷材料性能
当然，本发明还可有其他多种实施例，熟悉本领域的技术人员可根据本发明做出各种相应的改变和变形，但这些相应的改变和变形都应属于本发明所附的权利要求的保护范围。
Claims (7)
1.一种高居里温度高稳定性偏铌酸铅基压电陶瓷材料，其特征在于：用通式Pb(1+δ-x-y)BaxCay[Nb(1-z)Mnz]206表示的材料组成，式中x、y、z表示组成元素的摩尔数，δ表示A位Pb过量的摩尔数，其中，0≤x≤0.1,0≤y≤0.1,0≤x+y≤0.1,0≤z≤0.1,0≤δ≤0.05。
2.根据权利要求1所述的高居里温度高稳定性偏铌酸铅基压电陶瓷材料，其特征在于：在通式Pb(1+δ-x-y)BaxCay[Nb(1-z)Mnz]206表示的材料组成中，其中，0.01≤x≤0.08,0.01≤y≤0.08,0.02≤x+y≤0.1,0≤z≤0.08,0.02≤δ≤0.04。
3.根据权利要求1或2所述的高居里温度高稳定性偏铌酸铅基压电陶瓷材料，其特征在于：在A位采用Ba2+、Ca2+同时复合取代及Pb2+过量的形式，用于提升偏铌酸铅基压电陶瓷材料压电性能稳定性。
4.根据权利要求1或2所述的高居里温度高稳定性偏铌酸铅基压电陶瓷材料，其特征在于：所述偏铌酸铅基压电陶瓷材料的居里温度为550℃以上。
5.根据权利要求1或2所述的高居里温度高稳定性偏铌酸铅基压电陶瓷材料，其特征在于：所述偏铌酸铅基压电陶瓷材料的变温压电应变系数d* 33在室温～350℃温度范围内至少为75pC/N以上。
6.一种如权利要求1-5中任一项所述的高居里温度高稳定性偏铌酸铅基压电陶瓷材料的制备方法，其特征在于，包括下述步骤：
1)混料：根据高居里温度高稳定性偏铌酸铅基压电陶瓷材料的组成通式Pb(1+δ-x-y)BaxCay[Nb(1-z)Mnz]206，以Pb304、BaC03、CaC03、Nb205、Mn02为原料，按照化学计量比进行称量后，加入到滚筒磨中湿法混料18～20小时，充分混合均匀后出浆；
2)预烧：将混合好的料浆烘干，压块后置于氧化铝坩埚中，然后在800～900℃，保温2小时预烧合成；
3)造粒：预烧后的料块粉碎，然后置于搅拌磨中进行搅拌细磨，搅拌时按重量比，预烧料：锆球：纯净水＝1：2：0.7比例进行，搅拌3小时后加入聚乙烯醇粘结剂，然后在喷雾塔中进行造粒；
4)成型：通过干压法成型制得坯体；
5)排塑：坯体在700～750℃保温2小时排塑；
6)烧结：排塑后坯体在Al203坩埚中密封，于1250～1300℃保温2-3小时烧结；
7)被银：烧结后瓷体经研磨、清洗后被银，于780℃烧银；
8)极化：在170℃硅油中，施加4.0～5.0kv/mm直流电场极化，制得高居里温度高稳定性偏铌酸铅基压电陶瓷材料。
7.根据权利要求6所述高居里温度高稳定性偏铌酸铅基压电陶瓷材料的制备方法，其特征在于，所述步骤6)的烧结温度为1270～1290℃。
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