CN116813339A - 一种无铅压电陶瓷及其制备方法 - Google Patents

一种无铅压电陶瓷及其制备方法 Download PDF

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CN116813339A
CN116813339A CN202310540861.8A CN202310540861A CN116813339A CN 116813339 A CN116813339 A CN 116813339A CN 202310540861 A CN202310540861 A CN 202310540861A CN 116813339 A CN116813339 A CN 116813339A
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piezoelectric ceramic
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CN116813339B (zh
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廖忠新
邱
黄仕华
张曙光
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Audiowell Electronics Guangdong Co ltd
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Abstract

本发明公开了一种无铅压电陶瓷及其制备方法，涉及陶瓷技术领域。无铅压电陶瓷的化学通式为：aK0.48Na0.54Nb0.96O3‑bSb2O3‑cZrO2‑dBi2O3‑xFe2O3‑yCuO‑zMnO2，其中0.92≤a≤0.98,0.02≤b≤0.08,0.02≤c≤0.08,0.01≤d≤0.05,0≤x≤0.03，0≤y≤0.03，0≤z≤0.03。本申请通过引入氧化铁、氧化铜、氧化锰三者协同辅助铌酸钾钠基陶瓷的烧结，可以降低陶瓷的烧结温度，避免高温下钾钠元素的挥发，在该较低烧结温度的条件下提高铌酸钾钠基陶瓷的烧结性能，减少气孔率，提高了压电陶瓷的致密度和压电性能。

Description

一种无铅压电陶瓷及其制备方法
技术领域
本发明涉及陶瓷技术领域，尤其涉及一种无铅压电陶瓷及其制备方法。
背景技术
压电陶瓷由于其具有良好的机电耦合特性，在传感器、换能器、制动器等领域有着广泛的应用。市场上主流的压电陶瓷材料是PZT铅基陶瓷，有毒的铅元素含量超过质量分数的60％。随着人们环保意识的逐渐增强，各国出台了相关的法律法规，PZT在未来的持续大规模应用受到了限制，压电陶瓷的无铅化迫在眉睫。其中铌酸钾钠基陶瓷由于良好的电学特性和较高的居里温度而被广泛认可是最有潜力在某些领域替代铅基陶瓷的无铅压电陶瓷之一。
然而，铌酸钾钠基陶瓷存在烧结性差的问题，在高温下钾钠元素容易挥发，造成配方成分偏离设计组成，同时陶瓷极化产生的漏电流偏大，导致陶瓷难以极化，压电性能偏低；而在低温下陶瓷晶粒难以成型生长，陶瓷致密度低，压电性能低。而铌酸钾钠基陶瓷的电性能与致密度有着极为密切的联系，陶瓷烧结性差导致其致密度难以提升，压电性能难以提高，这极大地限制了铌酸钾钠基陶瓷的发展和应用。
发明内容
本发明提供了一种无铅压电陶瓷及其制备方法，可以降低压电陶瓷的烧结温度，提高烧结性能，制备获得致密度高且压电性能优越的陶瓷。
为了解决上述技术问题，本发明目的之一提供了一种无铅压电陶瓷，所述无铅压电陶瓷的化学通式为：aK0.48Na0.54Nb0.96O3-bSb2O3-cZrO2-dBi2O3-xFe2O3-yCuO-zMnO2，其中0.92≤a≤0.98,0.02≤b≤0.08,0.02≤c≤0.08,0.01≤d≤0.05,0≤x≤0.03，0≤y≤0.03，0≤z≤0.03。
作为优选方案，x为0-0.01，y为0-0.01，z为0-0.01。
作为优选方案，a为0.94-0.96，b为0.04-0.06，c为0.04-0.06，d为0.01-0.03。
为了解决上述技术问题，本发明目的之二提供一种无铅压电陶瓷的制备方法，包括以下步骤：
(1)将碳酸钾、碳酸钠、五氧化二铌、三氧化二锑、氧化锆、氧化铋原料按化学计量比称量，球磨、烘干获得混合料；
(2)将混合料进行预烧，制得预烧粉料；
(3)将预烧粉料、氧化铜、氧化锰、氧化铁分别以无水乙醇作为球磨介质单独进行第一次球磨，之后按化学计量比将预烧粉料、氧化铜、氧化锰、氧化铁混合进行第二次球磨，烘干第二次球磨后获得的粉料，加入PVA溶液并造粒，用模具干压成陶瓷生胚；
(4)陶瓷生胚排完胶后进行烧结，烧结温度为1120-1210℃，保温时间为2-6h，对烧结得到的陶瓷平磨，然后印银烧银，得到陶瓷片，最后对陶瓷片进行极化处理，获得无铅压电陶瓷。
作为优选方案，在步骤(1)中，以无水乙醇作为球磨介质，球磨时间为2-10h。
作为优选方案，在步骤(2)中，预烧温度为750-950℃，保温时间为3-9h。
作为优选方案，在步骤(3)中，第一次球磨5-20h，第二次球磨5-20h，PVA溶液的质量分数为3-10％。
作为优选方案，在步骤(3)中，第二次球磨后最终平均粒径为0.6-1.0μm。
作为优选方案，在步骤(3)中，PVA溶液占粉料和PVA溶液总质量的3％-10％。
作为优选方案，在步骤(4)中，烧银温度为600-800℃，保温时间20-50mi n，极化温度为70-120℃，极化电压为2-4KV/mm，极化时间为10-30mi n。
相比于现有技术，本发明实施例具有如下有益效果：
本申请通过引入氧化铁、氧化铜、氧化锰三者协同辅助铌酸钾钠基陶瓷的烧结，可以降低陶瓷的烧结温度，避免高温下钾钠元素的挥发，在该较低烧结温度的条件下提高铌酸钾钠基陶瓷的烧结性能，减少气孔率，预烧后加入金属氧化物可以防止预烧时金属氧化物固溶进铌酸钾钠晶格中从而达不到形成液相降低陶瓷烧结温度的目的，提高了压电陶瓷的致密度和压电性能。
附图说明
图1：为本发明实施例二中一种无铅压电陶瓷的XRD图谱。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例一
一种无铅压电陶瓷，其化学结构式为：aK0.48Na0.54Nb0.96O3-bSb2O3-cZrO2-dBi2O3-xFe2O3-yCuO-zMnO2，其中x＝0.001,y＝0.001,z＝0.001,a为0.95,b为0.05,c为0.05,d为0.03；其制备方法包括以下步骤：
(1)将碳酸钾、碳酸钠、五氧化二铌、三氧化二锑、氧化锆、氧化铋原料按化学计量比称量，以无水乙醇作为球磨介质，用行星球磨机球磨10h，烘干获得混合料；
(2)将混合料送入马弗炉预烧，预烧温度为900℃，保温时间为8h，制得预烧粉料；
(3)预烧粉料、氧化铜、氧化锰、氧化铁分别以无水乙醇作为球磨介质单独进行第一次球磨10h，之后按化学计量比将预烧粉料、氧化铜、氧化锰、氧化铁混合进行第二次球磨10h，第二次球磨后的粒度为1μm，烘干球磨后获得的粉料，在粉料中加入占总质量5％的PVA溶液并在造粒塔造粒，用模具干压成陶瓷生胚；
(4)陶瓷生胚排完胶后送入马弗炉中烧结，烧结温度为1150℃，保温时间为4h，对烧结得到的陶瓷平磨，测试密度，然后印银烧银，烧银温度为800℃，保温时间30mi n，最后对陶瓷片进行极化处理，极化温度为100℃，极化电压为3KV/mm，极化时间为20mi n，极化的陶瓷片放置一天，之后测试瓷片的电性能。
实施例二
一种无铅压电陶瓷，各步骤及各步骤使用的试剂、工艺参数均与实施例一相同，不同的地方在于，在步骤(3)中，第二次球磨后粒径为0.6μm。
实施例三
一种无铅压电陶瓷，各步骤及各步骤使用的试剂、工艺参数均与实施例一相同，不同的地方在于，在步骤(3)中，第二次球磨后粒径为1.5μm。
对比例一
一种无铅压电陶瓷，各步骤及各步骤使用的试剂、工艺参数均与实施例一相同，不同的地方在于，其化学结构式为：aK0.48Na0.54Nb0.96O3-bSb2O3-cZrO2-dBi2O3-xFe2O3-yCuO-zMnO2，其中x＝0.001,y＝0,z＝0,a为0.95,b为0.05,c为0.05,d为0.03。
对比例二
一种无铅压电陶瓷，各步骤及各步骤使用的试剂、工艺参数均与实施例一相同，不同的地方在于，其化学结构式为：aK0.48Na0.54Nb0.96O3-bSb2O3-cZrO2-dBi2O3-xFe2O3-yCuO-zMnO2，其中x＝0.003,y＝0,z＝0,a为0.95,b为0.05,c为0.05,d为0.03。
对比例三
一种无铅压电陶瓷，各步骤及各步骤使用的试剂、工艺参数均与实施例一相同，不同的地方在于，其化学结构式为：aK0.48Na0.54Nb0.96O3-bSb2O3-cZrO2-dBi2O3-xFe2O3-yCuO-zMnO2，其中x＝0,y＝0.001,z＝0,a为0.95,b为0.05,c为0.05,d为0.03。
对比例四
一种无铅压电陶瓷，各步骤及各步骤使用的试剂、工艺参数均与实施例一相同，不同的地方在于，其化学结构式为：aK0.48Na0.54Nb0.96O3-bSb2O3-cZrO2-dBi2O3-xFe2O3-yCuO-zMnO2，其中x＝0,y＝0.003,z＝0,a为0.95,b为0.05,c为0.05,d为0.03。
对比例五
一种无铅压电陶瓷，各步骤及各步骤使用的试剂、工艺参数均与实施例一相同，不同的地方在于，其化学结构式为：aK0.48Na0.54Nb0.96O3-bSb2O3-cZrO2-dBi2O3-xFe2O3-yCuO-zMnO2，其中x＝0,y＝0,z＝0.001,a为0.95,b为0.05,c为0.05,d为0.03。
对比例六
一种无铅压电陶瓷，各步骤及各步骤使用的试剂、工艺参数均与实施例一相同，不同的地方在于，其化学结构式为：aK0.48Na0.54Nb0.96O3-bSb2O3-cZrO2-dBi2O3-xFe2O3-yCuO-zMnO2，其中x＝0,y＝0,z＝0.003,a为0.95,b为0.05,c为0.05,d为0.03。
对比例七
一种无铅压电陶瓷，各步骤及各步骤使用的试剂、工艺参数均与实施例一相同，不同的地方在于，其化学结构式为：aK0.48Na0.54Nb0.96O3-bSb2O3-cZrO2-dBi2O3-xFe2O3-yCuO-zMnO2，其中x＝0,y＝0,z＝0,a为0.95,b为0.05,c为0.05,d为0.03。
对比例八
一种无铅压电陶瓷，其化学结构式为：aK0.48Na0.54Nb0.96O3-bSb2O3-cZrO2-dBi2O3-xFe2O3-yCuO-zMnO2，其中x＝0.001,y＝0.001,z＝0.001,a为0.95,b为0.05,c为0.05,d为0.03；其制备方法包括以下步骤：
(1)将碳酸钾、碳酸钠、五氧化二铌、三氧化二锑、氧化锆、氧化铋、氧化铜、氧化锰、氧化铁原料按化学计量比称量，以无水乙醇作为球磨介质，用行星球磨机球磨10h，烘干获得混合料；
(2)将混合料送入马弗炉预烧，预烧温度为900℃，保温时间为8h，制得预烧粉料；
(3)预烧粉料球磨20h，以无水乙醇作为球磨介质，球磨后的粒度为0.8μm，烘干球磨后获得的粉料，在粉料中加入占总质量5％的PVA溶液并在造粒塔造粒，用模具干压成陶瓷生胚；
(4)陶瓷生胚排完胶后送入马弗炉中烧结，烧结温度为1150℃，保温时间为4h，对烧结得到的陶瓷平磨，测试密度，然后印银烧银，烧银温度为800℃，保温时间30mi n，最后对陶瓷片进行极化处理，极化温度为100℃，极化时间为20mi n，极化的陶瓷片放置一天，之后测试瓷片的电性能。
对比例九
一种无铅压电陶瓷，各步骤及各步骤使用的试剂、工艺参数均与实施例一相同，不同的地方在于，其化学结构式为：aK0.48Na0.54Nb0.96O3-bSb2O3-cZrO2-dBi2O3-xFe2O3-yCuO-zB2O3，其中x＝0.001,y＝0.001,z＝0.001，a为0.95,b为0.05,c为0.05,d为0.03。
性能检测试验
1、致密度：致密度大小主要由体积密度判断，依据国标GB/T 2413测定，结果如下表1所示。
2、压电系数：纵向压电应变常数d33依据国标GB 3389.2-82测定，结果如下表2所示。
表1-本申请实施例和对比例中无铅压电陶瓷的性能检测结果
结合表1中实施例1和对比例1-7的性能检测结果可知，本申请通过同时引入氧化铁、氧化铜、氧化锰三者协同辅助铌酸钾钠基陶瓷的烧结，可以降低陶瓷的烧结温度，避免高温下钾钠元素的挥发，在该较低烧结温度的条件下提高铌酸钾钠基陶瓷的烧结性能，减少气孔率，提高压电陶瓷的致密度和压电性能。
结合表1中实施例1和对比例8的性能检测结果可知，本申请铌酸钾钠基陶瓷主体成分先预烧合成钙钛矿型结构，预烧后加入金属氧化物可以防止预烧时金属氧化物固溶进铌酸钾钠晶格中，从而防止达不到形成液相降低陶瓷烧结温度的目的，同时防止可能产生价态不平衡、缺陷、空位等现象影响陶瓷的压电性能。
结合表1中实施例1-3的性能检测结果可知，球磨粒度影响烧结后陶瓷的收缩率，粒度越小，所需的烧结温度越低，烧结后的陶瓷收缩率大，致密度高，压电性能更强。
如图1所示，为实施例二获得无铅压电陶瓷的X射线衍射图谱，从图中可以看出铋、锆、锑元素很好地固溶进铌酸钾钠晶格中，陶瓷呈现单一的钙钛矿结构，而微量的氧化铁、氧化锰、氧化铜引入并未在陶瓷内部形成第二相。
本申请铌酸钾钠基陶瓷主体成分先预烧合成钙钛矿型结构，随后在烧结过程中引入氧化铁、氧化铜、氧化锰辅助烧结，可以防止预烧时金属氧化物固溶进铌酸钾钠晶格中，从而防止达不到形成液相降低陶瓷烧结温度的目的，同时防止可能产生价态不平衡、缺陷、空位等现象影响陶瓷的压电性能，所需烧结温度降低，烧结性能提高，最终可以获得气孔率少、致密度高且压电性能优越的陶瓷产品。
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步的详细说明，应当理解，以上所述仅为本发明的具体实施例而已，并不用于限定本发明的保护范围。特别指出，对于本领域技术人员来说，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

1.一种无铅压电陶瓷，其特征在于，所述无铅压电陶瓷的化学通式为：aK0.48Na0.54Nb0.96O3-bSb2O3-cZrO2-dBi2O3-xFe2O3-yCuO-zMnO2，其中0.92≤a≤0.98,0.02≤b≤0.08,0.02≤c≤0.08,0.01≤d≤0.05,0≤x≤0.03，0≤y≤0.03，0≤z≤0.03。
2.如权利要求1所述的一种无铅压电陶瓷，优选地，其特征在于，x为0-0.01，y为0-0.01，z为0-0.01。
3.如权利要求1所述的一种无铅压电陶瓷，优选地，其特征在于，a为0.94-0.96，b为0.04-0.06，c为0.04-0.06，d为0.01-0.03。
4.一种基于如权利要求1-3任一所述的无铅压电陶瓷的制备方法，其特征在于，包括以下步骤：
(1)将碳酸钾、碳酸钠、五氧化二铌、三氧化二锑、氧化锆、氧化铋原料按化学计量比称量，球磨、烘干获得混合料；
(2)将混合料进行预烧，制得预烧粉料；
(3)将预烧粉料、氧化铜、氧化锰、氧化铁分别以无水乙醇作为球磨介质单独进行第一次球磨，之后按化学计量比将预烧粉料、氧化铜、氧化锰、氧化铁混合进行第二次球磨，烘干第二次球磨后获得的粉料，加入PVA溶液并造粒，用模具干压成陶瓷生胚；
(4)陶瓷生胚排完胶后进行烧结，烧结温度为1120-1210℃，保温时间为2-6h，对烧结得到的陶瓷平磨，然后印银烧银，得到陶瓷片，最后对陶瓷片进行极化处理，获得无铅压电陶瓷。
5.如权利要求4所述的一种无铅压电陶瓷的制备方法，其特征在于，在步骤(1)中，以无水乙醇作为球磨介质，球磨时间为2-10h。
6.如权利要求4所述的一种无铅压电陶瓷的制备方法，其特征在于，在步骤(2)中，预烧温度为750-950℃，保温时间为3-9h。
7.如权利要求4所述的一种无铅压电陶瓷的制备方法，其特征在于，在步骤(3)中，第一次球磨5-20h，第二次球磨5-20h，PVA溶液的质量分数为3-10％。
8.如权利要求4所述的一种无铅压电陶瓷的制备方法，其特征在于，在步骤(3)中，第二次球磨后最终平均粒径为0.6-1.0μm。
9.如权利要求4所述的一种无铅压电陶瓷的制备方法，其特征在于，在步骤(4)中，烧银温度为600-800℃，保温时间20-50min，极化温度为70-120℃，极化电压为2-4KV/mm，极化时间为10-30min。
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