CN111635229A - 一种无铅压电陶瓷材料的制备方法 - Google Patents

一种无铅压电陶瓷材料的制备方法 Download PDF

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CN111635229A
CN111635229A CN202010474375.7A CN202010474375A CN111635229A CN 111635229 A CN111635229 A CN 111635229A CN 202010474375 A CN202010474375 A CN 202010474375A CN 111635229 A CN111635229 A CN 111635229A
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刘运有
朱凯
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Shanghai Qiheng Biotechnology Co ltd
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Abstract

本发明属于无铅压电陶瓷材料及其制备方法技术领域，尤其涉及一种无铅压电陶瓷材料的制备方法，目的就是提供一种经济有效、无铅污染的制备铌酸钾钠(KNN)压电陶瓷的方法。通过固相合成法制备KNN‑xCZ陶瓷，经过预烧、破碎、球磨之后，晶粒尺寸尺寸分布变得均匀，致密度提高，CaZrO3的引入使Tc与T0‑T低温方向移动，造成在室温附近的O‑T相共存，弛豫程度不断增加，当x=0.03时具有最佳的电学性能:压电常数d33=442pC/N，居里温度Tc=245°C，这主要得益于该组分具有O‑T共存的PPB，导致在外电场下畴壁运动与电畴翻转更加容易翻转，压电性能得以增强，本发明优化了材料的压电介电性能，并且优化了无铅压电陶瓷的工业化制备方法。

Description

一种无铅压电陶瓷材料的制备方法
技术领域
本发明属于无铅压电陶瓷材料及其制备方法技术领域，尤其涉及一种无铅压电陶瓷材料的制备方法。
背景技术
21世纪的科技迎来了高速发展的浪潮，新型的铁电、压电陶瓷材料被广泛地应用于微位移器、致动器、信号发生器、压电换能器等诸多领域，压电陶瓷是一类重要的功能材料，具有电信号和机械应变互相转化的特殊性能，其中，锆钛酸铅(PZT)为主的铅基压电陶瓷，锆钛酸铅(PZT)压电陶瓷具有高压电常数d33(200～750pC/N)和高居里温度(Tc)(180～320℃)，因而，在传感器、执行器及超声变换器等方面得到了广泛应用，因其优异的综合性能在实际应用中占据主导地位。
然而，但高达60％的含铅量将带来环境负担，故必须开发无铅压电材料，尤其是高性能的无铅压电材料，钙钛矿无铅压电陶瓷有钛酸钡(BT)、碱金属铌酸盐系(KNN)、钛酸铋钠系(BNT)三大无铅压电材料均具有优良的性能，并得到深入的研究，尤其是其中碱金属铌酸盐系的KNbO3及NaNbO3具有较高的压电常数，较高的机电耦合系数，较高的品质因数和高的居里温度，因此，在过去10多年里成为无铅压电材料的研究热点，且已成为当今新材料的研究前沿，具有广泛的应用空间和研究价值。
铌酸钾钠(KNN)压电陶瓷是三大无铅压电材料中的一种，由于其结构的特殊性，在通电后能够进行电能及机械能的转换，虽然其机理和性能还没有确定的报道，但在精密传感器和医学成像、声传感器、声换能器、超声马达等方面具有广泛应用，在2004年Saito等通过Li、Ta、Sb共掺杂制备KNN基织构化陶瓷，具有超高的压电性能(d33达416pC/N)引起了学者的广泛关注(Saito Y，Takao H，Tael T，et al.Lead-free piezo ceramics[J]-Nature，2004，432:8437.)，此后，学者通过离子掺杂或引入ABO3型结构钙钛矿第二组元构建多相共存的多晶型相界(polymorphic phase boundary PPB)以提高KNN陶瓷的压电性能，其中，正交-四方相界(orthorhombic-tetragonal O-T)的构建被广泛采用，压电性能得到了很大提高，Guo等研究LiNbO3掺杂KNN陶瓷，得到具有O-T共存的PPB最大d33达415pC/N(Guo Y P，Kakimoto K I，Ohsato H.Phase transitional behavior and piezoelectricproperties of NbO3-LiNbO3 ceramics[J]-Applied Physics Letters，2004，85:41215123.)，Wang等研究了CaZrO3改性KNN基无铅陶瓷的电致应变性能，得到了较高的压电性能，在室温下的单极应变达0.16％，然而Tc仅200℃限制了其实际应用(Wang K，Yao F Z，Jo W，et al.Temperature-insensitive(K，Na)NbO3-based lead-free piezoactuatorceramics[J]-Advanced Functional，Materials，2013，23：40795086.)，本申请的发明人对铌酸钾钠(KNN)压电陶瓷的文献综述(任豆豆，赵林，马健，等.ABO3型化合物掺杂KNN基无铅压电陶瓷的研究进展[J].现代技术陶瓷，2015(6):47-53.已经表明，大多数研究工作都是借助固相合成法来制备钛酸钡(BT)及钛酸铋钠系(BNT)为主的铅基压电陶瓷，使用此方法制备铌酸钾钠(KNN)还未涉及，并且，利用CaZrO3掺杂改良压电陶瓷性能，并结合改性PVA制备铌酸钾钠(KNN)压电陶瓷的方法也未见报道。
发明内容
针对现有技术存在的问题，本发明提供了一种经济有效、无铅污染的制备铌酸钾钠(KNN)压电陶瓷的方法，本发明采用固相合成法制备压电陶瓷片，其过程为将预处理后的陶瓷颗粒加入改性PVA粘结剂中造粒，并通过高压加热进行排胶，冷却后制得圆形压电陶瓷晶片。
本发明是这样实现的，一种无铅压电陶瓷材料的制备方法，铌酸钾钠(KNN)压电陶瓷的制备方法，该方法步骤如下：采用固相合成法制备KNN基压电陶瓷，以分析纯的Na2CO3、K2CO3、Li2CO3、Nb2O5、Sb2O3、CaCO3、CaZrO3为原料制备铌酸钾钠(KNN)压电陶瓷，在实验中额外加入1.5mol％的Na2CO3、K2CO3以补偿高温时Na、K的挥发，同时采用预烧保证钙钛矿相结构的稳定存在，预烧温度区间为850-880℃，保温4h，通过二次球磨、过筛后的陶瓷颗粒加入量分数为7％的改性PVA粘结剂进行造粒，在400℃恒温条件下，30MPa下压制成直径12mm，厚度约为1.5mm，密度为5.61～7.23g/cm3的圆形生坯，经排胶工艺(最高温度500℃)后，对样品进行烧结，从室温经6h升温至1280℃，保温2h，改性PVA排胶完成后，制成直径为16mm，厚度为0.88～0.90mm，密度≥7.70g/cm3的圆形压电陶瓷晶片。
作为本发明优选的，所述分散剂优选的是易挥发有机溶剂，如乙醇、异丙醇等，酒精与异丙醇的摩尔比优选为0.5：3～3：3，最优选的是0.75:3～1.5:3。
作为本发明优选的，所述陶瓷粉与CaZrO3的质量比优选为80：1～60：1最优选的是70:1～75:1。
作为本发明优选的，所述排胶过程优选为400～500℃。
作为本发明优选的，所述聚合反应温度优选为20～30MPa。
与现有技术相比，本发明的有益效果如下：
1、本发明经X射线衍射分析，该压电陶瓷为典型的四方结构体系，且杂相少，经介电常数εr和介电损耗tanδ随温度的变化曲线分析，陶瓷片的居里温度Tc约为245℃，居里点附近为尖峰，峰的位置与所加频率无关，为正常铁电体，且介电损耗随温度变化不大，通过固相合成法制备KNN-xCZ陶瓷，经过预烧、破碎、球磨之后，晶粒尺寸尺寸分布变得均匀，致密度提高，CaZrO3的引入使Tc与T0-T低温方向移动，造成在室温附近的O-T相共存，弛豫程度不断增加，当x＝0.03时具有最佳的电学性能:压电常数d33＝442pC/N，居里温度Tc＝245℃，这主要得益于该组分具有O-T共存的PPB，导致在外电场下畴壁运动与电畴翻转更加容易翻转，压电性能得以增强，其中，KNN系无铅压电陶瓷压电性能增强的物理根源为：通过合理的掺杂，将正交四方多型相转变温度移至室温附近，而完全依赖非传统的MPB效应(即存在三方-四方准同型相界)，进而使得铌酸钾钠(KNN)系压电陶瓷的压电性能有良好的稳定性，本发明优化了材料的压电介电性能，并且优化了无铅压电陶瓷的工业化制备方法。
2、本发明通过设置球磨制备陶瓷颗粒，能够使分散剂的加入使得球磨更加充分均匀。
3、本发明通过设置CaZrO3，能够使Tc与T0-T与向低温方向移动，导致畴壁运动与电畴翻转在外电场下更加容易，压电性能得以增强。
4、本发明通过胶过程优选为400～500℃，由于排胶过程的温度对陶瓷片的成型都有极大影响，温度过低，则胶黏剂无法顺利排出，固化凝结在陶瓷可以之间，造成陶瓷配位缺陷，温度过高，往往制备出来的陶瓷内部有许多孔洞和缺陷，因此设定在400～500℃。
5、本发明通过聚合反应温度优选为20～30MPa，排胶过程的压力同样对陶瓷片的成型都有极大影响，压力过低则无法将多余的粘结剂彻底排出，压力过大则可能导致陶瓷粉末的破裂。
附图说明
图1为压电陶瓷的X射线衍射图谱，陶瓷片的衍射峰与文献中所查得的KNN陶瓷结构结果相吻合，无杂峰，表明制备反应充分，无杂相生成；在2θ约39°时为单峰，约45°时为双峰，为典型的四方结构体系。
图2为压电陶瓷的压电性能谱，即压电常数极化电场的变化曲线，随着极化电场的增大，压电常数d33也随之增大，当极化电场为500～600V/mm时，压电陶瓷片的压电常数d33为430～450时，达到符合正常量产标准的压电常数d33值。
图3为改性PVA红外光谱图，经红外光谱图分析，经FT-IR分析，改性PVA的红外图谱与常用的PVA明显不同，普通PVA呈现多重吸收峰，1600～1700cm－1吸收表明C＝C双键的存在，而改性PVA在此波数范围内呈现一个较高的吸收峰，表明聚合物中除了C＝C双键外，还有C＝O双键的存在，预示着改性官能团的生成。
图4、图5为压电陶瓷的SEM图片，从图中可以看出，烧制后的陶瓷片样品的晶粒大小较为均匀，约为5um；排胶彻底，没有残余的PVA粘结剂残留。
图6为陶瓷样品的介电温谱，介电温谱是在不同测试频率下的介电常数εr和介电损耗tanδ随温度的变化曲线，从图6可看出:陶瓷片的居里温度Tc约为245℃，居里点附近为尖峰，峰的位置与所加频率无关，为正常铁电体；介电损耗随温度变化不大。
具体实施方式
为能进一步了解本发明的发明内容、特点及功效，兹例举以下实施例，并配合附图详细说明如下。
下面结合附图对本发明的结构作详细的描述。
实施例1
按照表1的比例，以分析纯的Na2CO3、K2CO3、Li2CO3、Nb2O5、Sb2O3、CaCO3、CaZrO3为原料制备铌酸钾钠(KNN)压电陶瓷，在实验中额外加入少量的Na2CO3、K2CO3以补偿高温时Na、K的挥发，同时采用预烧保证钙钛矿相结构的稳定存在，预烧温度区间为850-880℃，保温4h，m(料)：m(磨球)：m(乙醇)＝1:2:1混合球磨12h，球磨后干燥浆料，过筛后的陶瓷颗粒加入量分数为7％的改性PVA粘结剂进行造粒，在400℃恒温条件下，30MPa下压制成直径12mm，厚度约为1.5mm，密度为5.61～7.23g/cm3的圆形生坯，保温2h，经排胶工艺(最高温度500℃)后，对样品进行烧结，从室温经6h升温至1280℃，保温2h，改性PVA排胶完成后，制成直径为16mm，厚度为0.88～0.90mm，密度≥7.70g/cm3的圆形压电陶瓷晶片，将烧结样品涂银浆后在600℃下保温30min，然后放置在120℃的硅油中，以3.8kV/mm的电场极化30min，经SEM观察，该压电陶瓷形貌为不规则块状颗粒，颗径约为10-20um。
原料 Na<sub>2</sub>CO<sub>3</sub> K<sub>2</sub>CO<sub>3</sub> Li<sub>2</sub>CO<sub>3</sub> Nb<sub>2</sub>O<sub>5</sub> Sb<sub>2</sub>O<sub>3</sub> CaCO<sub>3</sub> CaZrO<sub>3</sub>
纯度 99.985％ 99.98％ 99.915％ 99.99％ 99.905％ 99.95％ 99.9％
添加量(g) 155～160 45～60 110～160 310～360 15～26 60～80 15～20
表1为铌酸钾钠(KNN)压电陶瓷原料的纯度及用量一览表
实施例2
重复实施例1，但用下表2的原料的纯度及用量制备铌酸钾钠(KNN)压电陶瓷。
原料 Na<sub>2</sub>CO<sub>3</sub> K<sub>2</sub>CO<sub>3</sub> Li<sub>2</sub>CO<sub>3</sub> Nb<sub>2</sub>O<sub>5</sub> Sb<sub>2</sub>O<sub>3</sub> CaCO<sub>3</sub> CaZrO<sub>3</sub>
纯度 99.985％ 99.98％ 99.915％ 99.99％ 99.905％ 99.95％ 99.9％
添加量(g) 105～120 35～40 100～120 380～400 45～50 70～90 10～15
表2为铌酸钾钠(KNN)压电陶瓷原料的纯度及用量一览表
实施例3
重复实施例1，但改用m(料)：m(磨球)：m(乙醇)＝2:2:1混合球磨6h，球磨后干燥浆料，过筛后的陶瓷颗粒加入量分数为5％的改性PVA粘结剂进行造粒。
实施例4
重复实施例1，改变预烧的温度和时间，但在600℃恒温条件下，20MPa下压制成直径10mm，厚度约为1.35mm，密度为7.81～8.96g/cm3的圆形生坯，保温1h。
实施例5
重复实施例1，改变二次烧结的温度和时间，经排胶工艺(最高温度600℃)后，对样品进行烧结，从室温经6h升温至1380℃，保温1h。
实施例6
重复实施例1，改变极化电压和时间，得将烧结样品涂银浆后在600℃下保温30min，然后放置在160℃的硅油中，以4.8kV/mm的电场极化50min。
需要说明的是，在本文中，诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。

Claims (5)

1.一种无铅压电陶瓷材料的制备方法，铌酸钾钠(KNN)压电陶瓷的制备方法，该方法步骤如下：采用固相合成法制备KNN基压电陶瓷，以分析纯的Na2CO3、K2CO3、Li2CO3、Nb2O5、Sb2O3、CaCO3、CaZrO3为原料制备铌酸钾钠(KNN)压电陶瓷，在实验中额外加入1.5mol%的Na2CO3、K2CO3以补偿高温时Na、K的挥发，同时采用预烧保证钙钛矿相结构的稳定存在，预烧温度区间为850-880°C，保温4h，通过二次球磨、过筛后的陶瓷颗粒加入量分数为７％的改性PVA粘结剂进行造粒，在400°C恒温条件下，30MPa下压制成直径12mm，厚度约为1.5mm，密度为5.61～7.23g/cm3的圆形生坯，经排胶工艺(最高温度500℃)后，对样品进行烧结，从室温经6h升温至1280℃，保温2h，改性PVA排胶完成后，制成直径为16mm，厚度为0.88～0.90mm，密度≥7.70g/cm3的圆形压电陶瓷晶片。
2.如权利要求1所述的一种无铅压电陶瓷材料的制备方法，其特征在于：所述分散剂优选的是易挥发有机溶剂，如乙醇、异丙醇等，酒精与异丙醇的摩尔比优选为0.5：3～3：3，最优选的是0.75:3～1.5:3。
3.如权利要求1所述的一种无铅压电陶瓷材料的制备方法，其特征在于：所述陶瓷粉与CaZrO3的质量比优选为80：1～60：1最优选的是70:1～75:1。
4.如权利要求1所述的一种无铅压电陶瓷材料的制备方法，其特征在于：所述排胶过程优选为400～500℃。
5.如权利要求1所述的一种无铅压电陶瓷材料的制备方法，其特征在于：所述聚合反应温度优选为20～30MPa。
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