CN114409400A - 一种铌酸钾钠基无铅压电陶瓷及其制备方法 - Google Patents
一种铌酸钾钠基无铅压电陶瓷及其制备方法 Download PDFInfo
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- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000000919 ceramic Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 36
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000009694 cold isostatic pressing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 244000137852 Petrea volubilis Species 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000010287 polarization Effects 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 230000007704 transition Effects 0.000 abstract description 10
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 4
- 238000010344 co-firing Methods 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 27
- 239000012071 phase Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
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Abstract
本发明涉及功能陶瓷材料技术领域，具体而言涉及一种铌酸钾钠基无铅压电陶瓷及其制备方法。本发明制备方法采用固相法，直接将陶瓷粉制备成多层结构铌酸钾钠基无铅压电陶瓷，从而实现良好的温度稳定性。本发明制备方法制备的多层结构铌酸钾钠基无铅压电陶瓷中每层的成分可调控，每层陶瓷均具有多相共存结构，转变温度从一层依次上升到另一层。每层组分采用相似的化学成分，以确保良好的共烧和易于控制在高温下的扩散。最终使得到的多层铌酸钾钠基压电陶瓷样品在保留较高的压电性能的同时兼具较好的温度稳定性。本发明制备方法操作简便、周期短、成本低、能耗少。
Description
技术领域
本发明涉及功能陶瓷材料技术领域，具体而言涉及一种铌酸钾钠基无铅压电陶瓷及其制备方法。
背景技术
压电材料可以通过正逆压电效应实现电能与机械能的直接转换，是传感器与致动器的关键材料，广泛应用于生物医疗、先进制造、电子信息以及航空航天等领域。在各种无铅陶瓷中，铌酸钾钠(KNN)陶瓷因其较高的压电特性和居里温度引起了研究人员的兴趣。广泛的研究集中在构建菱方-四方R-T(或菱方-正交-四方R-O-T)相界实现超高压电系数(d33)(>500pC/N)，使其可以与铅基压电材料相媲美。但许多应用场景要求压电材料具有优异的温度稳定性。与PZT基压电陶瓷的几乎温度无关的准同型相界(MPB)不同，KNN基陶瓷的相界具有很强的压电温度依赖性，不仅受成分的影响，还受温度的影响。如果环境温度偏离相变温度，铌酸钾钠基陶瓷的压电响应会迅速下降，导致温度稳定性较差。虽然，在室温附近构建相变可以显著改善电性能，但与此同时温度稳定性会下降。压电材料的稳定性除了增强压电特性外，对实际应用也具有重要意义，特别是对于那些涉及喷油器、气体速度传感器等高温操作的材料。在改变KNN基陶瓷多相共存的同时，保持温度的稳定性是很重要的。现有专利均采用流延法制备多层陶瓷来提高KNN基陶瓷的应变稳定性。然而，较高的生产成本和复杂的合成工艺严重限制了其在压电器件中的广泛应用。
发明内容
本发明旨在部分解决已有技术中的问题，基于本申请人以前研究的单层Lix(K0.48-xNa0.52)Nb1-ySbyO3-BaZrO3-(Na0.5Bi0.5)HfO3-MnO2系列陶瓷，当环境温度超过相变温度后，压电性能迅速下降，导致其温度稳定性差，严重限制了陶瓷材料的实际应用。
有鉴于此，本发明的目的在于提出一种铌酸钾钠基无铅压电陶瓷及其制备方法，采用固相法，以多个具有R-O-T相变铌酸钾钠基压电陶瓷粉体为基础，制备在较宽的温度范围内具有连续R-O-T相变的多层结构铌酸钾钠基无铅压电陶瓷，以实现在较宽温度范围内保留较大压电性能的同时兼具良好的温度稳定性。
本发明的实施例提出了一种铌酸钾钠基无铅压电陶瓷，该铌酸钾钠基无铅压电陶瓷为多层，每层铌酸钾钠基无铅压电陶瓷的分子结构式为：
Lix(K0.48-xNa0.52)Nb1-ySbyO3-BaZrO3-(Na0.5Bi0.5)HfO3-MnO2
其中x和y为摩尔分数，0≤x＜0.48，0≤y＜0.5。
在一些实施例中，所述每层铌酸钾钠基无铅压电陶瓷中，每层的x值互不相等，且每层的y值互不相等。
本发明的实施例提出了一种铌酸钾钠基无铅压电陶瓷的制备方法，包括以下步骤：
(1)制备多种不同成分的铌酸钾钠基压电陶瓷粉体；
(2)将步骤(1)得到的多种不同成分的铌酸钾钠基压电陶瓷粉体铺成多层，进行冷等静压处理，制备得到多层铌酸钾钠基压电材料胚体；
(3)对步骤(2)的多层铌酸钾钠基压电材料胚体进行煅烧，得到多层铌酸钾钠基压电陶瓷材料；
(4)将步骤(3)的多层铌酸钾钠基压电陶瓷陶瓷材料用砂纸抛光，在多层铌酸钾钠基压电陶瓷材料的上表面和下表面分别被覆银电极。而后进行在100℃、30kV下极化处理，以便测试所述铌酸钾钠基无铅压电陶瓷的压电性能。
本发明上述实施例的优点是：采用固相法直接将Lix(K0.48-xNa0.52)Nb1-ySbyO3-BaZrO3-(Na0.5Bi0.5)HfO3-MnO2系列陶瓷粉制备成多层结构铌酸钾钠基无铅压电陶瓷，其中的成分可调控，从而实现在保留较大的d33的同时兼具良好的温度稳定性。
在一些实施例中，所述步骤(1)中，制备多种不同成分的铌酸钾钠基压电陶瓷粉体，包括以下步骤：
(1)根据铌酸钾钠基无铅压电陶瓷的分子结构式Lix(K0.48-xNa0.52)Nb1-ySbyO3-BaZrO3-(Na0.5Bi0.5)HfO3-MnO2的化学计量比，分别称取Na2CO3、Li2CO3、K2CO3、Nb2O5、Ba2CO3、ZrO2、HfO2和Bi2O3，原料混合后球磨处理，得到浆料，烘干后得到粉体；
(2)预烧步骤(1)的粉体，得到预烧粉；
(3)将步骤(2)的预烧粉进行球磨，得到浆料，烘干后得到铌酸钾钠基压电陶瓷粉体；
(4)多次改变铌酸钾钠基无铅压电陶瓷的分子结构式中的x、y值，分别重复步骤(1)～步骤(3)，得到多种不同成分的铌酸钾钠基压电陶瓷粉体。
在一些实施例中，所述球磨的条件为：磨球与原料比为(10～20):1，转速为200～350r/分钟，球磨时间为16～30小时。
在一些实施例中，所述预烧的温度为800～1000℃，预烧时间为2～6小时。
在一些实施例中，所述多种不同成分的铌酸钾钠基压电陶瓷粉体铺成多层，得到的多层陶瓷材料中，每层陶瓷粉体的厚度为0.5～2毫米，层数为2～5。
在一些实施例中，所述对多层陶瓷材料进行冷等静压时间为2～5分钟，压力为200Mpa。
在一些实施例中，所述多层铌酸钾钠基压电陶瓷材料胚体的煅烧温度为1000～1200℃，煅烧时间为3～8小时。
根据本发明实施例制备得到的铌酸钾钠基无铅压电陶瓷，其优点是：
1、与已有技术做多层的方法相比，本发明制备方法操作简便、周期短、成本低、能耗少。每层组分采用相似的化学成分，以确保良好的共烧和易于控制在高温下的扩散。本发明实施例制备得到的多层铌酸钾钠基压电陶瓷材料结构致密，层与层之间没有明显的界线。
2、本发明通过调控成分制备的多层结构铌酸钾钠基无铅压电陶瓷，每层陶瓷均具有多相共存结构，转变温度从一层依次上升到另一层。最终使得到的多层铌酸钾钠基压电陶瓷样品在保留较高的压电性能同时兼具较好的温度稳定性。
本发明附加的方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。
附图说明
为了更清楚的说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍。显然，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来说，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是根据本发明的一个实施例制备得到的多层铌酸钾钠基压电陶瓷与已有的单层铌酸钾钠基压电陶瓷的相变温度比较示意图。
图2是根据本发明的实施例1、实施例2、实施例3和实施例4的压电常数变化率示意图。
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做出创造性劳动的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。
本发明实施例提出了一种铌酸钾钠基无铅压电陶瓷，该铌酸钾钠基无铅压电陶瓷为多层，每层铌酸钾钠基无铅压电陶瓷的分子结构式为：
Lix(K0.48-xNa0.52)Nb1-ySbyO3-BaZrO3-(Na0.5Bi0.5)HfO3-MnO2
其中x和y为摩尔分数，0≤x＜0.48，0≤y＜0.5。
根据本发明实施例的铌酸钾钠基无铅压电陶瓷，所述每层铌酸钾钠基无铅压电陶瓷中，每层的x值互不相等，且每层的y值互不相等。
本发明实施例提出的铌酸钾钠基无铅压电陶瓷中，成分可调控，为多层结构，每一层铌酸钾钠基层压陶瓷均具有多相共存结构，转变温度从一层依次上升到另一层。最终使得到的多层铌酸钾钠基压电陶瓷样品在保留较高的压电性能同时，兼具了较好的温度稳定性。
本发明实施例提出了一种铌酸钾钠基无铅压电陶瓷的制备方法，包括以下步骤：
(1)制备多种不同成分的铌酸钾钠基压电陶瓷粉体；
(2)将步骤(1)得到的多种不同成分的铌酸钾钠基压电陶瓷粉体铺成多层，进行冷等静压处理，制备得到多层铌酸钾钠基压电材料胚体；
(3)对步骤(2)的多层铌酸钾钠基压电材料胚体煅烧，得到多层铌酸钾钠基压电陶瓷材料；
(4)将步骤(3)的多层铌酸钾钠基压电陶瓷陶瓷材料用砂纸抛光，在多层铌酸钾钠基压电陶瓷材料的上表面和下表面分别被覆银电极。而后进行在100℃、30kV下极化处理，以便测试所述铌酸钾钠基无铅压电陶瓷的压电性能。
本发明实施例提出的铌酸钾钠基无铅压电陶瓷的制备方法，以Na2CO3、K2CO3、Nb2O5、Ba2CO3、ZrO2、HfO2、Bi2O3和金属氧化物为原料，通过控制固相法制备的R-O-T相变峰值在不同温度范围的陶瓷粉体的层数和厚度，制得结构致密、电学性能良好、温度度稳定性优异的多层结构铌酸钾钠基压电材料。
根据本发明的铌酸钾钠基无铅压电陶瓷的制备方法，其中，所述步骤(1)中，制备多种不同成分的铌酸钾钠基压电陶瓷粉体，包括以下步骤：
(1)根据铌酸钾钠基无铅压电陶瓷的分子结构式Lix(K0.48-xNa0.52)Nb1-ySbyO3-BaZrO3-(Na0.5Bi0.5)HfO3-MnO2的化学计量比，分别称取Na2CO3、Li2CO3、K2CO3、Nb2O5、Ba2CO3、ZrO2、HfO2和Bi2O3，原料混合后球磨处理，得到浆料，烘干后得到粉体；
(2)预烧步骤(1)的粉体，得到预烧粉；
(3)将步骤(2)的预烧粉进行球磨，得到浆料，烘干后得到铌酸钾钠基压电陶瓷粉体；
(4)多次改变铌酸钾钠基无铅压电陶瓷的分子结构式中的x、y值，分别重复步骤(1)～步骤(3)，得到多种不同成分的铌酸钾钠基压电陶瓷粉体。
在一些实施例中，所述球磨条件为：磨球与原料比为(10～20):1，转速为200～350r/分钟，球磨时间为16～30小时。
在一些实施例中，所述预烧的温度为800～1000℃，预烧时间为2～6小时。
在一些实施例中，所述多种不同成分的铌酸钾钠基压电陶瓷粉体铺成多层，得到的多层陶瓷材料中，每层陶瓷粉体的厚度为0.5～2毫米，层数为2～5。
在一些实施例中，所述对多层陶瓷材料进行冷等静压时间为2～5分钟，压力为200Mpa。
在一些实施例中，所述多层铌酸钾钠基压电陶瓷材料胚体的煅烧温度为1000～1200℃，煅烧时间为3～8小时。
以下对本发明的实施例进行详细描述。所有的实施例都是示例性的，旨在解释本发明，而不能理解为对本发明的限制。
表1本发明为Lix(K0.48-xNa0.52)Nb1-ySbyO3-BaZrO3-(Na0.5Bi0.5)HfO3-MnO2多层无铅压电陶瓷的实施例
图2给出了实施例1、实施例2、实施例3和实施例4制备的2～5层铌酸钾钠基无铅压电陶瓷的压电常数的变化率，从图2中可以看出，本发明实施例制备的多层铌酸钾钠基无铅压电陶瓷，随着层数的增加，压电常数的变化率逐渐变小。实施例4制备的五层铌酸钾钠基无铅压电陶瓷的压电常数的峰更宽泛，在50～75℃温度区间可达508pC/N；在25～150℃温度区间压电系数d33变化率仅为13％。本发明制备的多层铌酸钾钠无铅压电材料具有优异的温度稳定性，在实际应用中有巨大潜力。
Claims (9)
1.一种铌酸钾钠基无铅压电陶瓷，其特征在于，铌酸钾钠基无铅压电陶瓷为多层，每层铌酸钾钠基无铅压电陶瓷的分子结构式为：
Lix(K0.48-xNa0.52)Nb1-ySbyO3-BaZrO3-(Na0.5Bi0.5)HfO3-MnO2
其中x和y为摩尔分数，0≤x＜0.48，0≤y＜0.5。
2.根据权利要求1所述的铌酸钾钠基无铅压电陶瓷，其特征在于，所述每层铌酸钾钠基无铅压电陶瓷中，每层的x值互不相等，且每层的y值互不相等。
3.一种铌酸钾钠基无铅压电陶瓷的制备方法，其特征在于，包括：
(1)制备多种不同成分的铌酸钾钠基压电陶瓷粉体；
(2)将步骤(1)得到的多种不同成分的铌酸钾钠基压电陶瓷粉体铺成多层，进行冷等静压处理，制备得到多层铌酸钾钠基压电材料胚体；
(3)对步骤(2)的多层铌酸钾钠基压电材料胚体进行煅烧，得到多层铌酸钾钠基压电陶瓷材料；
(4)将步骤(3)的多层铌酸钾钠基压电陶瓷陶瓷材料用砂纸抛光，在多层铌酸钾钠基压电陶瓷材料的上表面和下表面分别被覆银电极。而后进行在100℃、30kV下极化处理，以便测试所述铌酸钾钠基无铅压电陶瓷的压电性能。
4.根据权利要求3所述的制备方法，其特征在于，步骤(1)中，所述制备多种不同成分的铌酸钾钠基压电陶瓷粉体包括：
(1)根据铌酸钾钠基无铅压电陶瓷的分子结构式Lix(K0.48-xNa0.52)Nb1-ySbyO3-BaZrO3-(Na0.5Bi0.5)HfO3-MnO2的化学计量比，分别称取Na2CO3、Li2CO3、K2CO3、Nb2O5、Ba2CO3、ZrO2、HfO2和Bi2O3，原料混合后球磨处理，得到浆料，烘干后得到粉体；
(2)预烧步骤(1)的粉体，得到预烧粉；
(3)将步骤(2)的预烧粉进行球磨，得到浆料，烘干后得到铌酸钾钠基压电陶瓷粉体；
(4)多次改变铌酸钾钠基无铅压电陶瓷的分子结构式中的x、y值，分别重复步骤(1)～步骤(3)，得到多种不同成分的铌酸钾钠基压电陶瓷粉体。
5.根据权利要求4所述的制备方法，其特征在于，步骤(1)和步骤(3)中，所述球磨条件为：磨球与原料比为(10～20):1，转速为200～350r/分钟，球磨时间为16～30小时。
6.根据权利要求4所述的制备方法，其特征在于，步骤(2)中，所述预烧的温度为800～1000℃，预烧时间为2～6小时。
7.根据权利要求3或4所述的制备方法，其特征在于，所述多种不同成分的铌酸钾钠基压电陶瓷粉体铺成多层，得到的多层陶瓷材料中，每层陶瓷粉体的厚度为0.5～2毫米，层数为2～5。
8.根据权利要求3或4所述的制备方法，其特征在于，所述对多层陶瓷材料进行冷等静压时间为2～5分钟，压力为200Mpa。
9.根据权利要求3或4所述的制备方法，其特征在于，所述多层铌酸钾钠基压电陶瓷材料胚体的煅烧温度为1000～1200℃，煅烧时间为3～8小时。
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| CN116496083A (zh) * | 2023-04-11 | 2023-07-28 | 四川大学 | 一种核壳结构硬化铌酸钾钠基无铅压电陶瓷及其制备方法 |
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| CN116730722B (zh) * | 2023-08-16 | 2023-10-20 | 兰州大学 | 一种钙钛矿型铌酸钾钠基陶瓷及其制备方法 |
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