CN105645957A - 一种高机电耦合性能锆钛酸铅细晶压电陶瓷及其制备方法 - Google Patents
一种高机电耦合性能锆钛酸铅细晶压电陶瓷及其制备方法 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 56
- 229910052451 lead zirconate titanate Inorganic materials 0.000 title claims abstract description 31
- 230000008878 coupling Effects 0.000 title claims abstract description 27
- 238000010168 coupling process Methods 0.000 title claims abstract description 27
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 27
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 9
- 229910007879 ZraTi1−a Inorganic materials 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 3
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010955 niobium Substances 0.000 abstract description 7
- 238000006467 substitution reaction Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 229910052788 barium Inorganic materials 0.000 abstract description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052758 niobium Inorganic materials 0.000 abstract description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LIABKAQKQSUQJX-UHFFFAOYSA-N [Mn].[Pb] Chemical compound [Mn].[Pb] LIABKAQKQSUQJX-UHFFFAOYSA-N 0.000 description 1
- BOUHOYYXLIKKRM-UHFFFAOYSA-N [Pb].[Nb].[Mn] Chemical compound [Pb].[Nb].[Mn] BOUHOYYXLIKKRM-UHFFFAOYSA-N 0.000 description 1
- HWHWBMBTCNLBGY-UHFFFAOYSA-N [Pb].[Ni].[Nb] Chemical compound [Pb].[Ni].[Nb] HWHWBMBTCNLBGY-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Abstract
本发明提供了一种高机电耦合性能锆钛酸铅细晶压电陶瓷，其分子式为Pb1-x-y-zBaxNbyNiz（ZraTi1-a）O3，其中0＜x≤0.1，0＜y≤0.08，0＜z≤0.08，0.51＜a≤0.6。本发明通过采用钡、铌、镍对锆钛酸铅压电陶瓷进行改性，获得了一种改性的高性能压电陶瓷。特别是当Pb1-x-y-zBaxNbyNiz（ZraTi1-a）O3，取代量x？=0.06，y=0.05，z=0.03，a=0.55，合成反应温度为850℃时，获得的改性的压电陶瓷综合压电性能最好，其中，介电常数为3600，压电系数d33为620pC/N，机电耦合系数kp值为80%，介电损耗小于1%，平均晶粒控制在2-4微米，在保持较高的压电性能的同时具有优异的机械性能。相应的，本发明还提供了该细晶压电陶瓷的制备方法。
Description
技术领域
本发明涉及一种压电陶瓷材料，具体涉及一种高机电耦合性能锆钛酸铅细晶压电陶瓷，同时还涉及该细晶压电陶瓷的制备方法。
背景技术
压电陶瓷是通过高温烧结制成的，具有高介电常数、压电性及优异的机电耦合性能的一种新兴的陶瓷材料，能够将机械能和电能互相转换。其中最具有代表性的是锆钛酸铅(PZT)压电陶瓷，PZT压电陶瓷由于其压电性能以及由压电性而引起的多种介电性能，在宇航、电子、计算机、激光、超声和能源等领域都得到了广泛的应用。
随着各行业的不断的发展，对PZT压电陶瓷的压电性能要求也不断提高，因此，对纯的PZT压电陶瓷进行改性获得改性的PZT压电陶瓷材料，以提高其压电性能，使其能够满足日益提高的压电性能的需求，已经成为PZT压电陶瓷发展的必然趋势。压电陶瓷在需要良好的压电性能的同时，同样需要良好的力学性能。由于压电陶瓷本身存在的断裂韧性低的固有弱点，限制了其在实际应用中的范围。
通过对压电陶瓷的断裂行为及增韧机理进行总结分析得出：对于穿晶断裂的压电陶瓷，主要增韧机理是微裂纹增韧，气孔率对韧性有负面影响；对于沿晶断裂的压电陶瓷，主要增韧机理是晶界解离，气孔率对其韧性有负面影响。通过对压电陶瓷的典型实验现象和己有的各种解释分析发现：通过加入第二相来增韧压电陶瓷，虽然显著改变了这些压电陶瓷的断裂韧性，但是会严重损害其压电性能；而通过自增韧的压电陶瓷不仅改善了断裂韧性，且保持了其优良的压电性能。
中国专利CN201510179552.8公开了一种锰锑酸铅掺杂的铌镍-锆钛酸铅压电陶瓷（PMN-PZT），获得了一种化学式为（1-x）Pb（Ni1/3Nb2/3）0.5ZryTi0.5-yO3-xPbMn1/3Sb2/3O3（其中y=0.10~0.20，x=0~0.06）具有高压电系数以及优异的力学性能的（E~120GPa，K1C~1.4MPa·m1 /2），但是该压电陶瓷的机电耦合系数仅达到0.53，能量转化效率过低，无法达到应用的要求。
中国专利CN200410016324.0中公开了一种掺杂铌锰酸铅-锆钛酸铅压电陶瓷材料及其制备工艺，以SrCO3置换部分PbO和添加MnCO3，获得了一种弯曲强度为97MPa、介电损耗小于0.5%、机电耦合系数最高达0.59的压电陶瓷材料，过低的机电耦合系数使其在应用时能量转化效率过低，无法达到应用的要求。
在另一份天津大学的硕士学位论文“低损耗PMS-PZT压电陶瓷材料的研究”中，公开了一种组成为Pb1.02(Mn1/3Sb2/3)x(Zr0.47Ti0.48)(1-x)/0.95O3三元系压电陶瓷，其最佳压电系数d33为340pC/N，机械品质因数kp=0.585，相对介电常数为1369，介电损耗为0.31%的压电陶瓷材料，其相应的机械品质因数为0.585，远无法达到应用的要求。
通过对现有技术文件的分析中发现，锆钛酸铅产品晶粒过大（7-12微米），气孔多，产品的脆性大，易在振动工作中开裂，导致性能不稳定，影响产品的机械性能和可靠性。通过采用细化晶粒（通常取2-4微米）的方式可以大幅度提高压电陶瓷产品的可靠性，但按通常该方法会同时降低锆钛酸铅的压电性能（如介电常数εr及机电耦合系数Kp等性能）。例如同样的PZT锆钛酸铅的基础配方，在晶粒为7-12微米时，其介电常数可达3500、机电耦合系数Kp可达0.75；但将烧后产品晶粒控制在2-4微米时，其压电性能会出现急剧下降，介电常数εmax达1700、机电耦合系数Kp最高达0.70。
因而，如何获得一种具有综合机械性能优异、同时又具有较好的压电性能的压电陶瓷材料成为目前研究中极富挑战性的课题。
发明内容
为了解决现有技术中存在的问题，本发明提供了一种高机电耦合性能锆钛酸铅细晶压电陶瓷，相应的，本发明还提供了该细晶压电陶瓷的制备方法。
为了实现本发明的技术目的，本发明采用以下技术方案。
一种高机电耦合性能锆钛酸铅细晶压电陶瓷，其分子式为Pb1-x-y-zBaxNbyNiz（ZraTi1-a）O3，其中0＜x≤0.1，0＜y≤0.08，0＜z≤0.08，0.51＜a≤0.6。
优选的，一种高机电耦合性能锆钛酸铅细晶压电陶瓷，其分子式为Pb1-x-y- zBaxNbyNiz（ZraTi1-a）O3，其中x=0.06，y=0.05，z=0.03，a=0.55。
一种高机电耦合性能锆钛酸铅细晶压电陶瓷的制备方法，包括如下步骤：
（a）配料：按照压电陶瓷的成分及其化学计量比计算，称取原料，并将所述原料于球磨罐中球磨混合2.5小时，得到混合后的粉体；
（b）预烧：将步骤（a）得到的混合后的粉体于氧化铝坩埚内密封，在800℃~900℃反应2.5h，得到预烧后粉体；
（c）成型及排塑：将步骤（b）得到的预烧后粉体经球磨、烘干后流延成膜，冲制成坯体，采用两段升温排出有机物；
（d）烧结：将步骤（c）得到的排出有机物后的坯体在步骤（b）中预烧后的粉体中于1210℃埋烧2小时，升温速度为5℃/min；
（e）被电极：将步骤（d）得到的烧结后的坯体经超声水洗后烘干被银电极，于780℃保温10min后自然冷却，得到被电极制品；
（f）极化：将步骤（e）得到的被电极制品于100℃的空气中，施加1.4kV/mm的直流电场，极化10min，得到压电陶瓷。
优选的，所述步骤（a）中的原料为分析纯的Pb3O4、BaCO3、Nb2O5、NiO、ZrO2和TiO2；所述球磨混合的条件是原料：去离子水：球磨介质为1:2.5:1，转速为750rpm，所述球磨介质为ZrO2球。
优选的，所述步骤（b）的预烧反应温度为850℃。
优选的，所述步骤（b）中烘干温度为60~100℃。
优选的，所述步骤（c）中坯体直径为17.20mm，厚度为12.5±0.5μm。
优选的，所述步骤（c）中的两段升温是指先以3℃/min的升温速率升温至200℃，再以2℃/min的升温速率继续升温至400℃，保温30min后，再以5℃/min的升温速率升温至650℃，保温15min，排出坯体中有机物。
优选的，所述步骤（e）中被电极采用丝网印刷工艺。
本发明的有益效果是：本发明通过采用钡、铌、镍对锆钛酸铅压电陶瓷进行改性，获得了一种改性的高性能压电陶瓷。特别是当Pb1-x-y-zBaxNbyNiz（ZraTi1-a）O3，取代量x=0.06，y=0.05，z=0.03，a=0.55，合成反应温度为850℃时，获得的改性的压电陶瓷综合压电性能最好，其中，介电常数为3600，压电系数d33为620pC/N，机电耦合系数kp值为80%，介电损耗小于1%，平均晶粒控制在2-4微米，在保持较高的压电性能的同时具有优异的机械性能，产品的可靠性大大提高，可以广泛应用于大功率的压电陶瓷领域，如大功率压电换能器、超声马达、超英焊接等大功率压电陶瓷器件方面。
本发明提供的一种高机电耦合性能锆钛酸铅细晶压电陶瓷，采用普通的分析纯原材料，并没有使用到价格高昂的超细纳米材料，无需分段烧结法、快速烧结法等高昂的设备，生产工艺简单，克服了分段烧结法、快速烧结法产品合格率较低的问题，大大拓展产品的应用范围。
说明书附图
图1是本发明实施例1的SEM图。
具体实施方式
为了更好的理解本发明，下面结合具体实施例对发明作详细的说明。
本发明的制备方法如下：
（a）配料：按照化学式Pb1-x-y-zBaxNbyNiz（ZraTi1-a）O3的化学计量比计算，其中0＜x≤0.1，0＜y≤0.08，0＜z≤0.08，0.51＜a≤0.6，称取分析纯的Pb3O4、BaCO3、Nb2O5、NiO、ZrO2和TiO2为原料，并将所述原料于球磨罐中球磨混合2.5小时，其中，原料：去离子水：球磨介质为1:2.5:1，转速为750rpm，所述球磨介质为ZrO2球，得到混合后的粉体；
（b）预烧：将步骤（a）得到的混合后的粉体于氧化铝坩埚内密封，在800℃~900℃反应2.5h，得到预烧后粉体；
（c）成型及排塑：将步骤（b）得到的预烧后粉体球磨，在60~100℃烘干后流延成膜，冲制成直径为17.20mm，厚度为12.5±0.5μm坯体，将坯体以3℃/min的升温速率升温至200℃，再以2℃/min的升温速率继续升温至400℃，保温30min后，再以5℃/min的升温速率升温至650℃，保温15min，排出坯体中有机物；
（d）烧结：将步骤（c）得到的排出有机物后的坯体在步骤（b）中预烧后的粉体中于1210℃埋烧2小时，升温速度为5℃/min；
（e）被电极：将步骤（d）得到的烧结后的坯体经超声水洗后烘干被银电极，于780℃保温10min后自然冷却，得到被电极制品；
（f）极化：将步骤（e）得到的被电极制品于100℃的空气中，施加1.4kV/mm的直流电场，极化10min，得到压电陶瓷。
具体实施例和对比例组分如表1所示，表2是各实施例对应的性能检测数据。
表1具体实施例组分表
| x的取代量 | y，z的取代量 | a的取代量 | 合成反应温度 ℃ | |
| 实施例1-1 | 0．04 | y=0.05，z=0.01 | 0.53 | 800 |
| 实施例1-2 | 0．06 | y=0.05，z=0.01 | 0.52 | 800 |
| 实施例1-3 | 0．08 | y=0.04，z=0.01 | 0.54 | 800 |
| 对比例1 | 0．06 | y=0.00，z=0.00 | 0.5 | 8003 --> |
| 实施例2-1 | 0．1 | y=0.01，z=0.03 | 0.55 | 850 |
| 实施例2-2 | 0．06 | y=0.05，z=0.03 | 0.55 | 850 |
| 实施例2-3 | 0．02 | y=0.08，z=0.03 | 0.55 | 850 |
| 对比例2 | 0．06 | y=0.00，z=0.03 | 0.55 | 850 |
| 实施例3-1 | 0．04 | y=0.05，z=0.08 | 0.58 | 900 |
| 实施例3-2 | 0．06 | y=0.05，z=0.03 | 0.58 | 900 |
| 实施例3-3 | 0．08 | y=0.05，z=0.04 | 0.60 | 900 |
| 对比例3 | 0 | y=0.05，z=0.00 | 0.58 | 900 |
表2各实施例与对比例性能检测数据
根据上表数据可以明显看出，本发明提供的高机电耦合性能锆钛酸铅细晶压电陶瓷，在取代量x=0.06，y=0.05，z=0.03，a=0.55（实施例2-2），合成反应温度为850℃时，获得的改性的压电陶瓷综合压电性能最好，其介电常数为3600，压电系数d33为620pC/N，机电耦合系数kp值为80%，介电损耗小于1%，平均晶粒控制在2-4微米，相比于现有的细晶压电陶瓷，综合性能得到了大幅度提升和改善。
以上显示和描述了本发明的基本原理、主要特征和优点。本行业的技术人员应该了解，上述实施例不以任何形式限制本发明，凡采用等同替换或等效变换的方式所获得的技术方案，均落在本发明的保护范围内。
Claims (7)
1.一种高机电耦合性能锆钛酸铅细晶压电陶瓷，其特征在于：其分子式为Pb1-x-y- zBaxNbyNiz（ZraTi1-a）O3，其中0＜x≤0.1，0＜y≤0.08，0＜z≤0.08，0.51＜a≤0.6。
2.根据权利要求1所述的一种高机电耦合性能锆钛酸铅细晶压电陶瓷，其特征在于：其分子式为Pb1-x-y-zBaxNbyNiz（ZraTi1-a）O3，其中x=0.06，y=0.05，z=0.03，a=0.55。
3.如权利要求1或2所述的一种高机电耦合性能锆钛酸铅细晶压电陶瓷的制备方法，其特征在于，包括如下步骤：
（a）配料：按照压电陶瓷的成分及其化学计量比计算，称取原料，并将所述原料于球磨罐中球磨混合2.5小时，得到混合后的粉体；
（b）预烧：将步骤（a）得到的混合后的粉体于氧化铝坩埚内密封，在800℃~900℃反应2.5h，得到预烧后粉体；
（c）成型及排塑：将步骤（b）得到的预烧后粉体经球磨、烘干后流延成膜，冲制成坯体，采用两段升温排出有机物；
（d）烧结：将步骤（c）得到的排出有机物后的坯体在步骤（b）中预烧后的粉体中于1210℃埋烧2小时，升温速度为5℃/min；
（e）被电极：将步骤（d）得到的烧结后的坯体经超声水洗后烘干被银电极，于780℃保温10min后自然冷却，得到被电极制品；
（f）极化：将步骤（e）得到的被电极制品于100℃的空气中，施加1.4kV/mm的直流电场，极化10min，得到压电陶瓷。
4.根据权利要求3所述的一种高机电耦合性能锆钛酸铅细晶压电陶瓷的制备方法，其特征在于：所述步骤（a）中的原料为分析纯的Pb3O4、BaCO3、Nb2O5、NiO、ZrO2和TiO2,；所述球磨混合的条件是原料：去离子水：球磨介质为1:2.5:1，转速为750rpm，所述球磨介质为ZrO2球。
5.根据权利要求3所述的一种高机电耦合性能锆钛酸铅细晶压电陶瓷的制备方法，其特征在于：所述步骤（b）的预烧反应温度为850℃。
6.根据权利要求3所述的一种高机电耦合性能锆钛酸铅细晶压电陶瓷的制备方法，其特征在于：所述步骤（c）中的两段升温是指先以3℃/min的升温速率升温至200℃，再以2℃/min的升温速率继续升温至400℃，保温30min后，再以5℃/min的升温速率升温至650℃，保温15min，排出坯体中有机物。
7.根据权利要求3所述的一种高机电耦合性能锆钛酸铅细晶压电陶瓷的制备方法，其特征在于：所述步骤（e）中被电极采用丝网印刷工艺。
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| CN113511892A (zh) * | 2021-08-09 | 2021-10-19 | 湖南省美程陶瓷科技有限公司 | 一种高压电常数的压电陶瓷材料及其制备方法 |
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| CN113185289B (zh) * | 2021-03-31 | 2022-06-03 | 哈尔滨工业大学 | 一种超低介电损耗的铌锰酸铅-铌镍酸铅-锆钛酸铅高压电性铁电陶瓷及其制备方法 |
| CN113511892A (zh) * | 2021-08-09 | 2021-10-19 | 湖南省美程陶瓷科技有限公司 | 一种高压电常数的压电陶瓷材料及其制备方法 |
| CN113511892B (zh) * | 2021-08-09 | 2022-06-14 | 湖南省美程陶瓷科技有限公司 | 一种高压电常数的压电陶瓷材料及其制备方法 |
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