CN104379535A - 压电陶瓷组合物 - Google Patents
压电陶瓷组合物 Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 86
- 239000000919 ceramic Substances 0.000 title claims abstract description 75
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 230000008878 coupling Effects 0.000 claims description 10
- 238000010168 coupling process Methods 0.000 claims description 10
- 238000005859 coupling reaction Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 13
- 239000010953 base metal Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical group [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001483 high-temperature X-ray diffraction Methods 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
提供一种能够不含铅地组成并具有良好压电特性的压电陶瓷组合物。压电陶瓷组合物（10）由化学式｛Lix（K1-yNay）1-x｝（Nb1-zSbz）O3表示、并含有Bi和Fe作为添加物的金属元素。以摩尔比表示的Bi的添加量为v、以摩尔比表示的Fe的添加量为w时，满足0.03≤x≤0.045、0.5≤y≤0.58、0.03≤ｚ≤0.045、0.006≤v≤ｗ≤0.010的范围。
Description
技术领域
本发明涉及用于致动器、超声波传感器、超声波振子等的碱金属铌酸盐系压电陶瓷组合物。
背景技术
压电陶瓷组合物用于致动器、超声波传感器、超声波振子等压电元件。目前，虽然如锆钛酸铅（PZT）等含铅化合物的压电陶瓷组合物作为压电特性优良的压电陶瓷组合物已经实用化，但是担心含铅化合物的压电陶瓷组合物对环境产生不良影响。因此，近年来不含铅化合物的压电陶瓷组合物受到关注，其研究开发得到推进。作为不含该铅化合物的压电陶瓷组合物，在专利文献1等中公开了碱金属铌酸盐系压电陶瓷组合物。
专利文献1中公开的压电陶瓷组合物由化学式｛Lix（K1-yNay）1-x｝（Nb1-zSbz）O3表示，并且x、y、z的组成范围为，0<x≤0.2、0<y<1、0<ｚ≤0.2。
现有技术文献
专利文献1：特许第4631246号公报；
不过，本发明人利用专利文献1公开的制造方法尝试制造了上述组成的碱金属铌酸盐系压电陶瓷组合物，但是难以得到致密的陶瓷，也未能获得压电特性良好的压电陶瓷组合物。
发明内容
本发明是鉴于上述课题作出的，其目的在于提供一种能够不含铅地组成并且具有良好的压电特性的碱金属铌酸盐系压电陶瓷组合物。
为解决上述课题，方案1的发明的要旨是一种压电陶瓷组合物，其特征在于，由化学式｛Lix（K1-yNay）1-x｝（Nb1-zSbz）O3表示、并含有Bi和Fe作为添加物的金属元素，以摩尔比表示的Bi的添加量为v、以摩尔比表示的Fe的添加量为w时，满足下述关系式的范围，0.03≤x≤0.045、0.5≤y≤0.58、0.03≤ｚ≤0.045、0.006≤v≤ｗ≤0.010。
根据方案1的发明，对由化学式｛Lix（K1-yNay）1-x｝（Nb1-zSbz）O3表示的碱金属铌酸盐系组合物，以适当比例添加Bi和Fe金属元素。这样，在组成不含铅的压电陶瓷组合物中能够获得良好的压电特性。
方案2的发明的主旨是，在方案1中，压电常数d33为250pC/N以上，居里温度为330℃以上。
根据方案2的发明，由于压电常数d33为250pC/N以上，居里温度为330℃以上，故通过采用本发明的压电陶瓷组合物，能够构成压电特性良好并且耐热性优良的机电转换元件（压电致动器、超声波传感器等）。
方案3的发明的主旨是，在方案1或2中，上述压电陶瓷组合物是具有表面和背面的圆板状，径向机电耦合系数Kp为0.44以上、相对介电常数ε33 T/ε0为1390以上。
根据方案3的发明，由于径向机电耦合系数Kp为0.44以上、相对介电常数ε33 T/ε0为1390以上，所以通过采用本发明的压电陶瓷组合物，能够构成压电性能良好的机电转换元件（压电致动器、超声波传感器等）。
方案4的发明的主旨是，在方案1或2中，上述压电陶瓷组合物是具有表面和背面的圆板状，径向机电耦合系数Kp为0.44以上、相对介电常数ε33 T/ε0为1390以上、介电损耗tanδ为0.03以下。
根据方案4的发明，由于径向机电耦合系数Kp为0.44以上、相对介电常数ε33 T/ε0为1390以上、介电损耗tanδ为0.03以下，所以通过采用本发明的压电陶瓷组合物，能够构成压电性能良好的机电转换元件（压电致动器、超声波传感器等）。
发明效果
如上详细所述，根据方案1-4的发明，能够提供一种可以不含铅地组成并且具有良好的压电特性的压电陶瓷组合物。
附图说明
图1是表示一实施方式的压电陶瓷组合物的立体图。
具体实施方式
下面基于附图详细说明本发明具体化的压电陶瓷组合物的一实施方式。
图1是表示本实施方式的压电陶瓷组合物10的立体图。压电陶瓷组合物10是具有表面和背面的圆板形状，具有直径15mm、厚度1mm的尺寸。压电陶瓷组合物10用作例如构成超声波流量计的超声波传感器。
本实施方式的压电陶瓷组合物10是铌酸钾钠系（碱金属铌酸盐系）压电陶瓷组合物，含有钙钛矿结构的结晶相而构成。更详细而言，压电陶瓷组合物10由以下化学式（1）表示，作为添加物的金属元素含有Bi（铋）以及Fe（铁）。
｛Lix（K1-yNay）1-x｝（Nb1-zSbz）O3 …(1)
但是，当Bi的添加量（摩尔比）为v、Fe的添加量（摩尔比）为w时，具有满足下述范围的组成，0.03≤x≤0.045、0.5≤y≤0.58、0.03≤ｚ≤0.045、0.006≤v≤ｗ≤0.010。
以下详细说明压电陶瓷组合物10的制造方法。
首先，准备K2CO3、Na2CO3、Li2CO3、Nb2O5、Sb2O3、Bi2O3、Fe2O3的原料粉末（纯度99%以上）。然后，称量含有各金属元素的原料粉末以满足表1所示实施例1-18以及比较例1-19的各组成，并用球磨机在乙醇中混合24小时而获得混合浆料。另外，对含有各金属元素的原料粉末（化合物）的种类没有特别限制，但是可优选使用各金属元素的氧化物、碳酸盐等。
接着，干燥所获得的混合浆料，在900℃下煅烧3小时后，利用球磨机粉碎24小时。进而，添加聚乙烯醇水溶液作为粘合剂，并造粒。然后，将造粒后的粉体在200MPa的压力下加压成形为直径18mm、厚度2mm的圆板状，将该成形体在1000-1200℃下烧结2.5小时，制作烧结体。另外，此时的烧结温度选定在1000-1200℃之间、使烧结体成为最大密度的温度。
接着，对烧结后的各烧结体的两个面进行平行研磨，加工成图1所示的直径约15mm、厚度1mm的圆板形状后，在该圆板试样的两面涂敷银浆，并在700℃下烧银，形成对置电极。接着，在130℃的硅油中于电极间施加3kV/mm的直流电压20分钟，使之在厚度方向上极化，制成压电陶瓷组合物10。
【表1】
这样，分别制造了实施例1-18以及比较例1-19的压电陶瓷组合物10的样品。此外本发明人对实施例1-18以及比较例1-19的压电陶瓷组合物10的电特性进行了测量。其测量结果也示于表1。
本实施方式中，用阻抗分析仪（Agilent公司制4294A）在25℃的温度下对径向的机电耦合系数Kp、相对介电常数ε33 T/ε0、介电损耗tanδ的电特性分别进行了测量。而且，采用d33/d31测量仪（ZJ-6B型，中国科学院声学研究所）在25℃的温度下测量了压电常数d33。另外，关于居里温度Tc，采用阻抗分析仪（Agilent公司制4294A）测量介电常数的温度变化，将介电常数为最大时的温度作为居里温度Tc。另外，本实施方式中，通过一边降低温度一边测量介电常数的降温时的测量来求出居里温度Tc。并且利用X射线衍射装置（RIGAKU公司制SmartLab，X射线源：CuKα）进行高温XRD分析，确认了在居里温度Tc附近产生了从正方晶向立方晶的相变。
如表1所示，实施例1-18的压电陶瓷组合物10满足上述化学式（1）中的0.03≤x≤0.045、0.5≤y≤0.58、0.03≤ｚ≤0.045、0.006≤v≤ｗ≤0.010的组成范围。实施例1-18的压电陶瓷组合物10具有压电常数d33为250pC/N以上、居里温度Tc为330℃以上这样的良好的压电特性。推测是通过在实施例1-18的压电陶瓷组合物10中添加了适量的Bi和Fe而获得了如下的良好的压电特性。即，认为通过添加Bi和Fe，为晶格结构引入点缺位，从而增加了由ABO3表示的钙钛矿结构中的A位缺位的容许量。而且，在A位缺位为最大时获得了该组成下的最佳特性。认为这是因为通过产生A位缺位而容易生成畴壁。并推测通过减小畴尺寸，压电特性变好。
表2中示出了与Bi的添加量v（摩尔比）和Fe的添加量w（摩尔比）相对应的压电常数d33(pC/N)。另外，表2中示出了各组成比x、y、z为x=0.04、y=0.54、z=0.04的实施例1-12、比较例1-17的样品中与Bi的添加量v和Fe的添加量w相对应的压电常数d33。如表2所示，在0.006≤v≤ｗ≤0.010的组成范围（实施例1-12的组成范围）中，压电常数d33为250pC/N以上，获得了所希望的压电特性。
【表2】
实施例13中，Na的组成比y为0.50，实施例14中Na的组成比y为0.58，Li、Sb的组成比x、z以及Bi、Fe的添加量v、w与实施例8的值相同。如实施例13、实施例14所示，能够确认到当将Na的组成比y变为0.50～0.58时，压电常数d33为250pC/N以上，也获得了良好的压电特性。
实施例15中，组成比x、z为0.03，实施例16中，组成比x、z为0.045，组成比y以及Bi、Fe的添加量v、w与实施例8的值相同。另外，实施例8、15、16中，组成比x和组成比z为相同的比率。此外，实施例17中，组成比x为0.03、组成比z为0.045，实施例18中，组成比x为0.045、组成比z为0.03，关于组成比y、以及Bi、Fe的添加量v、w与实施例8的值相同。如各实施例15-18所示，将组成比x、z变为0.03～0.045时，相较于实施例8，压电常数d33稍微降低，但是能够确保250pC/N以上的压电常数d33，可确认到获得了良好的压电特性。
比较例1～7中，Bi的添加量v为0.005以下，比较例8、12中，Bi的添加量v比Fe的添加量w多。此外，比较例13～17中，Bi的添加量v为0.012以上，比较例9、14、17中，Fe的添加量w为0.012以上。而且，比较例10、11中，Fe的添加量w为0.004以下。此外，比较例18、19中，Li的组成比x为0.05以上，Sb的组成比z为0.05以上。另外，没有添加Bi和Fe的比较例1是专利文献1公开的与现有技术组成相对应的压电陶瓷组合物。
如表1和表2所示，Bi的添加量v和Fe的添加量w不在0.006≤v≤ｗ≤0.010的组成范围（表2中粗线围起的范围）的比较例1～17的压电常数d33为240pC/N以下。此外，比较例18、19不在0.03≤x≤0.045、0.03≤ｚ≤0.045的组成范围，压电常数d33为240pC/N以下。
另外，上述压电陶瓷组合物10中，如果由ABO3表示的钙钛矿结构中的A位缺位以适度比例（2%左右）存在，则压电特性变好。因此，也可以进行组成调和使得A位元素（Li、K、Na）和B位元素（Nb、Sb）的比例（A/B）为0.95以上不满1.0地来制造压电陶瓷组合物10。这样，即使在B位元素过剩的组成中，通过以上述的0.006≤v≤ｗ≤0.010的组成范围来添加Bi和Fe，也能够提高压电特性。
因此，根据本实施方式，能够获得以下效果。
（1）本实施方式中的实施例1～18的压电陶瓷组合物10以上述化学式中组成范围为0.03≤x≤0.045、0.5≤y≤0.58、0.03≤ｚ≤0.045、0.006≤v≤ｗ≤0.010地来制造。如果以这样的组成范围来制造压电陶瓷组合物10，则能够获得压电常数d33为250pC/N以上、居里温度Tc为330℃以上这样的良好的压电特性。此外，实施例1～18的压电陶瓷组合物10的径向机电耦合系数Kp为0.44以上、相对介电常数ε33 T/ε0为1390以上、介电损耗tanδ为0.03以下，具有优良的电特性。因此，采用实施例1～18的压电陶瓷组合物10来构成例如超声波流量计的超声波传感器时，能够有效地产生超声波。此外，即使在较高温度（例如，200℃）下使用该超声波流量计，也能够精度良好地进行流量测量。
（2）本实施方式中的实施例6～8、10的压电陶瓷组合物10以组成范围为0.007≤v≤ｗ≤0.009地来制造。以这样的组成范围来制造压电陶瓷组合物10，则能够获得压电常数d33为270pC/N以上、居里温度为340℃以上、径向机电耦合系数Kp为0.47以上、相对介电常数ε33 T/ε0为1450以上、介电损耗tanδ为0.025以下这样优良的电特性。
（3）本实施方式中的实施例1～18的压电陶瓷组合物10由于不含铅地被制造，所以废弃压电陶瓷组合物10时，能够避免对环境产生不好影响。
（4）本实施方式中的实施例1～18的压电陶瓷组合物10不含有Ta（钽）来作为由ABO3表示的钙钛矿结构中的B位元素。虽然已知的是，铌酸钾钠系压电陶瓷组合物中，作为B位元素通过含有Ta使得压电特性良好，但是Ta相比于其他元素（Nb、Sb）是比较贵的材料。因此，本实施方式中，即使不含有Ta也能够制造压电特性良好的压电陶瓷组合物10，能够将制造成本抑制得较低。
另外，本发明的实施方式也可以做如下变更。
上述实施方式的压电陶瓷组合物10用作超声波流量计的超声波传感器，但是并不限于此。具体而言，也可以在例如测量液体中传播的超声波的衰减率、并基于该衰减率来判断有无气泡的气泡检测传感器、以及基于超声波的衰减率检测液体浓度的超声波浓度计等中采用压电陶瓷组合物10。除了上述用途之外，压电陶瓷组合物10也可以用于发动机的爆震传感器、压电致动器以及超声波清洗机的超声波振子等。另外，本实施方式的压电陶瓷组合物10虽是圆板状元件，但是也可以根据用途适当改变元件的形状和尺寸。
接着，除了权利要求书所记载的技术思想外，将根据上述实施方式所把握的技术思想列举如下。
（1）方案1至4的任一项的压电陶瓷组合物的特征在于，上述Bi的添加量v和上述Fe的添加量w满足0.007≤v≤ｗ≤0.009的关系。
（2）技术思想（1）的压电陶瓷组合物的特征在于，压电常数d33为270pC/N以上、居里温度为340℃以上。
（3）技术思想（2）的压电陶瓷组合物的特征在于，径向机电耦合系数Kp为0.47以上、相对介电常数ε33 T/ε0为1450以上、介电损耗tanδ为0.025以下。
（4）方案1至4的任一项的压电陶瓷组合物的特征在于，上述Fe的添加量w比上述Bi的添加量v多。
（5）方案1至4的任一项的压电陶瓷组合物的特征在于，上述压电陶瓷组合物不含铅。
（6）方案1至4的任一项的压电陶瓷组合物的特征在于，上述压电陶瓷组合物用于超声波传感器。
（7）方案1至4的任一项的压电陶瓷组合物的特征在于，上述压电陶瓷组合物用于致动器。
附图标记说明
10 压电陶瓷组合物
Claims (4)
1.一种压电陶瓷组合物，其特征在于，由化学式｛Lix（K1-yNay）1-x｝（Nb1-zSbz）O3表示、并含有Bi和Fe作为添加物的金属元素，以摩尔比表示的Bi的添加量为v、以摩尔比表示的Fe的添加量为w时，满足下述关系式的范围，
0.03≤x≤0.045、0.5≤y≤0.58、0.03≤ｚ≤0.045、0.006≤v≤ｗ≤0.010。
2.如权利要求1所述的压电陶瓷组合物，其特征在于，压电常数d33为250pC/N以上，居里温度为330℃以上。
3.如权利要求1或2所述的压电陶瓷组合物，其特征在于，上述压电陶瓷组合物是具有表面和背面的圆板状，径向机电耦合系数Kp为0.44以上、相对介电常数ε33 T/ε0为1390以上。
4.如权利要求1或2所述的压电陶瓷组合物，其特征在于，上述压电陶瓷组合物是具有表面和背面的圆板状，径向机电耦合系数Kp为0.44以上、相对介电常数ε33 T/ε0为1390以上、介电损耗tanδ为0.03以下。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733650A (zh) * | 2004-06-17 | 2006-02-15 | 株式会社电装 | 晶粒取向陶瓷及其制造方法 |
| CN1765797A (zh) * | 2004-10-29 | 2006-05-03 | 株式会社电装 | 多晶陶瓷体的制备方法 |
| WO2008032500A1 (fr) * | 2006-09-12 | 2008-03-20 | Konica Minolta Holdings, Inc. | Procédé de production d'une substance piézoélectrique et substance piézoélectrique |
| CN101423391A (zh) * | 2008-11-12 | 2009-05-06 | 桂林电子科技大学 | 一种新型铌酸钾钠基无铅压电陶瓷及其制备方法 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4631246B2 (ja) | 2002-03-20 | 2011-02-16 | 株式会社豊田中央研究所 | 圧電磁器組成物及びその製造方法並びに圧電素子及び誘電素子 |
| EP1382588B9 (en) * | 2002-07-16 | 2012-06-27 | Denso Corporation | Piezoelectric ceramic composition and method of production of same |
| JP4541985B2 (ja) | 2004-10-29 | 2010-09-08 | 株式会社デンソー | 多結晶体の製造方法 |
| CN101291889B (zh) * | 2005-10-27 | 2011-09-07 | 京瓷株式会社 | 压电陶瓷组成物和压电陶瓷 |
| JP5177565B2 (ja) | 2009-03-13 | 2013-04-03 | 国立大学法人金沢大学 | 強誘電体、圧電体及びこれらの製造方法 |
| JP5885931B2 (ja) * | 2010-03-15 | 2016-03-16 | キヤノン株式会社 | ビスマス鉄酸化物粉体、その製造方法、誘電体セラミックス、圧電素子、液体吐出ヘッドおよび超音波モータ |
-
2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733650A (zh) * | 2004-06-17 | 2006-02-15 | 株式会社电装 | 晶粒取向陶瓷及其制造方法 |
| CN1765797A (zh) * | 2004-10-29 | 2006-05-03 | 株式会社电装 | 多晶陶瓷体的制备方法 |
| WO2008032500A1 (fr) * | 2006-09-12 | 2008-03-20 | Konica Minolta Holdings, Inc. | Procédé de production d'une substance piézoélectrique et substance piézoélectrique |
| CN101423391A (zh) * | 2008-11-12 | 2009-05-06 | 桂林电子科技大学 | 一种新型铌酸钾钠基无铅压电陶瓷及其制备方法 |
Non-Patent Citations (5)
| Title |
|---|
| MINHONG JIANG 等: ""Dielectric and piezoelectric properties of LiSbO3 doped 0.995 K0.5Na0.5NbO3–0.005BiFeO3 piezoelectric ceramics"", 《MATERIALS LETTERS》 * |
| MINHONG JIANG 等: ""Phase structures and electrical properties of new lead-free Na0.5K0.5NbO3–LiSbO3–BiFeO3 ceramics"", 《SCRIPTA MATERIALIA》 * |
| 江民红 等: ""BiFeO3掺杂K0.5Na0.5NbO3-LiSbO3无铅压电陶瓷的相变及退极化性能研究"", 《航空材料学报》 * |
| 江民红 等: ""K0.5Na0.5NbO3–LiSbO3–BiFeO3无铅压电陶瓷的烧结特性"", 《硅酸盐学报》 * |
| 江民红 等: ""准同型相界内KNN-LS-BF无铅压电陶瓷的烧结与压电性能"", 《中南大学学报（自然科学版）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017071643A1 (zh) * | 2015-10-29 | 2017-05-04 | 武汉依麦德新材料科技有限责任公司 | 具有阻隔紫外线作用的透明聚酰亚胺薄膜及其制备和应用 |
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