CN104628383A - 压电陶瓷、其制造方法及具有压电陶瓷的压电陶瓷扬声器 - Google Patents
压电陶瓷、其制造方法及具有压电陶瓷的压电陶瓷扬声器 Download PDFInfo
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- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052745 lead Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明提供压电陶瓷、其制造方法及具有压电陶瓷的压电陶瓷扬声器,上述压电陶瓷为呈现高kr、高相对介电常数的可低温焙烧的特性差异小的压电陶瓷。该压电陶瓷包括:包含陶瓷颗粒的主相,上述陶瓷颗粒含有Pb、Nb、Zn、Ti、Zr并具有钙钛矿型结晶构造;和包含ZnO颗粒的副相。
Description
技术领域
本发明涉及压电陶瓷、压电陶瓷的制造方法及具有压电陶瓷的压电陶瓷扬声器。
背景技术
对于具有将电能转换为机械能、或将机械能转换为电能的功能(压电效果)的压电陶瓷,正在被应用于大量的电子器件中。
以锆钛酸铅(Pb(Ti,Zr)O3,以下称为“PZT”)为主成分的压电瓷器组成物在准同型相界(MPB)附近具有优异的压电性。因此,PZT被广泛用作音响元件、压电促动器等压电器件的材料。
作为压电器件中使用的压电瓷器组成物的特性,根据作为其产品的用途,需要具备高kr、低杨氏模量、一定程度的电阻、高居里温度等。而且,作为满足这种特性的压电瓷器组成物提出了各种组成物。
为了改善PZT类压电瓷器组成物的特性,专利文献1和专利文献2中记载有通过对PZT固溶Pb(Ni1/3Nb2/3)O3(以下称为“PNN”)、Pb(Zn1/3Nb2/3)O3(以下称为“PZN”)等,将作为B位成分的Ti和Zr置换为其它原子。例如,在专利文献1中记载有,在PNN-PZN-PZ-PT这4成分类复合氧化物中,在将作为A位成分的Pb置换为Ca、Sr、Ba等其它元素的基础上,还以比化学计量成分只过剩规定摩尔量地添加比Ti或Zr价数小的受主元素(Ni,Zn),而使B位组成为受主过剩,并且使其它各成分的含有摩尔比在规定范围,由此,可以进行低温焙烧。在专利文献2中公开有由钙钛矿组成物和该钙钛矿组成物中所含的Ag2O构成的特定组成的压电瓷器组成物,该压电瓷器组成物可以在900℃以下的低的温度下进行烧结,而且陶瓷颗粒的粒径小,机械强度高。
现有技术文献
专利文献
专利文献1:国际公开WO/2006/075449号公报
专利文献2:日本特开2003-238248号公报
发明内容
发明所要解决的课题
本发明的课题在于提供一种高kr、高相对介电常数能够低温焙烧的特性高且特性不均小的压电陶瓷。
本发明的压电陶瓷包括:包含陶瓷颗粒的主相,所述陶瓷颗粒含有Pb、Nb、Zn、Ti、Zr并具有钙钛矿型结晶构造;和包含ZnO颗粒的副相。
优选主相包含成为Pb{(Zr(1-a)Tia)x·(Ni1/3Nb2/3)y·(Zn1/3Nb2/3)z}O3(其中,0<x≦0.85、0≦y<1、0<z<1、x+y+z=1、0.45≦a≦0.60)组成的陶瓷颗粒,更优选上述x和y满足0<x<0.75并且0<y<1。另外,优选作为副相的ZnO颗粒的大小为0.4~1.6μm。
作为本发明提供的压电陶瓷的优选制造方法,其包括:取得成为Pb{(Zr(1-a)Tia)x·(Ni1/3Nb2/3)y·(Zn1/3Nb2/3)z}O3(其中,0<x≦0.75、0≦y<1、0<z<1、x+y+z=1、0.45≦a≦0.60)组成的具有钙钛矿型结晶构造的陶瓷颗粒构成的组成物的步骤;和将所取得的组成物和ZnO颗粒进行混合、成形、焙烧的步骤。在上述制造方法中,优选0<x<0.75,0<y<1。
根据本发明,还提供一种具备音响元件的压电陶瓷扬声器,该音响元件具有上述压电陶瓷。
发明效果
根据本发明,能够提供一种可在900℃以下进行焙烧,并且一举实现高kr和高相对介电常数以及低的特性差异(不均)的压电陶瓷。通过该压电陶瓷的使用,期待高性能的扬声器的实现。
附图说明
图1是压电陶瓷扬声器的制造的说明图。
符号说明
10:压电发音元件
12:振动板
12A:粘接剂
14:驱动板
14A~14C:层叠片
14D~14F:通孔
16:振动抑制材料
20:框体
32,34:电极
36:通孔导体
具体实施方式
本发明的压电陶瓷具有主相和副相。
主相的陶瓷颗粒含有Pb、Nb、Zn、Ti、Zr的全部、优选还含有Ni并具备钙钛矿型结晶构造。本发明的压电陶瓷主要是主相占居,在主相中分散有副相。副相含有ZnO颗粒。
主相优选由成为Pb{(Zr(1-a)Tia)x·(Ni1/3Nb2/3)y·(Zn1/3Nb2/3)z}O3组成的陶瓷颗粒构成。在此,0<x≦0.85、0≦y<1、0<z<1、x+y+z=1、0.45≦a≦0.60。关于x和y,更优选0<x<0.75,0<y<1。x为0.85以下,更优选小于0.75,由此,能够实现焙烧温度的降低。通过使y和z在上述范围内,能够通过a值的选择容易地调整压电特性和居里温度。通过使a值在上述范围内,能够增大压电常数。
主相的陶瓷颗粒的化学组成可以使用能量分散型X射线分析的方法进行测定。此外,在本发明的陶瓷类中,通过原材料的调整,能够调节陶瓷颗粒的组成。
副相分散在主相中。副相由ZnO颗粒构成。由于副相的存在,构成为能量性非常低的稳定的构造。即,即使施加比通常低的热能也可取得稳定的构造。换言之,副相的存在具有促进烧结的效果。另外,通过粒界牢固地结合,期待主体烧结体的强度也变大。由于这些效果,可更稳定地得到良好的体积密度的陶瓷,可进行低温下的焙烧。
作为副相的ZnO颗粒的大小优选0.4~1.6μm。ZnO颗粒的大小通过图像分析求得在压电陶瓷的截面的SEM观察图像中看到的例如100个以上的ZnO颗粒的直径,作为它们的平均值(平均粒径)计算出来。
本发明的压电陶瓷可以适当使用现有公知的压电陶瓷的制法进行制造。作为非限定的制法的一例,可以举出具有如下步骤的制造,即:取得由具有Pb{(Zr(1-a)Tia)x·(Ni1/3Nb2/3)y·(Zn1/3Nb2/3)z}O3的组成的钙钛矿型结晶构造的陶瓷颗粒构成的组成物的步骤;和将所取得的组成物和ZnO颗粒进行混合、成形、焙烧的步骤。在此,如上所述,其中,0<x≦0.85、0≦y<1、0<z<1、x+y+z=1、0.45≦a≦0.60,关于x和y,更优选0<x<0.75、0<y<1。
关于获得由具有钙钛矿型结晶构造的陶瓷颗粒构成的组成物的步骤,可以适当参照现有公知的陶瓷颗粒的制法。例如可举出将各金属原料例如PbO、ZrO2、TiO2、NiO、ZnO、Nb2O5等粉末进行湿式混合,使所得到的悬浊液干燥,将通过干燥得到的混合物在例如大气气氛下使用电炉优选在900℃以下进行焙烧等。通过该处理,混合物内的各金属氧化物进行固相反应,形成钙钛矿化合物。各处理的具体例在后述的实施例中表示。
将所得到的钙钛矿化合物、作为副相原料的ZnO颗粒通过例如湿式粉碎进行混合,并使之干燥,由此可获得成品粉状体(焙烧前的粉状体)。在该成品粉状体中根据需要混合有机粘合剂之后,通过压缩成型等成型为规定的形状,进行焙烧,由此能够获得压电陶瓷。焙烧气氛没有特别限定,优选在大气气氛下进行。焙烧温度优选850~900℃。可以在焙烧后的压电陶瓷上印刷含有Ag等的导电膏。
在本发明中,也可以提供使用上述压电陶瓷的压电陶瓷扬声器。压电陶瓷适宜用作音响元件的构成要素。例如,通过在由压电陶瓷构成的层叠体的两面连接电极端子并施加直流电压进行分极处理,获得压电驱动板,可以将该压电驱动板粘接于振动板。也可以在上述振动板形成振动抑制材料。这样一来,能够获得音响元件,要由该音响元件获得作为产品的扬声器,可以适当参照现有公知的方法。另外,具体的制造例在后述的实施例中记载。
实施例
下面,通过实施例更具体地说明本发明。但是,本发明不仅限于这些实施例中记载的方式。
〔实施例1、2、比较例1〕
首先,分别准备由PbO、ZrO2、TiO2、NiO、ZnO、Nb2O5构成的原料粉末,秤量这些原料粉末,将其与氧化锆珠、离子交换水一起加入罐磨机内,进行16小时湿式混合,将所得的浆料移至搪瓷盆,放入干燥器内,在150℃下进行干燥。原料的投入量反映成为Pb{(Zr(1-a)Tia)x·(Ni1/3Nb2/3)y·(Zn1/3Nb2/3)z}O3组成的陶瓷颗粒的各金属的存在量比。在此,a=0.548、x=0.636、y=0.14、z=0.224。
然后,将通过干燥获得的混合物在大气气氛下使用电炉在830℃进行3小时焙烧。混合物内的各金属氧化物通过该焙烧而相互地发生固相反应,形成钙钛矿化合物。该化合物相当于主相。
接着,将该钙钛矿化合物、在实施例1、2中相当于副相的具有规定的颗粒尺寸的ZnO颗粒、氧化锆珠、离子交换水一起放入罐磨机内,进行16小时湿式粉碎,将得到的悬浊液移至搪瓷盆,放入干燥器内,使之在150℃下干燥,获得成品粉状体。作为副相的原料的ZnO的量相对于钙钛矿化合物的100重量份为0.2~0.25重量份。在比较例1中,不添加ZnO颗粒进行上述操作。接着,向该成品粉状体中混合少量有机粘合剂,使用加压冲压机,以压力1.5MPa进行压缩成型,获得直径8mm、厚度0.5mm的圆板形的试样。接着,将该试样放入电炉内,在大气气氛下在900℃进行2小时焙烧,之后将该试样从电炉中取出,在试样的两面印刷无玻璃料(frit less)Ag膏,在大气气氛下在870℃进行焙烧,将其作为外部电极。
接着,对带有该外部电极的试样,在150℃下施加2.0kV/mm的电压15分钟,使试样进行分极。接着,测定该分极的试样的相对介电常数,按照电子信息技术产业界标准(JEITA EM-4501)进行阻抗测定,计算压电特性kr。
〔实施例3、比较例2〕
除了将主相的钙钛矿化合物的组成构成为Pb{(Zr(1-a)Tia)x·(Ni1 /3Nb2/3)y·(Zn1/3Nb2/3)z}O3的组成(其中,a=0.49、x=0.8、y=0、z=0.2)之外,与上述同样地操作(因此,未使用NiO。),制造添加作为副相的ZnO颗粒而成的实施例3和没有进行这种添加的比较例2的试样,如上所述进行分极处理、压电特性的计算。
对试样进行截面观察,其结果是,在实施例1、2、3中看到了主相和副相,在比较例1、2中未看到与副相相当的部分。还进行了主相和副相的化学分析,确认原料粉末的添加比率直接反映在陶瓷组成中。
在实施例1、2、3中,仅看见100个副相部分,根据图像测定它们的直径并进行平均,由此计算ZnO颗粒的大小。
上述的测定、评价结果如下。
音压由kr和相对介电常数的关系决定。
即,只要kr为69以上、相对介电常数为1900以上,即可确保规定的音压。或只要kr为67以上、相对介电常数为3000以上,即可确保规定的音压。
在本实施例中判明,在含有Ni时,相对介电常数变高,在本实施例中,在不含Ni时,Kr变高。
使用与上述实施例2、3及比较例1、2相同的压电陶瓷,分别各制造5个压电陶瓷扬声器进行评价。图1是压电陶瓷扬声器的制造的说明图。首先,从成为驱动板14的层叠体进行说明时,制成向上述成品粉状体中添加了粘合剂的浆料,用刮刀等方法由此获得生片。将这样获得的生片切断,并且,用网版印刷法印刷Ag膏(电极32、34),形成图1(A)所示的层叠片14A~14C。此外,在该部位分别形成通孔14D~14F。之后,如该图(B)所示,将各层叠片14A~14C在层叠的同时进行压接。然后,如该图(C)所示,在通孔内部填充Ag膏(通孔导体36)。之后,切断为规定形状,并且在900℃温度下进行焙烧,获得外径15mm、厚度60μm(20μm×3层)的层叠体。
通过在该层叠体的两面连接电极端子并施加直流电压而进行分极处理,获得压电驱动板。将所得的驱动板14如图1(C)所示与形成有振动抑制材料16的振动板12粘接。振动板12和驱动板14的粘接是通过在振动板12的主面用网版印刷均匀地印刷粘接剂12A,在其上粘贴驱动板14而进行。这时,作为粘接剂12A使用了导电性粘接剂。这样一来,获得音响元件10,通过将该音响元件组装在框体20而获得压电陶瓷扬声器。
对所得的压电陶瓷扬声器评价了电气机械结合常数k31(%)、压电应变常数d31(%)、800、1000、1500、2000Hz的平均音压(dB)。平均音压的5个样品的平均值反映压电陶瓷扬声器的特性的大小,平均音压的5个样品的偏差反映特性的差异(不均)的大小。
将上述的评价结果汇总于以下的表(分别为5个样品)。表1表示实施例2的结果。
表1
表2表示比较例1的结果。
表2
表3表示实施例3的结果。
表3
表4表示比较例2的结果。
表4
与比较例1相比,在实施例2中,k31、d31普遍都大,平均音压也大,且平均音压的偏差(相当于特性差异)小。关于与比较例2对比时的实施例3也同样。
工业上的应用
根据本发明,能够实现压电扬声器的特性提高和差异减少,能够期待音响产品等的品质的进一步提高。
Claims (7)
1.一种压电陶瓷,其特征在于,包括:
包含陶瓷颗粒的主相,所述陶瓷颗粒含有Pb、Nb、Zn、Ti、Zr并具有钙钛矿型结晶构造;和
包含ZnO颗粒的副相。
2.如权利要求1所述的压电陶瓷,其特征在于:
所述ZnO颗粒的平均粒径为0.4~1.6μm。
3.如权利要求1或2所述的压电陶瓷,其特征在于:
所述主相包含由组成式Pb{(Zr(1-a)Tia)x·(Ni1/3Nb2/3)y·(Zn1 /3Nb2/3)z}O3表示的陶瓷颗粒,其中,0<x≦0.85、0≦y<1、0<z<1、x+y+z=1、0.45≦a≦0.60。
4.如权利要求3所述的压电陶瓷,其特征在于:
所述x和y满足0<x<0.75且0<y<1。
5.一种压电陶瓷扬声器,其特征在于:
具备音响元件,该音响元件具有权利要求1~4中任一项记载的压电陶瓷。
6.一种压电陶瓷的制造方法,其特征在于,包括:
得到成为Pb{(Zr(1-a)Tia)x·(Ni1/3Nb2/3)y·(Zn1/3Nb2/3)z}O3组成的具有钙钛矿型结晶构造的陶瓷颗粒构成的组成物的步骤,其中,0<x≦0.85、0≦y<1、0<z<1、x+y+z=1、0.45≦a≦0.60;和
将所得到的组成物和ZnO颗粒进行混合、成形、焙烧的步骤。
7.如权利要求6所述的制造方法,其特征在于:
所述x和y满足0<x<0.75并且0<y<1。
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