CN102531594A - 铅系压电材料及其制造方法 - Google Patents

铅系压电材料及其制造方法 Download PDF

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CN102531594A
CN102531594A CN2011103511965A CN201110351196A CN102531594A CN 102531594 A CN102531594 A CN 102531594A CN 2011103511965 A CN2011103511965 A CN 2011103511965A CN 201110351196 A CN201110351196 A CN 201110351196A CN 102531594 A CN102531594 A CN 102531594A
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lead
piezoelectric
particle
size
pzt
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小泉贵昭
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NGK Insulators Ltd
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NGK Insulators Ltd
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Abstract

本发明的课题在于提供适宜地用作晶体取向陶瓷生长的晶种的铅系压电材料及其制造方法。上述课题通过铅系压电材料来解决，所述铅系压电材料为粒子状的铅系压电材料，中位径小于1μm，由[粒径算术偏差/平均粒径]所表示的粒度分布为15％以下，全部粒子中85％以上具有立方体形状。

Description

铅系压电材料及其制造方法
技术领域
本发明涉及铅系压电材料及其制造方法。
背景技术
锆钛酸铅(PZT)等铅系压电材料用于各种设备中。
专利文献1中，作为将PZT适用于设备的方法之一，举出了烧结PZT粒子的方法。而且，专利文献1中，关于作为PZT粒子的制造方法的通常的固相法的问题点，举出了由于所得的PZT粒子的粒径大，因此需要高烧结温度这一点。
专利文献1中，为了降低烧结温度，提出了制造具有小粒径的PZT粒子的方法。特别是专利文献1中记载了通过搅拌Pb(NO3)2水溶液、ZrOCl2水溶液、TiCl4水溶液以及KOH水溶液来形成前体粒子，进而通过对该前体粒子进行水热处理来得到PZT粉末。
现有技术文献
专利文献
专利文献1：日本特开平11-116395号公报
发明内容
发明要解决的课题
于是，本发明人等注目于通过将压电材料的粒子用作晶种，能够使取向度高的晶体取向陶瓷生长这一点。晶种也被称作模板。
本发明的目的在于实现在二维排列时被覆率大、能够适宜地用作晶种的铅系压电材料。
解决课题的方法
本发明人等实现了尺寸小、粒径的均匀性高的新的铅系压电材料来作为能够用作晶种的铅系压电材料。而且发现了为了得到这种铅系压电材料而优选使用的材料。
本发明的第1观点的粒子状的铅系压电材料的平均粒径在5～30nm的范围内，由[粒径算术偏差/平均粒径]所表示的粒度分布为10％以下。方便起见，有时将该铅系压电材料称作“纳米粉体”。纳米粉体优选用于得到下述第2观点的铅系压电材料。
本发明的第2观点的粒子状的铅系压电材料的中位径小于1μm，由[粒径算术偏差/平均粒径]所表示的粒度分布为15％以下，全部粒子中85％以上具有立方体形状。
本发明的第3观点的铅系压电材料的制造方法是包含将用以形成上述第2观点的粒子的纳米粒子为核、通过水热法使粒子生长的工序的上述第2观点的铅系压电材料的制造方法。
发明效果
中位径小于1μm、由[粒径算术偏差/平均粒径]所表示的粒度分布为15％以下、全部粒子中85％以上具有立方体形状的粒子状的铅系压电材料在二维排列时被覆率大，优选用于晶体取向陶瓷的制造。
附图说明
图1是实施例1中所得的亚微粒子(サズミクロン粒子)的SEM图像。
具体实施方式
1.纳米粉体
在本说明书中，“纳米粉体”是指具有5～30nm的范围内的平均粒径以及由[粒径算术偏差/平均粒径]所表示的10％以下的粒度分布的粒子状的铅系压电材料。也就是说，纳米粉体是纳米尺寸的铅系压电材料的粒子(即纳米粒子)的集合体。
在本说明书中，“铅系压电材料”是指至少含有铅(Pb)的压电材料。
在本说明书中，“压电材料”包含被施加压力时产生电荷的物质以及被施加电场时变形的物质。在本说明书中，“压电”的概念包含“电致伸缩”。
铅系压电材料可以具有由通式ABO3所表示的钙钛矿型晶体结构。另外，铅系压电材料可以含有氧，也可以除了铅和氧以外还含有2种以上的元素。具体而言，铅系压电材料可以具有在A位置和B位置含有总计3种以上元素的钙钛矿型晶体结构。
更加具体而言，铅系压电材料可以是选自由Pb(Zr，Ti)O3、Pb(Mg，Nb)(Zr，Ti)O3、Pb(Ni，Nb)(Zr，Ti)O3、Pb(Zn，Nb)(Zr，Ti)O3、Pb(Yb，Nb)(Zr，Ti)O3、(Pb，Sr)(Zr，Ti)O3、(Pb，Ba)(Zr，Ti)O3、(Pb，La)(Zr，Ti)O3、(Bi，Pb)(Ni，Nb)(Zr，Ti)O3、(Bi，Pb)(Mg，Nb)(Zr，Ti)O3、(Bi，Pb)(Zn，Nb)(Zr，Ti)O3、(Pb，Sr，La)(Mg，Ni，Nb)(Zr，Ti)O3、PbTiO3、Pb(Mg，Nb)TiO3、Pb(Ni，Nb)TiO3和Pb(Zn，Nb)TiO3所组成的组中的至少一种氧化物。
纳米粉体中所含的粒子的直径可以通过例如利用SEM(电子扫描显微镜)或TEM(透射电子显微镜)进行观察来测定。这里，粒子的直径是指圆当量直径，具体是指投影面积的圆当量直径(Heywood直径)。
纳米粉体的粒度分度可以通过例如利用SEM、TEM，选择在视场内包含20个～50个圆当量直径为5nm以上的粒子的倍率，使用图像分析式粒度分度软件对所得的图像数据进行粒子识别后，换算成投影面积的圆当量直径来算出。
另外，纳米粉体的平均粒径可以将圆当量直径的频率直方图通过正态分布进行近似，从而统计地算出平均粒径。
纳米粉体可适宜地用于后述的亚微粉体的制造。
纳米粉体可以与其他物质混合，也可以在介质中扩散。
另外，为了用于后述的亚微粉体的制造，就纳米粉体而言，PZT强度比优选为20％以上，更加优选为50％以上，进一步优选为90％以上。PZT强度比可以换种说法叫PZT合成率，是在2θ＝20～60°的XRD(X射线衍射)谱图中，相对于总强度，表示PZT相的强度的比例。
2.纳米粉体组合物
纳米粉体组合物含有上述铅系压电材料中所含的元素中的至少一种元素的氧化物和氢氧化物中的至少一方。也就是说，铅系压电材料含有Pb、Zr和Ti的情况下，纳米粉体组合物除了上述粒子以外，还含有选自由PbO、Pb(OH)2、ZrO2、Zr(OH)4、TiO2和Ti(OH)4所组成的组中的至少一种化合物。
纳米粉体组合物可以含有水等介质。氧化物和氢氧化物、以及上述的纳米粉体可以在介质中扩散和/或溶解。
纳米粉体组合物适用于后述的亚微粉体的制造。在亚微粉体的制造中使用EDTA等螯合剂的情况下，纳米粒子组合物中的氧化物或氢氧化物的元素的原子通过螯合剂而在络合物与游离体之间呈平衡状态，但由于存在剩余原子，因此存在可以适当地调整亚微粒子的生长速度的可能性。
3.亚微粉体
在本说明书中，亚微粉体是指具有小于1μm的中位径和由[粒径算术偏差/平均粒径]所表示的15％以下的粒度分布的粒子状的铅系压电材料。亚微粉体的全部粒子中85％以上具有立方体形状。也就是说，亚微粉体是亚微尺寸的铅系压电材料的粒子(即亚微粒子)的集合体。
在本说明书中，具有立方体形状的粒子还包含具有完整的立方体以外的大致立方体形状的粒子。即，具有立方体形状的粒子可以是如下所述的粒子：来自与粒子的某面垂直的方向的投影图像中，具有成为大致正方形的边(大致立方体的棱)的相对的2组边，与各组边正交的2轴的长轴与短轴之比为1.0～1.1，进而边的直线部分的长度至少为大致立方体形状的粒子中正对的面间隔(即粒子尺寸)的50％以上，优选为70％以上，进一步优选为80％以上。立方体形状的粒子的顶点部分可以呈圆形，也可以为被切割的形状、多面体。粒子的观察可以利用SEM或TEM进行观察。
亚微粉体的粒度分布可以利用通常的粒度计进行测定，例如，如后所述，可以利用动态光散射法进行测定。
另外，中位径是也可标记为D50的值。以中位径为边界值，将粉体分成2组时，各个组中所含的粒子的量相同。
4.制造方法
亚微粉体的制造方法包含以纳米粒子为核、通过水热法进行粒生长的工序。
水热法的实行条件根据作为目标的铅系压电材料的组成和作为目标的粒子的大小等来设定。
亚微粉体也可以通过将上述纳米粉体用作核的水热法进行制造。
作为纳米粉体的制造方法，可举出使用高分散反应场的方法作为例子。即，使含有纳米粉体的原料作为溶质的溶液(即原料液)与进行了薄膜化的原料的不良溶剂(即薄膜流体)接触。由此，原料析出，纳米粒子形成。原料液与薄膜流体反应后的液体包含在上述纳米粉体组成中。这里所述的不良溶剂是指原料液的溶质的溶解度低的状态，溶剂种类可以不同，即便是同种溶剂，温度、压力等也可以不同。
纳米粉体的制造方法的具体条件根据作为目标的铅系压电材料的组成和作为目标的粒子的大小等来设定。具体而言，在使用高分散反应场的方法中，优选满足下述条件中的至少一个条件：
·温度：室温～200℃，
·压力：0.01～2MPa，
·原料液与薄膜流体的流量比(薄膜流体/原料液)：0.5～12000，以及
·用于得到薄膜流体的转数：30～3500rpm。
实施例
1.PZT粒子的制造
1-1.核的形成
(实施例1～10)
准备含有醋酸铅三水合物(关东化学制)和氢氧化钾(关东化学制)的铅水溶液；含有氯化氧化锆八水合物(关东化学制)的锆水溶液；氯化钛水溶液(和光纯药制)；含有氢氧化钾(关东化学制)的氢氧化钾水溶液。按照Pb、Zr和Ti的摩尔比成为Pb∶Zr∶Ti＝1.1∶0.7∶0.3的方式混合各水溶液，从而得到原料液S。
将原料液S的成分、薄膜流体T的成分、反应温度和压力如表1的实施例1～10所示地进行组合，使PZT析出。
就析出而言，使用一方是固定盘、另一方由旋转盘构成、可以通过使旋转盘旋转来形成薄膜流体层的装置。作为这种装置，可以使用例如高分散粒子合成装置ULREA SS-11(M-Technique(エム·テクニツク)制)。
旋转盘的转数设为500rpm。通过在利用旋转盘的旋转进行了薄膜化的流体T中汇合原料液S，从而使PZT析出。将汇合后的流体(以下，称为浆料U)全部回收。浆料U相当于上述的纳米粉体组合物。
另外，实施例6中，首先使用含有上段所示成分(Pb、Ti和K)的原料液和薄膜流体来形成PbTiOx，从而得到中间溶液。在该中间溶液中添加Zr和K，从而得到含有下段所示成分(PbTiOx、Zr和K)的原料液。
使用由此得到的浆料U，进行后述的PZT粒子的形成。
(实施例11)
作为原料液S，准备如下：将醋酸铅(关东化学制)溶解在2-甲氧基乙醇(关东化学制)中，加入四异丙氧化物(テトライソプロポキシド)(高纯度化学研究所制)和四丁氧基锆(高纯度化学研究所制)，进一步加入乙酰丙酮(关东化学制)，充分搅拌，在其中加入水和异丙醇(关东化学制)的混合溶剂(水分1.5wt％)。另一方面，使用纯水作为薄膜流体T。
在表1所示的条件下，通过与上述实施例1～10同样的操作，得到浆料。
(实施例12)
作为PZT微粒的原料液S，准备如下：将二异丙氧基铅(高纯度化学研究所制)和四异丙氧化物、四丁氧基锆溶解在异丙醇中，进一步加入乙酰乙酸乙酯后，加入水异丙醇混合溶剂(水分1.5wt％)。另一方面，使用纯水作为薄膜流体T。
在表1所示的条件下，通过与上述实施例1～10同样的操作，得到浆料。
表1
Figure BSA00000609148200061
1-2.粒生长
(实施例1～12)
按照Pb、Zr和Ti的摩尔比成为Pb∶Zr∶Ti＝1.1∶0.7∶0.3的方式混合：含有醋酸铅三水合物(关东化学制)、乙二胺四乙酸(关东化学制)和氢氧化钾(关东化学制)的铅水溶液；含有氯化氧化锆八水合物(关东化学制)的锆水溶液；氯化钛水溶液(和光纯药制)；含有氢氧化钾(关东化学制)的氢氧化钾水溶液，从而配制用于粒生长工艺的原料液S’。
调整浆料U的pH，将10ml的浆料U与20ml的原料液S’一起加入具有用聚四氟乙烯形成的内壁、具有100ml的容量的SUS制的压力容器中。使用该压力容器，进行120℃、2小时的水热合成处理，从而得到PZT粒子。
使用实施例1～12的各浆料U来进行以上的操作。
(比较例1)
按照Pb、Zr和Ti的摩尔比成为Pb∶Zr∶Ti＝1.1∶0.7∶0.3的方式混合：含有醋酸铅三水合物(关东化学制)、乙二胺四乙酸(关东化学制)和氢氧化钾(关东化学制)的铅水溶液；含有氯化氧化锆八水合物(关东化学制)的锆水溶液；氯化钛水溶液(和光纯药制)；以及含有氢氧化钾(关东化学制)的氢氧化钾水溶液，从而配制原料液。将30ml的原料液加入内壁为聚四氟乙烯的SUS制的100ml压力容器中，进行165℃、4小时的水热合成处理，从而得到PZT粒子。
(比较例2)
按照摩尔比为Pb、Zr和Ti的摩尔比成为Pb∶Zr∶Ti＝1.1∶0.7∶0.3的方式混合：含有醋酸铅三水合物(关东化学制)、乙二胺四乙酸(关东化学制)和氢氧化钾(关东化学制)的铅水溶液；含有氯化氧化锆八水合物(关东化学制)的锆水溶液；氯化钛水溶液(和光纯药制)；以及含有氢氧化钾(关东化学制)的氢氧化钾水溶液。进一步加入明胶(Jellice(ゼライス)制)2.5wt％，使用分散机进行充分搅拌，从而配制原料液。将30ml的原料液加入内壁为聚四氟乙烯的SUS制的100ml压力容器中，进行165℃、4小时的水热合成处理，从而得到PZT粒子。
2.评价
2-1.关于核粒子
关于上述1-1所得的浆料，利用X射线衍射装置(PANalytical制造的X‘PertMPD Pro)，得到2θ＝20～60°的XRD谱图。将相对于2θ＝20～60°的总强度的PZT相强度比作为PZT合成率算出。
利用场致发射型电子显微镜(日本电子制，JSM-7000F)，选择在视场内包含20个～50个圆当量直径为大概5nm以上的粒子的倍率，使用图像分析式粒度分度软件(Mountech公司制，Mac-View)对所得的图像数据进行粒子识别，测定投影面积的圆当量直径作为粒径。从频率直方图的正态分布近似统计地算出平均粒径。
另外，同样统计地算出偏差，作为粒度分布的指标，如式(1)所示用偏差除以平均粒径从而算出粒度分布。
粒度分布＝近似的正态分布的偏差/近似的正态分布的平均(1)
2-2.生长后的PZT粒子
使用Spectris(スペクトリス)公司制造的动态散射式粒度分布测定装置Zetasizer nano-ZS测定生长后的PZT粒子的粒度分布，由所得的数据求出中位径和粒度分布。
进一步利用场致发射型电子显微镜(日本电子制，JSM-7000F)来确认PZT粒子的形状。将PZT粒子分散，在以粒子不重叠的方式薄薄地铺开在SEM试样台的状态下选择包含20个～50个的倍率进行观察，由所得的图像数据算出立方体形状的粒子的比例。对所得的图像用图像分析式粒度分布软件求出粒子的投影面积σ、投影周长λ、外接圆面积∑，算出圆度(＝4πσ/λ2)和相对于外接圆面积的投影面积比(＝σ/∑)。挑选圆度为1.092以上且面积比为0.637以上的粒子，其中，将在投影图像中平行地相对的边为偶数组的粒子作为立方体形状，算出比例。
将结果示于表2。另外，将实施例1的PZT粒子的图像示于图1。
表2
如表2和图1所示，实施例1～12的核粒子的平均粒径在5～30nm的范围内，粒度分布为10％以下。另外，以它们为核生长的PZT粒子是中位径为亚微级且粒度分布为15％以下、全部粒子中85％以上具有立方体形状的铅系压电材料。
另外，确认了所得的粒子的长轴与短轴之比为1.0～1.1，大致正方形的边的长度为粒子尺寸的80％以上。另一方面，确认了在比较例2中，20％以上的粒子不是大致立方体形状，而是球状或者球、立方体崩塌的不完整形状。
3.取向陶瓷的制造
为了评价上述1-2中所得的PZT粒子作为取向陶瓷的晶种的特性，进行PZT粒子的二维排列处理，由面内的被覆率评价粒子的填充程度。具体的制作方法如下。
利用丝网印刷在尺寸30mm×30mm、厚度150μm的锆基板上形成宽1mm、长40mm、厚10μm的铂成型体，使用电炉在1350℃下进行烧接，从而在基板上形成铂电极(第1电极)。另外，在30ml的纯水中以成为0.01mol/l(升)的方式添加十二烷基苯磺酸钠和吡咯，制作吡咯水溶液。将制作的水溶液加入烧杯中，向该水溶液中投入通过水热合成法制作的粒径3μm的立方体形状的PZT粒子1重量％，使用均质机进行分散处理，配制悬浮液(浆料单体溶液)。
接着，在加有该溶液的烧杯的底部放置上述锆基板，静置10分钟，直到PZT粒子沉降堆积。接着，以相对基板平行的方式将SUS制的对向电极以电极间隔1mm进行设置，按照以基板上的铂电极为负极、以对向电极为正极的方式与电源连接，以峰值电压5V施加2Hz的三角波30次，在铂电极上合成聚吡咯。
将成膜有聚吡咯的基板在水溶液中摇动，大体上除去多余的粒子以后，在纯水中进行超声波清洗，除去在铂电极以外的地方附着的PZT粒子。由此，得到仅在铂电极上具有膜状地固定PZT粒子的固定层的粒子固定体。用SEM观察形成了粘着层的第1电极的表面，通过图像分析将每电极面积的粒子的被覆面积进行数值化，求出被覆率(在电极的每单位面积上被覆的粒子的比例)。
表3
  被覆率
  实施例1   93％
  比较例2   69％
如表3所示，使用实施例1的亚微粉体的一方可以得到比使用比较例2的粉体高的被覆率。
工业实用性
本发明提供的亚微级的粒子状的铅系压电材料具有立方体形状，粒度分布小。这种铅系压电材料由于具有容易进行二维排列的性质，因此作为取向陶瓷生长的晶种是有用的。

Claims (7)

1.一种铅系压电材料，其为粒子状的铅系压电材料，
平均粒径在5～30nm的范围内，
由粒径算术偏差/平均粒径所表示的粒度分布为10％以下。
2.如权利要求1所述的铅系压电材料，除了铅和氧以外，还含有2种以上的元素。
3.一种压电材料组合物，含有权利要求1或2所述的铅系压电材料、
以及所述铅系压电材料中所含的元素中的至少一种元素的氧化物和氢氧化物中的至少一方。
4.一种铅系压电材料，其为粒子状的铅系压电材料，
中位径小于1μm，
由粒径算术偏差/平均粒径所表示的粒度分布为15％以下，
全部粒子中85％以上具有立方体形状。
5.如权利要求4所述的铅系压电材料，除了铅和氧以外，还含有2种以上的元素。
6.一种铅系压电材料的制造方法，其为制造权利要求4所述的铅系压电材料的方法，
具备将用以形成权利要求4所述的粒子的纳米粒子为核、通过水热法使粒子生长的工序。
7.如权利要求6所述的制造方法，所述纳米粒子为，平均粒径在5～30nm的范围内，由粒径算术偏差/平均粒径所表示的粒度分布为10％以下。
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