CN103958438B - 压电取向陶瓷及其制造方法 - Google Patents

压电取向陶瓷及其制造方法 Download PDF

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CN103958438B
CN103958438B CN201280056588.1A CN201280056588A CN103958438B CN 103958438 B CN103958438 B CN 103958438B CN 201280056588 A CN201280056588 A CN 201280056588A CN 103958438 B CN103958438 B CN 103958438B
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piezoelectricity
orientation
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orientation ceramic
manufacture method
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三轮恭也
川田慎一郎
木村雅彦
铃木达
打越哲郎
目义雄
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Murata Manufacturing Co Ltd
National Institute for Materials Science
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Abstract

本发明提供作为具有钙钛矿结构的化合物而包含Pb(Ti，Zr)O3系化合物的压电取向陶瓷及其制造方法。本发明的压电取向陶瓷是包含具有钙钛矿结构的Pb(Ti，Zr)O3系化合物的压电取向陶瓷。该压电取向陶瓷是基于压电取向陶瓷的规定的截面的X射线衍射图样、利用Lotgering法计算出的取向度为0.64以上的高取向，且烧结密度为理论密度的85％以上的压电取向陶瓷。

Description

压电取向陶瓷及其制造方法
技术领域
本发明涉及压电材料，特别是结晶取向的压电取向陶瓷及其制造方法。
背景技术
一直以来，作为电介质材料、压电体材料，广泛使用具有钙钛矿结构的压电取向陶瓷。已知在这些具有钙钛矿结构的压电取向陶瓷中，通过使其结晶取向，从而压电取向陶瓷的电特性提高。
作为制作具有钙钛矿结构的压电取向陶瓷的方法，例如，提出了专利文献1中记载的技术。专利文献1中记载的技术有如下内容：使包含单一结晶的、例如包含以PbTiO3为主要成分的钙钛矿结构化合物的浆料在磁场中成形，由此制作陶瓷成形体，通过烧成该制作出的成形体，而得到结晶取向性高的压电取向陶瓷。
现有技术文献
专利文献
专利文献1：日本特开2010－090021号公报
发明内容
发明所要解决的课题
但是，将专利文献1中记载的制造方法适用于包含钛酸锆酸铅(以下称为Pb(Ti，Zr)O3系化合物)的压电取向陶瓷的制作时，在烧结过程中，失去结晶取向性，因此不能够得到包含Pb(Ti，Zr)O3系化合物的压电取向陶瓷。作为其理由认为如下：就Pb(Ti，Zr)O3系的化合物而言，占据ABO3型结晶的B位的元素存在2种，因此在烧结过程中，由于Ti和Zr的相互的扩散，因此结晶状态严重被打乱，其结果是失去结晶取向性。
因此，本发明主要目的在于，提供作为具有钙钛矿结构的化合物而以Pb(Ti，Zr)O3系化合物为主要成分、且结晶取向性高的压电取向陶瓷及其制造方法。
用于解决课题的方法
本发明的压电取向陶瓷，其特征在于，是以具有钙钛矿结构的Pb(Ti，Zr)O3系化合物为主要成分的压电取向陶瓷，就压电取向陶瓷而言，基于压电取向陶瓷的规定的截面的X射线衍射图样，利用Lotgering法计算出的取向度为0.64以上，且烧结密度为理论密度的85％以上。
另外，在本发明的压电取向陶瓷中，优选构成压电取向陶瓷的粒子为球状。
本发明的压电取向陶瓷的制造方法，是基于压电取向陶瓷的规定的截面的X射线衍射图样、利用Lotgering法计算出的取向度为0.64以上的压电取向陶瓷的制造方法，压电取向陶瓷的制造方法包括：准备包含具有钙钛矿结构的Pb(Ti，Zr)O3系化合物的单晶粉末的工序；制作包含单晶粉末作为分散相的浆料的工序；通过使浆料在磁场中成形，而得到成形体的工序；和烧成成形体的工序；就烧成成形体的工序而言，与在烧成温度的保持时间为3小时的条件下进行烧成时、烧结密度达到理论密度的85％以上的烧成温度中的最低烧成温度相比，在比该最低烧成温度低100℃以上的温度下保持24小时以上而进行烧成。
发明效果
根据本发明的压电取向陶瓷，能够得到以Pb(Ti，Zr)O3系的化合物为主要成分、结晶取向性高且烧结密度高的压电取向陶瓷。
虽然是包含Pb(Ti，Zr)O3系化合物的压电取向陶瓷但未失去结晶取向性的理由，可以推测如下。即，认为其原因在于，在烧成包含Pb(Ti，Zr)O3系化合物的成形体的工序中，通过抑制烧成温度、延长烧成时间，从而失去结晶取向性程度的剧烈的Ti和Zr的相互的扩散所导致的结晶状态的打乱得到抑制，并且能够给烧结带来充分的物质移动。
本发明的上述目的、其它目的、特征和优点，因参照附图来进行的以下发明的实施方式的说明而更加明确。
附图说明
图1是实验例中制作的试样1的Pb(Ti0.7Zr0.3)O3粒子的SEM图像。
图2是表示在压电取向陶瓷的烧成工序中，在改变烧成温度、保持3小时的条件下进行烧成的压电取向陶瓷的烧结体的与各烧成温度相对应的烧结密度的图。
图3表示相对于各烧成温度而得到的压电取向陶瓷的烧结体的比电阻ρ的图。
图4是压电取向陶瓷的烧结体的规定的截面的XRD曲线图，(a)是试样1的XRD曲线图，(b)是试样2的XRD曲线图，(c)是试样3的XRD曲线图。
具体实施方式
对本发明的压电取向陶瓷及其制造方法的一个实施方式进行说明。
(压电取向陶瓷)
本发明的压电取向陶瓷是以具有钙钛矿结构的Pb(Ti，Zr)O3系化合物为主要成分的压电取向陶瓷。另外，优选构成该压电取向陶瓷的粒子为球状。这是由于当构成压电取向陶瓷的粒子为球状时，能够使裂纹的产生、发展变得难以发生。
另外，本发明的压电取向陶瓷是依据规定的截面的X射线衍射(XRD)图样、利用Lotgering法计算出的第1轴的取向度为0.64以上，且结晶取向性高的压电取向陶瓷。需要说明的是，对于Lotgering法，在后面详细进行说明。
另外，本发明的压电取向陶瓷是烧结密度为该压电取向陶瓷的理论密度的85％以上的压电取向陶瓷。理论密度例如是由解析X射线衍射法的测定结果而得的晶胞的大小、和原子量求得的。需要说明的是，其理论密度ρtheo通过以下的数学式(1)表示。
[数1]
ρtheo＝Wunit/Vunit    (1)
在此，Wunit表示每个晶胞的重量，Vunit表示每个晶胞的体积。
因此，本发明的压电取向陶瓷是以陶瓷粒子的结晶轴的3轴中的1轴的结晶取向性高的Pb(Ti，Zr)O3系化合物为主要成分的压电取向陶瓷。
(压电取向陶瓷的制造方法)
接着，对本发明的压电取向陶瓷的制造方法的实施方式进行说明。
为了制造本发明的压电取向陶瓷，准备包含具有钙钛矿结构的Pb(Ti，Zr)O3系化合物的粉末。为了准备包含Pb(Ti，Zr)O3系化合物的粉末，例如，将PbO、TiO2和ZrO2等原料湿式混合后，煅烧干燥来制作Pb(Ti，Zr)O3系化合物的煅烧物。并且将该煅烧物干式粉碎而制作煅烧粉末。然后将该煅烧粉末在助熔剂中热处理。由此，钙钛矿结构化合物结晶成长，准备包含Pb(Ti，Zr)O3系化合物的单晶粉末。需要说明的是，该单晶粒子为球状。另外，可有利地使用KCl和NaCl中的至少一种作为助熔剂。
然后，制作包含利用上述方法准备的单晶粉末作为分散相的浆料。并且，通过使用制作好的浆料在磁场中成形而得到成形体。这样，通过使浆料在磁场中成形，从而成形体所包含的结晶的结晶轴根据所施加的磁场，沿规定的方向取向。
接着，对利用上述的方法制造的成形体进行烧成，得到压电取向陶瓷。首先，与在烧成温度的保持时间为3小时的条件下对成形体进行烧成时、烧结密度达到理论密度的85％以上的烧成温度中的最低烧成温度相比，在比该最低烧成温度低100℃以上的温度下保持24小时以上而进行烧成。
即，在烧成温度的保持时间为3小时的条件下对成形体进行烧成时，能够得到理论密度的85％的烧结密度的烧成温度为1100～1150℃。因此，通过将成形体在比该烧成温度低100℃以上的1000℃下保持24小时以上来进行烧成，从而能够制作期望的压电取向陶瓷。需要说明的是，像这样保持24小时以上的温度优选950℃以上且1000℃以下。
根据本发明的压电取向陶瓷的制造方法，能够得到如下的压电取向陶瓷的烧结体，就该压电取向陶瓷而言，包含Pb(Ti，Zr)O3系化合物作为具有钙钛矿结构的化合物，且基于压电取向陶瓷的规定的截面的X射线衍射(XRD)图样、利用Lotgering法计算出的第1轴的取向度为0.64以上。
接着，对为了确认本发明的压电取向陶瓷的制造方法和利用该制造方法制作的压电取向陶瓷的效果而进行的实验例进行以下说明。
1.试样的制作
(试样1)
试样1是利用以下记载的制作方法制作的。
以使Pb、Ti、Zr的摩尔比为1：0.7：0.3的方式秤量PbO、TiO2、ZrO2，利用球磨机湿式混合15小时后，以900℃煅烧干燥，得到Pb(Ti0.7Zr0.3)O3煅烧物。
然后，将得到的煅烧物干式粉碎，以与KCl的重量比为1：1的方式混合。将其在氧化铝坩埚中以1000℃热处理12小时，冷却至室温后，用水将KCl溶解、除去，进行干燥，得到结晶成长为由单晶构成的粒子的Pb(Ti0.7Zr0.3)O3粒子。在此，在图1中示出了所得的Pb(Ti0.7Zr0.3)O3结晶粒子的SEM图像。如图1中所示那样，Pb(Ti0.7Zr0.3)O3的结晶粒子为球状。
接着，取出30g结晶成长后的Pb(Ti0.7Zr0.3)O3粒子，相对于该Pb(Ti0.7Zr0.3)O3粒子100重量份，添加聚乙烯醇0.5重量份、纯水40重量份，用球磨机混合12小时，得到浆料。
接着，将得到的浆料在12T的磁场中浇铸成形，由此得到结晶取向化了的成形体。在烧成温度的保持时间为3小时的条件下，在1000℃至1200℃之间使烧成温度以50℃的梯度发生变化，对得到的成形体进行烧成，得到各烧成温度下的5个烧结体。
在此，测定通过改变烧成温度而得到的各烧结体的烧结密度，得到图2的结果。需要说明的是，在图2中，理论密度的85％用虚线表示。另外，将通过改变烧结温度而得到的各烧结体的比电阻ρ示于图3。在此，在进行极化处理方面优选比电阻ρ为1.0×108Ωm以上，作为图3中具有所需比电阻ρ的烧结体，由图2可以明确，需要烧结密度为理论密度的85％以上。另外，由图2可以明确，能够得到理论密度的85％的烧结密度的烧成温度为1100～1150℃之间。
需要说明的是，相对于上述的各烧成温度得到的各烧结体的烧结密度是使用阿基米德法测定的。另外，理论密度为8.05g/cm3。即，就每个晶胞的体积即Vunit而言，通过解析基于X射线衍射法的测定结果而得出6.52×10-23cm3，由于每个晶胞的重量即Wunit为5.25×10-22g，因此基于这些并通过数学式(1)计算出理论密度。另外，就各烧结体的比电阻ρ而言，对各烧结体施加直流电压100V预充电15秒钟后，通过测定各烧结体中流过的电流来计算。
基于图2和图3的结果，通过将利用上述方法得到的成形体在1000℃保持24小时来进行烧成，得到烧结体(试样1)。
(试样2)
试样2是利用以下记载的制作方法而制作的。
以使Pb、Ti、Zr的摩尔比为1：0.7：0.3的方式秤量PbO、TiO2、ZrO2，利用球磨机湿式混合15小时后，以900℃煅烧干燥，得到Pb(Ti0.7Zr0.3)O3煅烧物。
然后，将得到的煅烧物干式粉碎，以与KCl的重量比为1：1的方式混合。将其在氧化铝坩埚中以1000℃热处理12小时，冷却至室温后，用水将KCl溶解、除去，进行干燥，得到结晶成长为单晶粒子的Pb(Ti0.7Zr0.3)O3粒子。
接着，取出30g利用上述方法得到的结晶成长后的Pb(Ti0.7Zr0.3)O3粒子，相对于该Pb(Ti0.7Zr0.3)O3粒子100重量份，添加聚乙烯醇0.5重量份、纯水40重量份，用球磨机混合12小时，得到浆料。
接着，将得到的浆料在12T的磁场中浇铸成形，由此得到结晶取向化了的成形体。通过将该成形体在1150下℃保持3小时来进行烧成，而得到烧结体(试样2)。
(试样3)
试样3是利用以下记载的制作方法制作的。
以使Pb、Ti、Zr的摩尔比为1：0.7：0.3的方式秤量PbO、TiO2、ZrO2，利用球磨机湿式混合15小时后，以900℃煅烧干燥，得到Pb(Ti0.7Zr0.3)O3煅烧物。
然后，将得到的煅烧物干式粉碎，以与KCl的重量比为1：1的方式混合。将其在氧化铝坩埚中以1000℃热处理12小时，冷却至室温后，用水将KCl溶解、除去，进行干燥，得到结晶成长为单晶粒子的Pb(Ti0.7Zr0.3)O3粒子。
接着，取出30g利用上述方法得到的结晶成长后的Pb(Ti0.7Zr0.3)O3粒子，相对于该Pb(Ti0.7Zr0.3)O3粒子100重量份，添加聚乙烯醇0.5重量份、纯水40重量份，用球磨机混合12小时，得到浆料。
接着，将得到的浆料在12T的磁场中浇铸成形，由此得到结晶取向化了的成形体。通过将该成形体在1000℃下保持3小时来进行烧成，而得到烧结体(试样3)。
2.评价
接着，利用Lotgering法，根据下面的数学式(2)计算出利用上述的制作方法得到的各试样的烧结体的规定的截面的取向度。在取向度的计算中，在不施加磁场的状态下对成形后的成形体进行烧成，并将由此得到的Pb(Ti0.7Zr0.3)O3的烧结体为基准试样。
[数2]
在此，ΣI(HKL)是评价对象的烧结体的特定的结晶面(HKL)的X射线峰强度的总和，ΣI(hkl)是评价对象的烧结体的全部结晶面(hkl)的X射线峰强度的总和。另外，ΣI0(HKL)是基准试样的特定的结晶面(HKL)的X射线峰强度的总和，ΣI0(hkl)是基准试样的全部结晶面(hkl)的X射线峰强度的总和。
另外，测定条件为2θ＝20～60度(deg.)。另外，作为全部结晶面(hkl)的X射线峰的强度，使用＜100＞、＜110＞、＜111＞、＜200＞、＜210＞和＜211＞的各强度。作为特定的结晶面(HKL)，使用＜100＞和＜200＞的各强度。
另外，对于试样1至试样3的烧结体，利用上述方法测定烧结密度。
对于得到的试样1至试样3的烧结体的取向度、烧结密度和比电阻ρ的结果，与各试样的烧成条件一并示于表1中。另外，图4示出了压电取向陶瓷的烧结体的规定的截面的XRD曲线图，(a)是试样1的XRD曲线图，(b)是试样2的XRD曲线图，(c)是试样3的XRD曲线图。需要说明的是，就各试样的比电阻ρ而言，对各试样施加直流电压100V而预充电15秒钟后，通过测定各试样中流过的电流来计算。
表1
试样 试样1 试样2※ 试样3※
烧成条件 1000℃，24hr 1150℃，3hr 1000℃，3hr
取向度 64％ 25％ 70％
烧结密度 7.2g/cm3 7.4g/cm3 5.6g/cm3
比电阻ρ 8.1×108Ωm 1.6×109Ωm 3.4×107Ωm
表中的※为本发明的范围以外。
根据表1，就试样1而言，其取向度高，另外，烧结密度相对于理论密度高而得到较高的值。另一方面可知，就试样2而言，虽然与试样1同样地烧结密度相对于理论密度而得到较高的值，但是得到的烧结体的取向度低。另外可知，就试样3而言，虽然取向度高，但烧结密度相对于理论密度较低。还有可知，就试样3而言，为了进行极化处理，优选比电阻ρ为1.0×108Ωm以上，可知未满足该条件。
根据本发明的压电取向陶瓷的制造方法，在烧成包含Pb(Ti，Zr)O3系化合物的成形体的工序中，与在烧成温度的保持时间为3小时的条件下对成形体进行烧成时、烧结密度达到理论密度的85％以上的烧成温度中的最低烧成温度相比，在比该最低烧成温度低100℃以上的温度下保持24小时以上而进行烧成，由此能够得到包含Pb(Ti，Zr)O3系化合物且具有高结晶取向性的压电取向陶瓷。
需要说明的是，在本发明的实施方式中，是以Pb(Ti，Zr)O3系化合物即PZT系化合物为主要成分的压电取向陶瓷，但并不限定于此，本发明的压电取向陶瓷的制造方法在制作如下的压电取向陶瓷时也适用，即包含在该PZT系化合物中含有Pb(Ni，Nb)O3作为第3成分的Pb{(Ni，Nb)，Ti，Zr}O3系化合物的压电取向陶瓷。

Claims (3)

1.一种压电取向陶瓷，其特征在于，是以具有钙钛矿结构的Pb(Ti，Zr)O3系化合物为主要成分的压电取向陶瓷，
就所述压电取向陶瓷而言，
基于所述压电取向陶瓷的规定的截面的X射线衍射图样，利用Lotgering法计算出的取向度为0.64以上，且烧结密度为理论密度的85％以上。
2.根据权利要求1所述的压电取向陶瓷，其特征在于，构成所述压电取向陶瓷的粒子为球状。
3.一种压电取向陶瓷的制造方法，其特征在于，是基于所述压电取向陶瓷的规定的截面的X射线衍射图样、利用Lotgering法计算出的取向度为0.64以上的压电取向陶瓷的制造方法，
所述压电取向陶瓷的制造方法包括：
准备包含具有钙钛矿结构的Pb(Ti，Zr)O3系化合物的单晶粉末的工序；
制作包含所述单晶粉末作为分散相的浆料的工序；
通过使所述浆料在磁场中成形，而得到成形体的工序；和
烧成所述成形体的工序；
就所述烧成成形体的工序而言，
与在烧成温度的保持时间为3小时的条件下进行烧成时、烧结密度达到理论密度的85％以上的烧成温度1100～1150℃中的最低烧成温度相比，在比该最低烧成温度低100℃以上的温度即950℃以上1000℃以下保持24小时以上而进行烧成。
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