KR100481226B1 - Piezoelectric ceramic composition for ceramic actuators and Method of fabricating the piezoelectric ceramics - Google Patents

Piezoelectric ceramic composition for ceramic actuators and Method of fabricating the piezoelectric ceramics Download PDF

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KR100481226B1
KR100481226B1 KR10-2002-0033021A KR20020033021A KR100481226B1 KR 100481226 B1 KR100481226 B1 KR 100481226B1 KR 20020033021 A KR20020033021 A KR 20020033021A KR 100481226 B1 KR100481226 B1 KR 100481226B1
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송재성
정순종
이재신
최해윤
권정호
최문석
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한국전기연구원
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Abstract

본 발명은 적층형 압전변위소자용에 적합한 압전세라믹 조성 및 압전 세라믹 제조방법을 제공하기 위한 것이다. 본 발명은 (Pb1-3a/2Ya)[(Ni1/3Nb2/3 )x(TiyZr1-x-y)O3 + b wt.%CuO의 조성에서 x=0.05~0.2, y=0.4~0.55이고, Pb자리에 이트륨(Yittrium)의 치환량인 a = 0 ~ 5몰비로 치환되고, CuO 첨가량 b = 0 ~ 1중량비로 첨가된 압전세라믹스 조성물로 높은 압전상수와 저온소성이 가능한 소재를 제공한다. 그리고, 본 발명은 PbO, ZrO2, TiO2, NiO, Nb2O5, Y2O3 , CuO 세라믹 분말을 소정 조성을 갖도록 평량하는 제 1단계와; 상기 세라믹 분말을 습식 혼합하는 제 2단계와; 상기 혼합된 세라믹 혼합물을 건조후 하소하는 제 3단계와; 상기 하소된 세라믹 조성물에 소정량의 CuO를 첨가하여 습식 분쇄한 후에 성형하는 제 4단계와; 상기 성형된 성형체를 소결하고 이 소결체의 양면을 연마 가공하는 제 5단계와; 상기 연마된 소결체의 양면에 전극을 형성하는 제 6단계와; 상기 전극이 형성된 소결체를 분극 처리하는 제 7단계를 포함하여 이루어진 압전 세라믹 제조방법을 제공한다.The present invention is to provide a piezoceramic composition and piezoelectric ceramic manufacturing method suitable for a multilayer piezoelectric displacement element. The present invention provides the composition of (Pb 1-3a / 2 Y a ) [(Ni 1/3 Nb 2/3 ) x (Ti y Zr 1-xy ) O 3 + b wt.% CuO, wherein x = 0.05 to 0.2, y = 0.4 to 0.55, Pb is substituted by a yttrium substitution amount of a = 0 to 5 molar ratio, CuO addition amount b = 0 to 1 by weight ratio of the piezoceramic composition added to enable high piezoelectric constant and low temperature plasticity Provide the material. In addition, the present invention comprises a first step of weighing PbO, ZrO 2 , TiO 2 , NiO, Nb 2 O 5 , Y 2 O 3 , CuO ceramic powder to have a predetermined composition; A second step of wet mixing the ceramic powder; A third step of calcining the mixed ceramic mixture after drying; A fourth step of molding after wet grinding by adding a predetermined amount of CuO to the calcined ceramic composition; A fifth step of sintering the molded body and polishing both surfaces of the sintered body; A sixth step of forming electrodes on both surfaces of the polished sintered body; It provides a piezoelectric ceramic manufacturing method comprising a seventh step of polarizing the sintered body on which the electrode is formed.

Description

세라믹 액츄에이터용 압전 세라믹 조성물 및 압전 세라믹 제조방법{Piezoelectric ceramic composition for ceramic actuators and Method of fabricating the piezoelectric ceramics} Piezoelectric ceramic composition for ceramic actuators and Method of fabricating the piezoelectric ceramics

본 발명은 압전 상수가 우수하고 저온 소성이 가능하여 적층형 압전 액츄에이터용으로 적합한 특성을 갖는 압전 세라믹 조성물 및 압전 세라믹 제조방법에 관한 것이다.The present invention relates to a piezoelectric ceramic composition and a method of manufacturing a piezoelectric ceramic having excellent piezoelectric constant and low temperature firing, and having suitable properties for a laminated piezoelectric actuator.

최근 정밀기계산업과 정보산업의 발달에 따라 미소 변위를 제어하거나 진동을 제어하는 액츄에이터는 정밀광학기기, 반도체 장비, 기체유량제어 펌프, 밸브 등에 폭넓게 응용되고 있다. 메카트로닉스의 발전과 더불어 미소 변위 제어 부품은 종래의 스텝 모터를 이용하는 방식에서 압전 액츄에이터를 이용하는 방향으로 전환될 것이다. 종래의 기계식 구동소자에 비하여 압전 액츄에이터는 소형화가 가능하고, 정밀제어가 가능하며, 응답속도가 빠른 장점이 있기 때문이다. 이와 같은 압전 액츄에이터용 소재로는 PZT계 압전 세라믹스가 광범위하게 응용되고 있다. 압전체의 변형율과 압전체에 인가된 전계의 관계는 다음과 같은 수식으로 표현된다.Recently, actuators for controlling small displacements or vibrations have been widely applied to precision optical devices, semiconductor equipment, gas flow control pumps, and valves according to the development of the precision machinery industry and the information industry. With the development of mechatronics, micro-displacement control components will be diverted in the direction of using piezoelectric actuators in a manner using conventional step motors. This is because piezoelectric actuators can be miniaturized, precisely controllable, and have a fast response speed as compared with the conventional mechanical driving devices. As such a piezoelectric actuator material, PZT-based piezoelectric ceramics have been widely applied. The relationship between the strain of the piezoelectric body and the electric field applied to the piezoelectric body is expressed by the following equation.

............. (1) ............. (One)

식 (1)에서 S3는 z축 방향의 변형률, d33는 압전 계수, E3는 z축 방향의 전계이다. 따라서 높은 변위량을 얻으려면 d33값이 큰 소재가 필요함을 알 수 있다. 가장 널리 이용되는 압전 소재인 PbTiO3-PbZrO3(이하, PZT라 약칭함)계 세라믹스는 압전 상수 d33 값이 200pC/N정도로 알려져 있다.In Equation (1), S 3 is a strain in the z-axis direction, d 33 is a piezoelectric coefficient, and E 3 is an electric field in the z-axis direction. Therefore, it can be seen that a material having a large value of d 33 is required to obtain a high displacement amount. PbTiO 3 -PbZrO 3 (hereinafter, abbreviated as PZT) ceramics, the most widely used piezoelectric material, are known to have a piezoelectric constant d 33 of about 200 pC / N.

식 (1)에서 알 수 있는 바와 같이 액츄에이터의 변위량은 전계에 비례함을 알 수 있으며, 압전체의 높은 변위량을 얻기 위해서는 높은 전계(E)가 요구된다. 압전 재료가 두꺼울 경우 인가전압이 높아야 한다. 그러나 높은 구동전압은 회로구성상 바람직하지 않으며, 구동전압을 낮추려면 압전 재료의 두께를 얇게 하는 것이 바람직하다. 이와 같은 배경에서 두께가 0.1mm이하인 압전 세라믹스 후막과 금속전극재료를 다층 적층하여 제조한 적층 세라믹 액츄에이터는 저전압 구동이 가능하고, 적층수에 따라 변형량을 조절할 수 있으며, 높은 발생력도 가능한 장점이 있다.As can be seen from Equation (1), it can be seen that the displacement of the actuator is proportional to the electric field, and a high electric field E is required to obtain a high displacement of the piezoelectric body. If the piezoelectric material is thick, the applied voltage should be high. However, a high driving voltage is not preferable in the circuit configuration, and in order to lower the driving voltage, it is desirable to make the thickness of the piezoelectric material thin. In this background, a multilayer ceramic actuator manufactured by multilayering a piezoelectric ceramic thick film and a metal electrode material having a thickness of 0.1 mm or less is capable of low voltage driving, the amount of deformation can be adjusted according to the number of stacked layers, and high generation power is also provided.

이전 기술에서는 xPb(Ni1/3Nb2/3)O3 - yPbTiO3 - zPbZrO3 ( x=0.45, 0.3<y<0.4, 0.15<Z<0.25)에 첨가물로 0.5무게비의 MnO2와 0.5∼5 무게비의 BaO-CuO를 첨가하여 소결성을 향상시켰다(특허공개 제 2001-0045525호). 다른 이전 특허에서는 aPb(Ni1/3Nb2/3)O3 - bPbTiO3 - cPbZrO3 ( 0.2≤a≤0.4, 0.25≤b≤0.45, 0.25≤c≤0.45) 조성물에 0.1∼0.5 무게비의 MnO2를 첨가하여 1150oC에 소결하여 특성을 얻었다(특허공개 제2001-0060415호).In the prior art, xPb (Ni 1/3 Nb 2/3) O 3 -yPbTiO 3 -zPbZrO 3 (x = 0.45, 0.3 <y <0.4, 0.15 <Z <0.25) is added as an additive to 0.5 weight ratio of MnO 2 and 0.5 to 5 weight ratio. BaO-CuO was added to improve sinterability (Patent Publication No. 2001-0045525). In another previous patent, 0.1 to 0.5 weight ratio MnO 2 was added to aPb (Ni 1/3 Nb 2/3) O 3 -bPbTiO 3 -cPbZrO 3 (0.2≤a≤0.4, 0.25≤b≤0.45, 0.25≤c≤0.45) composition And sintered at 1150 ° C. to obtain properties (Patent Publication No. 2001-0060415).

압전 액츄에이터의 변위 특성을 높이기 위해서는 종래의 PZT보다 높은 압전상수 d33 값을 가진 소재가 필요하다. 그러나 적층형 액츄에이터는 세라믹스와 전극금속을 동시에 소성해야 하므로 고온에서 안정한 Ag-Pd 합금이 사용된다. 종래의 PZT계 소재는 소성온도가 1200℃이상의 높은 소성온도가 요구된다. Ag는 융점이 960℃정도이고 Pd은 융점이 1552℃이므로 전극재료인 Ag-Pd 합금에서 Pd의 함량이 높을수록 융점이 높아지므로 전극재료에 Pd함량이 높은 합금이 요구된다. 그런데 Pd은 Ag보다 가격이 매우 비싸므로 전체적으로 부품의 가격이 증가하는 문제가 발생하게 된다. 따라서 적층형 압전 세라믹 액츄에이터용 압전 세라믹스 소재는 소성온도가 가능한 한 낮고, 높은 압전 상수 값을 가질 필요가 있다.In order to increase the displacement characteristics of the piezoelectric actuator, a material having a piezoelectric constant d 33 higher than that of the conventional PZT is required. However, the stacked actuator requires firing ceramics and electrode metal at the same time, so Ag-Pd alloy, which is stable at high temperature, is used. Conventional PZT materials require a high firing temperature of 1200 ° C. or higher. Since Ag has a melting point of about 960 ° C and Pd has a melting point of 1552 ° C, the higher the content of Pd in the Ag-Pd alloy as an electrode material, the higher the melting point, and therefore, an alloy having a higher Pd content is required. However, since Pd is much more expensive than Ag, there is a problem in that the price of parts is increased as a whole. Therefore, the piezoelectric ceramic material for the laminated piezoelectric ceramic actuator needs to have a firing temperature as low as possible and have a high piezoelectric constant value.

본 발명은 상기한 종래의 문제점을 해결하기 위해 개발된 것으로, 본 발명의 목적은 압전 상수가 우수하고 저온소성이 가능하여 적층형 압전 액츄에이터용으로 적합한 특성을 갖는 압전 세라믹 조성물과 압전 세라믹 제조방법을 제공하기 위한 것이다.The present invention was developed to solve the above-mentioned problems, and an object of the present invention is to provide a piezoelectric ceramic composition and a piezoelectric ceramic manufacturing method having excellent piezoelectric constant and low temperature firing, which have suitable properties for a laminated piezoelectric actuator. It is to.

본 발명에서는 종래의 PZT가 가지는 높은 소성 온도와 낮은 압전 상수의 문제를 개선하기 위하여, 기존의 PZT에 Pb(Ni1/3Nb2/3)O3을 첨가하고 Pb자리에 Y를 소량 치환하고, CuO를 소량 첨가한 세라믹 조성물을 얻었다. 본 발명의 화학적 조성식은 다음과 같이 표기할 수 있다.In the present invention, in order to improve the problems of high firing temperature and low piezoelectric constant of the conventional PZT, Pb (Ni 1/3 Nb 2/3 ) O 3 is added to the existing PZT and a small amount of Y is substituted at the Pb site. The ceramic composition which added a small amount of CuO was obtained. The chemical composition of the present invention can be written as follows.

(Pb1-3a/2Ya)[(Ni1/3Nb2/3)x(TiyZr1-x-y )O3 + b wt.%CuO(Pb 1-3a / 2 Y a ) [(Ni 1/3 Nb 2/3 ) x (Ti y Zr 1-xy ) O 3 + b wt.% CuO

위 조성에서 x=0.05~0.2, y=0.4~0.55이고, 첨가제로 CuO가 0 ~ 1wt.%로 첨가되고, Pb자리에 이트륨(Yittrium)이 0 ~ 5mol%로 치환된다.In the above composition, x = 0.05 ~ 0.2, y = 0.4 ~ 0.55, CuO is added as 0 ~ 1wt.% As an additive, yttrium is substituted by 0 ~ 5mol% in place of Pb.

본 발명은, 적층형 압전 변위 소자용에 적합한 압전 세라믹 조성을 제공하기 위함이다. (Pb1-3a/2Ya)[(Ni1/3Nb2/3)x(Tiy Zr1-x-y)O3 + b wt.%CuO의 조성에서 x=0.05~0.2, y=0.4~0.55이고, Pb자리에 이트륨(Yittrium)의 치환량인 a = 0 ~ 5몰비로 치환되고, CuO 첨가량 b = 0 ~ 1중량비로 첨가된 압전 세라믹스 조성물로 높은 압전 상수와 저온소성이 가능한 소재를 제공한다.It is an object of the present invention to provide a piezoelectric ceramic composition suitable for laminated piezoelectric displacement elements. X = 0.05 to 0.2, y = 0.4 in the composition of (Pb 1-3a / 2 Y a ) [(Ni 1/3 Nb 2/3 ) x (Ti y Zr 1-xy ) O 3 + b wt.% CuO It is ˜0.55, a piezoelectric ceramic composition which is substituted at a molar ratio of a = 0 to 5 molar ratio of yttrium at Pb site and added at a ratio of CuO addition amount b = 0 to 1 by weight to provide a material capable of high piezoelectric constant and low temperature firing. do.

상기한 목적을 달성하기 위한 본 발명의 압전 세라믹 제조방법은, PbO, ZrO2, TiO2, NiO, Nb2O5, Y2O3, CuO 세라믹 분말을 소정 조성을 갖도록 평량하는 제 1단계와; 상기 세라믹 분말을 습식 혼합하는 제 2단계와; 상기 혼합된 세라믹 혼합물을 건조후 하소하는 제 3단계와; 상기 하소된 세라믹 조성물에 소정량의 CuO를 첨가하여 습식 분쇄한 후에 성형하는 제 4단계와; 상기 성형된 성형체를 소결하고 이 소결체의 양면을 연마 가공하는 제 5단계와; 상기 연마된 소결체의 양면에 전극을 형성하는 제 6단계와; 상기 전극이 형성된 소결체를 분극 처리하는 제 7단계를 포함하여 이루어진다.The piezoelectric ceramic manufacturing method of the present invention for achieving the above object comprises a first step of weighing PbO, ZrO 2 , TiO 2 , NiO, Nb 2 O 5 , Y 2 O 3 , CuO ceramic powder to have a predetermined composition; A second step of wet mixing the ceramic powder; A third step of calcining the mixed ceramic mixture after drying; A fourth step of molding after wet grinding by adding a predetermined amount of CuO to the calcined ceramic composition; A fifth step of sintering the molded body and polishing both surfaces of the sintered body; A sixth step of forming electrodes on both surfaces of the polished sintered body; And a seventh step of polarizing the sintered body on which the electrode is formed.

여기서, 상기 제 1단계에서의 소정 조성은, 압전 세라믹이 (Pb1-3a/2Ya)[(Ni1/3Nb2/3)x(TiyZr1-x-y)]O 3 + b wt.%CuO의 화학식으로 이루어지고,Here, the predetermined composition in the first step is that the piezoelectric ceramic is (Pb 1-3a / 2 Y a ) [(Ni 1/3 Nb 2/3 ) x (Ti y Zr 1-xy )] O 3 + b consisting of the chemical formula of wt.% CuO,

상기 식에서 x, y 및 a는 각각 원자%로서Where x, y and a are each atomic%

0.05 ≤ x ≤ 0.2  0.05 ≤ x ≤ 0.2

0.4 ≤ y ≤ 0.55 0.4 ≤ y ≤ 0.55

0 ≤ a ≤ 5 (Pb자리에 치환하는 이트륨의 분율) 0 ≤ a ≤ 5 (fraction of yttrium substituted in Pb)

0 ≤ b ≤1 (첨가제인 CuO의 분율)의 범위에 있도록 하는 조성이다. It is a composition made to exist in the range of 0 <= b <= 1 (the fraction of CuO which is an additive).

그리고, 제 2단계에서의 습식 혼합은 볼 밀링방법으로 12~48시간의 범위에서 이루어진다.Then, the wet mixing in the second step is made in the range of 12 to 48 hours by the ball milling method.

또, 상기 제 3단계에서의 하소는 850~1100℃에서 2~4시간 동안 수행된다.In addition, the calcination in the third step is performed for 2 to 4 hours at 850 ~ 1100 ℃.

또한, 상기 제 4단계에서의 성형은 프레스를 이용하여 압축성형법으로 이루어진다.Further, the molding in the fourth step is made by compression molding method using a press.

그리고, 상기 제 5단계에서의 소결은 전기로에서 약 900~1200℃의 온도범위에서 1~3시간 동안 행한다.Then, the sintering in the fifth step is performed for 1 to 3 hours in the temperature range of about 900 ~ 1200 ℃ in the electric furnace.

또, 상기 제 6단계에서의 전극은 상기 소결체의 양면에 인쇄 도포법으로 은전극을 바르고 소분하여 형성한다.The electrode in the sixth step is formed by applying and subdividing a silver electrode on both surfaces of the sintered body by a printing coating method.

또한, 상기 제 7단계에서의 분극처리는 상기 전극이 형성된 소결체를 2~4kV/mm, 유지시간 10~60분, 온도 100~150℃의 조건에서 행한다. In the seventh step, the polarization treatment is performed on the sintered body on which the electrode is formed under conditions of 2 to 4 kV / mm, a holding time of 10 to 60 minutes, and a temperature of 100 to 150 ° C.

이하, 본 발명의 바람직한 실시예에 따른 세라믹 액츄에이터용 압전 세라믹 조성물에 대하여 첨부된 도면을 참조하여 설명하면 다음과 같다.Hereinafter, the piezoelectric ceramic composition for a ceramic actuator according to a preferred embodiment of the present invention will be described with reference to the accompanying drawings.

본 발명에서는 Pb(Ni1/3Nb2/3)O3 (이하, PNN이라 약칭함)을 PbTiO3 -PbZrO3 (이하, PZT라 약칭함)에 소량 첨가되면 전반적으로 압전 특성을 향상시킨다. 그러나 PNN 첨가량이 너무 과다하면 압전 특성의 상실을 초래하는 문제가 발생한다. 본 발명에서 얻은 주소재인 PNN-PZ-PT의 조성영역을 도 1에 나타내었다. PNN의 량인 x=0.05~0.2이고, PT의 량인 y=0.4~0.55로 상경계 영역 부근이다.In the present invention, when a small amount of Pb (Ni 1/3 Nb 2/3 ) O 3 (hereinafter, abbreviated as PNN) is added to PbTiO 3 -PbZrO 3 (hereinafter, abbreviated as PZT), piezoelectric properties are generally improved. However, too much PNN content causes a problem of loss of piezoelectric properties. The composition region of the PNN-PZ-PT as an address material obtained in the present invention is shown in FIG. 1. The amount of PNN is x = 0.05 to 0.2, and the amount of PT is y = 0.4 to 0.55 and is near the upper boundary region.

본 발명에서 추가로 첨가한 CuO와 Y2O3는 PNN-PZT 압전체에 대하여 소결 촉진제 역할을 한다. 그러나 두 가지 물질의 역할은 원리적인 면에서 차이를 나타낸다. CuO는 PbO와의 반응으로 융점이 낮은 물질로 소성시에 액상을 형성하여 액상을 통한 물질이동을 촉진하여 소결을 촉진한다. 그러나 너무 과도한 량이 첨가되면 압전 재료의 전기저항이 낮아져 반도체화가 되는 문제가 발생한다. Y2O3는 치환제로써 3가의 Y이온이 Pb자리에 치환된다. 이때 전하중성을 유지하기 위하여 2가인 Pb의 공공이 형성되며, 이 공공이 소결시에 확산을 촉진하게 된다. Y2O3 역시 너무 과도한 량을 첨가하면 압전 재료의 전기적 저항이 낮아져 반도체화가 되는 문제가 발생한다.CuO and Y 2 O 3 further added in the present invention serve as a sintering accelerator for the PNN-PZT piezoelectric body. However, the roles of the two materials differ in principle. CuO is a material with low melting point by reaction with PbO, which forms a liquid phase at the time of firing, thereby promoting sintering by promoting material movement through the liquid phase. However, when an excessive amount is added, the electrical resistance of the piezoelectric material is lowered, resulting in a problem of semiconductorization. Y 2 O 3 is a substituent and trivalent Y ions are substituted at Pb sites. At this time, in order to maintain charge neutrality, vacancy of bivalent Pb is formed, which promotes diffusion during sintering. If too much Y 2 O 3 is added, the electrical resistance of the piezoelectric material is lowered, resulting in a problem of semiconductorization.

<실시예><Example>

공업용으로 통상 사용되는 순도의 PbO, ZrO2, TiO2, NiO, Nb2O5, Y2O3, CuO 세라믹 분말을 사용하여 표 1과 같은 조성을 갖도록 평량하고 볼 밀링방법으로 24시간 습식 혼합을 하였다.PbO, ZrO 2 , TiO 2 , NiO, Nb 2 O 5 , Y 2 O 3 , CuO ceramic powders of normal use for industrial use are weighed to have the composition shown in Table 1 and wet mixed by ball milling method for 24 hours. It was.

압전세라믹 시료의 화학조성Chemical Composition of Piezoceramic Samples 시편번호Psalm Number (Pb1-3a/2Ya)[(Ni1/3Nb2/3)xTiyZr1-x-y]O3 + b wt.%CuO(Pb 1-3a / 2 Y a ) [(Ni 1/3 Nb 2/3 ) x Ti y Zr 1-xy ] O 3 + b wt.% CuO xx yy aa bb 소결온도(℃)Sintering Temperature (℃) 1* 1 * 00 0.50.5 00 00 12001200 22 0.50.5 0.40.4 0.030.03 0.10.1 10001000 33 0.50.5 0.550.55 0.050.05 00 10001000 44 0.10.1 0.40.4 00 0.10.1 10001000 55 0.10.1 0.50.5 00 0.20.2 10001000 66 0.10.1 0.550.55 0.010.01 0.50.5 10001000 77 0.10.1 0.450.45 0.050.05 1One 10001000 8* 8 * 0.10.1 0.60.6 00 00 10001000 99 0.150.15 0.4250.425 0.50.5 00 10001000 1010 0.150.15 0.4250.425 0.10.1 00 10001000 1111 0.150.15 0.4250.425 00 00 10001000 1212 0.150.15 0.4250.425 00 0.20.2 10001000 1313 0.20.2 0.40.4 00 00 11001100 1414 0.20.2 0.550.55 00 00 11001100 1515 0.20.2 0.450.45 0.050.05 00 10001000 1616 0.20.2 0.50.5 0.10.1 0.20.2 10001000 17* 17 * 0.20.2 0.6750.675 0.050.05 0.50.5 10001000 18* 18 * 0.30.3 0.30.3 00 00 11001100 19* 19 * 0.40.4 0.50.5 0.10.1 00 11001100 20* 20 * 0.30.3 0.250.25 00 0.20.2 11001100 21* 21 * 0.30.3 0.5750.575 00 00 11001100 22* 22 * 0.150.15 0.50.5 0.050.05 1One 10001000

* : 본 발명의 청구범위 밖*: Outside the claims of the present invention

상기 반죽 상태의 혼합물을 건조시킨 다음에 고상 화학 반응을 일으키기 위하여 분말을 약 850~1100℃에서 2~4시간 동안 하소하였다. 하소된 세라믹 조성물에 CuO를 첨가하여 습식 분쇄하고 조립화 한 다음, 프레스를 이용하여 압축성형법으로 성형하였다. 성형시에 지름이 18mm인 금형을 사용하여 약 100MPa의 압력으로 성형하였다.After drying the dough mixture, the powder was calcined at about 850-1100 ° C. for 2-4 hours to cause a solid phase chemical reaction. CuO was added to the calcined ceramic composition, wet pulverized and granulated, and then formed by compression molding using a press. At the time of molding, a mold having a diameter of 18 mm was used to mold at a pressure of about 100 MPa.

성형체를 전기로에서 약 900~1200℃의 온도범위에서 2시간동안 소결하여 시편을 제조하였다. 이후, 소결체를 분극하기 위하여 두께가 약 1mm가 되도록 그 소결체의 양면을 연마 가공한 다음, 인쇄 도포법으로 시료 양면에 은전극을 바르고 소분하여 전극을 형성한 후, 시편을 3kV/mm, 유지시간 20-30분, 온도 약 120℃의 조건으로 분극처리하여 압전 세라믹스를 완성하였다.The molded body was sintered for 2 hours at a temperature range of about 900 ~ 1200 ℃ in an electric furnace to prepare a specimen. Subsequently, in order to polarize the sintered compact, the both surfaces of the sintered compact were polished to have a thickness of about 1 mm, and then a silver electrode was applied and subdivided on both sides of the sample by a printing coating method to form an electrode. The piezoelectric ceramics were completed by polarization treatment under conditions of 20-30 minutes at a temperature of about 120 ° C.

임피던스 해석기(HP4194A)로 압전 세라믹스의 공진주파수(fr), 반공진주파수(fa), 전전용량(C), 유전손실(tanδ)을 측정하였고, 압전 상수(d33)는 Berlincourt d33 meter를 이용하여 측정하였으며, 면진동 모드 전기기계결합계수(kp)와 유전율(εr)은 각각 다음 식을 이용하여 계산하였다. 여기서 △f=fa-fr, C는 1kHz에서의 정전용량, A는 시편의 면적, t는 시편의 두께, ε0는 진공의 유전율로 8.854×10-12F/m이다.The impedance analyzer (HP4194A) was used to measure the resonant frequency (f r ), antiresonant frequency (f a ), total capacitance ( C ), and dielectric loss (tanδ) of piezoelectric ceramics, and piezoelectric constant (d 33 ) was Berlincourt d 33 meter. The surface vibration mode electromechanical coupling coefficient (k p ) and dielectric constant (ε r ) were calculated using the following equation. Where Δf = f a -f r , where C is the capacitance at 1 kHz, A is the area of the specimen, t is the thickness of the specimen, and ε 0 is the dielectric constant of the vacuum at 8.854 × 10 -12 F / m.

표 1에 나타낸 조성을 가진 압전 세라믹스들의 유전 및 압전 특성을 정리하여 표 2에 나타내었다. 표 2의 1번 시편은 비교를 위하여 PNN을 첨가하지 않은 PZT 세라믹스로 1200도의 높은 온도에서 소결하였을 때 d33 값은 192 pC/N이다. 그러나 본 발명의 압전 세라믹스 조성물은 주성분인 xPb(Ni1/3Nb2/3)O3-yPbTiO 3-(1-x-y)PbZrO3의 조성에서 x=0.05~0.2, y=0.4~0.55에 이트륨을 납원소 자리에 일부 치환하고, CuO를 첨가함으로써 소결성을 향상시키고, 압전 특성을 향상시켰다. 표 2에 나타낸 바와 같이 CuO의 첨가량이 0.2wt.%일 때와 이트륨의 치환량이 0.5 원자백분율일 때는 1000℃의 낮은 소결 온도에서도 높은 압전 특성을 갖는 압전 세라믹스를 얻을 수 있었다.Table 2 summarizes the dielectric and piezoelectric characteristics of the piezoelectric ceramics having the composition shown in Table 1. For the comparison, specimen 1 in Table 2 has a d 33 value of 192 pC / N when sintered with PZT ceramics without PNN at a high temperature of 1200 degrees. However, the piezoelectric ceramic composition of the present invention has a composition of x = 0.05 to 0.2 and y = 0.4 to 0.55 in the composition of xPb (Ni 1/3 Nb 2/3 ) O 3 -yPbTiO 3- (1-xy) PbZrO 3 as a main component. Was partially substituted at the site of the lead element, and CuO was added to improve sinterability and to improve piezoelectric properties. As shown in Table 2, piezoelectric ceramics having high piezoelectric properties were obtained even at a low sintering temperature of 1000 DEG C when the addition amount of CuO was 0.2 wt.% And the yttrium substitution amount was 0.5 atomic percentage.

제작된 시편의 유전 및 압전 특성Dielectric and Piezoelectric Properties of Fabricated Specimens 시편번호Psalm Number (Pb1-3a/2Ya)[(Ni1/3Nb2/3)x(TiyZr1-x-y)O3 + b wt.%CuO(Pb 1-3a / 2 Y a ) [(Ni 1/3 Nb 2/3 ) x (Ti y Zr 1-xy ) O 3 + b wt.% CuO 유전율(εr)Permittivity (ε r ) 유전손실(%)Dielectric loss (%) kp(%)k p (%) d33(pC/N)d 33 (pC / N) 비 고Remarks 1One 685.05685.05 2.52.5 45.645.6 178178 22 685.05685.05 2.52.5 45.645.6 178178 33 1303.591303.59 2.052.05 53.1653.16 360360 44 1524.871524.87 1.311.31 50.8650.86 322322 55 1471.631471.63 1.11.1 44.9744.97 271271 66 1360.41360.4 1.361.36 31.2531.25 181181 77 1258.411258.41 1.41.4 47.547.5 320320 88 1203.731203.73 0.960.96 51.351.3 325325 99 1649.261649.26 16.2116.21 32.732.7 197197 1010 1980.161980.16 16.8916.89 31.531.5 188188 11* 11 * -- -- -- -- 분극곤란Polarization Difficulties 12* 12 * -- -- -- -- 분극곤란Polarization Difficulties 13* 13 * 4352.394352.39 4.54.5 14.914.9 5252 14* 14 * 5354.055354.05 4.854.85 12.912.9 4141 15* 15 * 865.46865.46 2.832.83 32.932.9 144144 16* 16 * 611.59611.59 0.70.7 21.721.7 8787 17* 17 * -- -- -- -- 분극곤란Polarization Difficulties PZTPZT 12001200 -- 4848 200200

*: 본 발명의 특허청구 범위 밖 *: Outside the claims of the present invention

한편, 본 발명은 전술한 전형적인 바람직한 실시예에만 한정되는 것이 아니라 본 발명의 요지를 벗어나지 않는 범위 내에서 여러 가지로 개량, 변경, 대체 또는 부가하여 실시할 수 있는 것임은 당해 기술분야에 통상의 지식을 가진 자라면 용이하게 이해할 수 있을 것이다. 이러한 개량, 변경, 대체 또는 부가에 의한 실시가 이하의 첨부된 특허청구범위의 범주에 속하는 것이라면 그 기술사상 역시 본 발명에 속하는 것으로 보아야 한다.On the other hand, the present invention is not limited to the above-described typical preferred embodiment, it can be carried out in various ways without departing from the gist of the present invention various modifications, changes, substitutions or additions in the art Anyone who has this can easily understand it. If the implementation by such improvement, change, replacement or addition falls within the scope of the appended claims, the technical idea should also be regarded as belonging to the present invention.

이상 상세히 설명한 바와 같이 본 발명에 따르면, 본 발명에서 얻은 압전 세라믹스 조성물은 소결 온도가 1000℃이하에서도 압전 특성이 우수하여 적층형 압전 액츄에이터, 압전 변압기 및 초음파 진동자, 착화소자와 같은 고 신뢰성 압전 부품을 제조할 수 있으며, 전극재료에 Pd함량을 낮춤으로 부품가격 감소와 Pb의 휘발에 의한 환경오염을 감소시킬 수 있는 효과가 있다.As described in detail above, according to the present invention, the piezoelectric ceramic composition obtained in the present invention has excellent piezoelectric properties even at a sintering temperature of 1000 ° C. or below, thereby manufacturing high reliability piezoelectric components such as multilayer piezoelectric actuators, piezoelectric transformers, ultrasonic vibrators, and ignition elements. In addition, by lowering the content of Pd in the electrode material, there is an effect that can reduce the environmental pollution due to the reduction of the part price and the volatilization of Pb.

도 1은 본 발명에 따른 세라믹 액츄에이터용 압전 세라믹 조성물의 기본 조성물의 영역을 표시한 상태도,1 is a state diagram showing a region of the basic composition of the piezoelectric ceramic composition for a ceramic actuator according to the present invention,

도 2는 본 발명에 따른 압전 세라믹 제조 방법의 순서도이다.2 is a flowchart of a piezoelectric ceramic manufacturing method according to the present invention.

Claims (9)

(Pb1-3a/2Ya)[(Ni1/3Nb2/3)x(TiyZr1-x-y )]O3 + b wt.%CuO의 화학식으로 이루어지고, 상기 식에서 x, y 및 a는 각각 원자%로서(Pb 1-3a / 2 Y a ) [(Ni 1/3 Nb 2/3 ) x (Ti y Zr 1-xy )] O 3 + b wt.% CuO, wherein x, y And a are each atomic% 0.05 ≤ x ≤ 0.2  0.05 ≤ x ≤ 0.2 0.4 ≤ y ≤ 0.55 0.4 ≤ y ≤ 0.55 0 ≤ a ≤ 5 (Pb자리에 치환하는 이트륨의 분율) 0 ≤ a ≤ 5 (fraction of yttrium substituted in Pb) 0 ≤ b ≤1 (첨가제인 CuO의 분율)의 범위인 것을 특징으로 하는 압전 세라믹 조성물. A piezoelectric ceramic composition, which is in a range of 0 ≦ b ≦ 1 (fraction of CuO as an additive). PbO, ZrO2, TiO2, NiO, Nb2O5, Y2O3, CuO 세라믹 분말을, 압전 세라믹이 (Pb1-3a/2Ya)[(Ni1/3Nb2/3)x(TiyZr1-x-y)]O3 + b wt.%CuO의 화학식으로 이루어지고,PbO, ZrO 2 , TiO 2 , NiO, Nb 2 O 5 , Y 2 O 3 , CuO ceramic powder, piezoelectric ceramics (Pb 1-3a / 2 Y a ) [(Ni 1/3 Nb 2/3 ) x (Ti y Zr 1-xy )] O 3 + b wt.% CuO 상기 식에서 x, y 및 a는 각각 원자%로서Where x, y and a are each atomic% 0.05 ≤ x ≤ 0.2  0.05 ≤ x ≤ 0.2 0.4 ≤ y ≤ 0.55 0.4 ≤ y ≤ 0.55 0 ≤ a ≤ 5 (Pb자리에 치환하는 이트륨의 분율) 0 ≤ a ≤ 5 (fraction of yttrium substituted in Pb) 0 ≤ b ≤1 (첨가제인 CuO의 분율)의 범위에 있도록 하는 조성을 갖도록 평량하는 제 1단계와; A first step of weighing to have a composition such that 0 ≦ b ≦ 1 (fraction of CuO as additive); 상기 세라믹 분말을 습식 혼합하는 제 2단계와;A second step of wet mixing the ceramic powder; 상기 혼합된 세라믹 혼합물을 건조후 하소하는 제 3단계와;A third step of calcining the mixed ceramic mixture after drying; 상기 하소된 세라믹 조성물에 소정량의 CuO를 첨가하여 습식 분쇄한 후에 성형하는 제 4단계와;A fourth step of molding after wet grinding by adding a predetermined amount of CuO to the calcined ceramic composition; 상기 성형된 성형체를 소결하고 이 소결체의 양면을 연마 가공하는 제 5단계와;A fifth step of sintering the molded body and polishing both surfaces of the sintered body; 상기 연마된 소결체의 양면에 전극을 형성하는 제 6단계와;A sixth step of forming electrodes on both surfaces of the polished sintered body; 상기 전극이 형성된 소결체를 분극 처리하는 제 7단계를 포함하여 이루어진 것을 특징으로 하는 압전 세라믹 제조방법.And a seventh step of polarizing the sintered body in which the electrode is formed. 삭제delete 제 2항에 있어서,The method of claim 2, 제 2단계에서의 습식 혼합은 볼 밀링방법으로 12~48시간의 범위에서 이루어지는 것을 특징으로 하는 압전 세라믹 제조방법.The wet mixing in the second step is a piezoelectric ceramic manufacturing method, characterized in that the ball milling method in the range of 12 to 48 hours. 제 2항에 있어서,The method of claim 2, 상기 제 3단계에서의 하소는 850~1100℃에서 2~4시간 동안 수행되는 것을 특징으로 하는 압전 세라믹 제조방법.The calcination in the third step is a piezoelectric ceramic manufacturing method, characterized in that performed for 2 to 4 hours at 850 ~ 1100 ℃. 제 2항에 있어서,The method of claim 2, 상기 제 4단계에서의 성형은 프레스를 이용하여 압축성형법으로 이루어지는 것을 특징으로 하는 압전 세라믹 제조방법.Forming in the fourth step is a piezoelectric ceramic manufacturing method, characterized in that the compression molding method using a press. 제 2항에 있어서,The method of claim 2, 상기 제 5단계에서의 소결은 전기로에서 약 900~1200℃의 온도범위에서 1~3 시간동안 행하는 것을 특징으로 하는 압전 세라믹 제조방법.The sintering in the fifth step is a piezoelectric ceramic manufacturing method, characterized in that performed for 1 to 3 hours in the temperature range of about 900 ~ 1200 ℃ in the electric furnace. 제 2항에 있어서,The method of claim 2, 상기 제 6단계에서의 전극은 상기 소결체의 양면에 인쇄 도포법으로 은전극을 바르고 소분하여 형성하는 것을 특징으로 하는 압전 세라믹 제조방법.The method of claim 6, wherein the electrode in the sixth step is formed by applying and subdividing a silver electrode on both surfaces of the sintered body by a printing coating method. 제 2항에 있어서,The method of claim 2, 상기 제 7단계에서의 분극처리는 상기 전극이 형성된 소결체를 2~4kV/mm, 유지시간 10~60분, 온도 100~150℃의 조건에서 행하는 것을 특징으로 하는 압전 세라믹 제조방법.The polarization treatment in the seventh step is a piezoelectric ceramic manufacturing method characterized in that the sintered body on which the electrode is formed is performed under conditions of 2 ~ 4kV / mm, holding time 10 ~ 60 minutes, temperature 100 ~ 150 ℃.
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