KR20040049383A - A piezo ceramic composition - Google Patents
A piezo ceramic composition Download PDFInfo
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Abstract
Description
본 발명은 압전 세라믹 조성물에 관한 것으로, 더욱 상세하게는 1000℃ 이하의 소결온도에서 소결이 가능하여 전기 기계 결합 계수 및 기계적 품질 계수가 우수하고 대량 생산이 가능한 압전 세라믹 조성물에 관한 것이다.The present invention relates to a piezoelectric ceramic composition, and more particularly, to a piezoelectric ceramic composition which is capable of sintering at a sintering temperature of 1000 ° C. or less and has excellent electromechanical coupling coefficient and mechanical quality coefficient and is capable of mass production.
일반적으로 압전 현상은 비대칭 결정구조를 가지고 있는 재료에 존재하는 현상으로, 그 명칭은 압력과 전기의 두가지 의미를 함축하고 있으며, 이들 간의 효과를 의미한다.In general, piezoelectric phenomenon is a phenomenon that exists in a material having an asymmetric crystal structure. The name implies two meanings of pressure and electricity, and means an effect between them.
그리고, 압전체에 힘을 가하면 전하를 발생시키는데 이것을 압전효과라고 하며, 반대로 전기를 인가하면 변형이 발생하게 되는데 이것을 역압전 효과라고 한다.When a force is applied to the piezoelectric body, electric charges are generated, which is called a piezoelectric effect. On the contrary, when electricity is applied, deformation occurs, which is called a reverse piezoelectric effect.
한편, 세라믹 재료 중에는 압전현상을 나타내는 몇가지 재료가 있지만 상업적으로 가장 중요한 소재는 크고 안정된 압전현상을 나타내는 Pb(Ti,Zr)O3(이하, PZT라 함.)이라 할 것이다.On the other hand, although there are some materials exhibiting piezoelectric phenomena among ceramic materials, the most important commercial material is Pb (Ti, Zr) O 3 (hereinafter referred to as PZT) which exhibits large and stable piezoelectric phenomena.
그리고, 상기 압전체는 전기 에너지와 기계 에너지의 상호변환이 가능한데 이러한 현상을 이용하여 이들 에너지를 변환하는 트랜스듀스로 사용할 수 있다.In addition, the piezoelectric body can mutually convert electrical energy and mechanical energy, and can be used as a transducer for converting these energies using this phenomenon.
또한, 압전 세라믹은 음향 센서, 초음파 센서, 액츄에이터 등 매우 다양한 응용분야를 가지고 있다.In addition, piezoelectric ceramics have a wide variety of applications such as acoustic sensors, ultrasonic sensors, actuators, and the like.
일반적인 압전재료인 Pb(Zr,Ti)O3는 소결시 1200℃ 전후의 높은 온도가 필요한데, 종래 기술에서는 높은 소결온도에서 PbO가 휘발하기 때문에 미세구조와 물성을 제어하기가 어려워서 제품의 균일성이 감소되는 문제점이 있어 왔다. 또한, 이러한 종래 기술은 소결시 분위기 분말을 사용해야 하는 번거로움 때문에 대량 생산이 어렵고 PbO의 휘발로 인한 환경오염도 우려된다는 문제점이 있었다.Pb (Zr, Ti) O 3, which is a general piezoelectric material, needs high temperature around 1200 ℃ for sintering. In the prior art, since the PbO volatilizes at high sintering temperature, it is difficult to control the microstructure and physical properties. There has been a problem of being reduced. In addition, such a prior art has a problem that the mass production is difficult due to the hassle to use the atmosphere powder during sintering and environmental pollution due to the volatilization of PbO.
따라서, PbO의 휘발이 없는 저온 소결재료가 개발된다면 공기 중에서도 분위기 조절 없이 압전 세라믹의 대량 생산이 가능해질 수 있을 것으로 기대된다.Therefore, if a low temperature sintered material without volatilization of PbO is developed, it is expected that mass production of piezoelectric ceramics can be possible in the air without controlling the atmosphere.
한편, 적층 압전 액츄에이터나 적층 트랜스포머 등의 종래의 적층 부품은 내부 전극과 동시에 소결되어야 하기 때문에 1200℃ 전후의 소결온도에서 동시 소결되는 전극으로 Ag-Pd 등과 같은 고가의 내부 전극을 사용하여야 했다. 내부 전극에 사용되는 Pd는 세계적으로 자원이 고갈되어 가는 물질이며 Ag 보다 수십 배의 가격을 형성하고 있어서 Ag-Pd 합금 내부 전극은 원가가 비싸질 수밖에 없다.On the other hand, conventional laminated parts such as multilayer piezoelectric actuators and multilayer transformers have to be sintered at the same time as internal electrodes, and thus expensive internal electrodes such as Ag-Pd have to be used as electrodes sintered at the sintering temperature of about 1200 ° C. Pd, which is used for internal electrodes, is a material that is depleted in resources around the world and forms a price several times higher than that of Ag. Therefore, Ag-Pd alloy internal electrodes are expensive.
그러나, 이 문제 또한 1000℃ 이하에서 저온 소결되는 압전 재료를 사용한다면 내부전극으로 순수 Ag만을 이용하여서도 동시 소결이 가능해 질 수 있다.However, this problem can also be achieved by simultaneous sintering using only pure Ag as the internal electrode if a piezoelectric material is sintered at a temperature lower than 1000 ° C.
본 발명의 목적은 1000℃ 이하의 저온에서 소결되는 압전 세라믹 조성물을 제공하는 것이다.It is an object of the present invention to provide a piezoelectric ceramic composition which is sintered at a low temperature of 1000 ° C or lower.
또한, 본 발명의 목적은 저온에서 소결되므로 PbO의 휘발을 방지하여 대량 생산이 가능하고 환경오염의 우려가 없으며 전기기계 결합 계수와 기계적 품질 계수가 우수한 압전 세라믹 조성물을 제공하는 것이다.In addition, an object of the present invention is to provide a piezoelectric ceramic composition having excellent electromechanical coupling coefficient and mechanical quality coefficient because it can be mass produced by sintering at low temperature to prevent volatilization of PbO.
상기와 같은 목적을 달성하기 위한 본 발명은, 화학식 Pb[(Zr1-xTix)1-y{(Mn1-zCoz)1/3Nb2/3}y]O3로 표시되고 상기 식에서 x, y, z는 각각 0.4≤x≤0.6, 0<y≤0.15, 0<z≤0.6인 것을 특징으로 한다.The present invention for achieving the above object, the formula Pb [(Zr1-xTix)1-y{(Mn1-zCoz)1/3Nb2/3}y] O3Is indicated by In the above formula, x, y, and z are each 0.4 ≦ x ≦ 0.6, 0 <y ≦ 0.15, and 0 <z ≦ 0.6.
그리고, 저온소결 첨가제로서 (1-a)BaO-aCuO 산화물을 전체 조성물의 중량에 대하여 5중량% 이하로 함유하는 것을 특징으로 한다.And it is characterized by containing (1-a) BaO-aCuO oxide as 5 weight% or less with respect to the weight of the whole composition as a low temperature sintering additive.
상기 식에서, a는 0.5≤a≤0.9이고, (1-a)BaO는 화합물 BaO 또는 BaCO3로부터 선택하여 얻어지고 aCuO는 화합물 CuO 또는 Cu2O로부터 선택하여 얻어진다.Wherein a is 0.5 ≦ a ≦ 0.9, (1-a) BaO is obtained by selecting from compound BaO or BaCO 3 and aCuO is obtained by selecting from compound CuO or Cu 2 O.
도 1은 본 발명에 따른 압전 세라믹 조성물의 소결온도에 따른 전기 기계 결합 계수와 기계적 품질 계수의 변화를 나타낸 그래프이다.1 is a graph showing the change of the electromechanical coupling coefficient and the mechanical quality coefficient according to the sintering temperature of the piezoelectric ceramic composition according to the present invention.
도 2는 본 발명에 따른 압전 세라믹 조성물을 이용한 압전 세라믹의 제조공정을 나타낸 흐름도이다.2 is a flowchart illustrating a manufacturing process of a piezoelectric ceramic using the piezoelectric ceramic composition according to the present invention.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 압전 세라믹 조성물은 PbO, ZrO2, TiO2, MnCO3, CoO, Nb2O5를각각 임의로 결정된 조성비에 따라 혼합하여 제조된다.The piezoelectric ceramic composition according to the present invention is prepared by mixing PbO, ZrO 2 , TiO 2 , MnCO 3 , CoO, Nb 2 O 5 according to an arbitrarily determined composition ratio.
본 발명의 압전 세라믹 조성물은 다음 화학식으로 표시된다.The piezoelectric ceramic composition of the present invention is represented by the following formula.
[화학식 1][Formula 1]
Pb[(Zr1-xTix)1-y{(Mn1-zCoz)1/3Nb2/3}y]O3 Pb [(Zr 1-x Ti x ) 1-y {(Mn 1-z Co z ) 1/3 Nb 2/3 } y ] O 3
상기 식에서, x, y, z는 각각 0.4≤x≤0.6, 0<y≤0.15, 0<z≤0.6이다.Wherein x, y and z are 0.4 ≦ x ≦ 0.6, 0 <y ≦ 0.15 and 0 <z ≦ 0.6, respectively.
본 발명에 따른 압전 세라믹의 조성이 상기한 범위를 벗어날 경우에는 전기 기계 결합계수(K) 또는 기계적 품질 계수(Q) 등의 전기적 압전 특성이 저하되거나 또는 소결온도가 1000℃ 이상으로 상승되어 압전 부품 재료로서의 작용을 기대하기 어렵게 된다.When the composition of the piezoelectric ceramic according to the present invention is out of the above range, the electrical piezoelectric properties such as the electromechanical coupling coefficient (K) or the mechanical quality factor (Q) are degraded or the sintering temperature is raised to 1000 ° C. or more, thereby the piezoelectric component It is difficult to expect the effect as a material.
본 발명에 있어서는, 상기한 PbO, ZrO2, TiO2, MnCO3, CoO, Nb2O5를 목적하는 조성비에 따라 전체 조성물의 양을 기준으로 각각의 첨가량을 측량하여 전자저울로 소수 둘째 자리 밀리그램 단위까지 정확히 취하여 혼합한 다음, 여기에 저온에서 소결이 가능하도록 첨가제 (1-a)BaO-aCuO 산화물을 첨가한 후 혼합하고 건조한다.In the present invention, the above-mentioned PbO, ZrO 2 , TiO 2 , MnCO 3 , CoO, Nb 2 O 5 in accordance with the desired composition ratio of the amount of each of the additives based on the amount of the composition to measure the decimal place second decimal After precisely taking the unit and mixing it, the additive (1-a) BaO-aCuO oxide is added thereto so as to be sintered at low temperature, followed by mixing and drying.
본 발명에 있어서는 저온 소결을 위하여 저온소결 첨가제로서 (1-a)BaO-aCuO 산화물(이하, BC로 기재함.)을 첨가한다; 상기 식에서, a는 0.5≤a≤0.9이고, (1-a)BaO는 화합물 BaO 또는 BaCO3 , 로부터 선택하여 얻어지고 aCuO는 화합물 CuO 또는 Cu2O로부터 선택하여 얻어진다.In the present invention, (1-a) BaO—aCuO oxide (hereinafter referred to as BC) is added as a low temperature sintering additive for low temperature sintering; Wherein a is 0.5 ≦ a ≦ 0.9, (1-a) BaO is obtained by selecting from compounds BaO or BaCO 3 , and aCuO is obtained by selecting from compounds CuO or Cu 2 O.
저온소결 첨가제 BC는 전체 조성물의 중량에 대하여 바람직하기로는 5중량%이하로 첨가되는데, BC는 첨가되기 이전의 세라믹 조성물의 압전특성을 크게 저하시키지 않으면서 저온소결이 유지되도록 하는 작용을 한다. BC가 5중량% 이상 첨가되면, 소결온도는 저하시킬 수 있으나 압전 세라믹의 압전 특성인 K값과 Q값도 동시에 저하된다.The low temperature sintering additive BC is preferably added in an amount of 5% by weight or less based on the total weight of the composition, and BC serves to maintain low temperature sintering without significantly lowering the piezoelectric properties of the ceramic composition before addition. When BC is added 5% by weight or more, the sintering temperature can be lowered, but the K and Q values, which are piezoelectric properties of the piezoelectric ceramic, are also lowered simultaneously.
압전특성을 나타내는 성능지수로서는 전기기계 결합 계수(electro- mechanical coupling factor) K와 기계적 품질 계수(electromechanical quality factor) Qm이 있다.The figure of merit showing piezoelectric characteristics is an electromechanical coupling factor K and an electromechanical quality factor Q m .
전기 기계 결합계수, K는 다음과 같이 정의된다.The electromechanical coefficient, K, is defined as
전기기계 결합 계수의 물리적 의미는 압전체에 전기적 에너지를 가했을 때 그중에 몇%가 기계적 에너지로 변환되었는가에 대한 정도(변환율로서 변환되지 않은 나머지 에너지는 소모되지 않고 그대로 반납되는 형태, 그 역으로 기계적 에너지가 몇% 전기적에너지로 변환된 정도)를 의미하는 것으로, 1 방향 전기적 에너지가 인가될 때 1방향 기계적 에너지로 변환된 비율은 (K11)2, 1방향 전기 에너지 인가시 3방향 기계 에너지 변환은 (K13)2로 표현된다.The physical meaning of the electromechanical coupling factor is the degree to which electrical energy is applied to the piezoelectric body and how much of it is converted into mechanical energy (the conversion rate is the form in which the remaining unconverted energy is not consumed and returned as it is). a percentage as referring to a degree), converted into an electrical energy, one-way electrically, when energy is applied rate of transformation in a direction of the mechanical energy (K 11) 2, when applying the one-way electric energy three-way mechanical energy conversion ( K 13 ) 2 .
따라서, 전기기계 결합 계수는 에너지 변환율의 제곱근으로 표현된다. 예를 들어 K13가 0.3이라면, 1방향으로 100이란 힘을 가했을 때 3방향으로 9 정도의 전기에너지가 발생된다는 개념이다.Thus, the electromechanical coupling coefficient is expressed as the square root of the energy conversion rate. For example, if K 13 is 0.3, the concept is that electrical energy of about 9 is generated in three directions when 100 is applied in one direction.
한편, 품질계수는 전기적 품질계수(Qe)와 기계적 품질계수(Qm)가 있다.On the other hand, the quality factor is an electrical quality factor (Q e ) and a mechanical quality factor (Q m ).
Qe는 전기적 손실(tanδ)의 역수를 뜻한다. 반면에 Qm은 진동체의 기계적 진동 흡수(damping) 때문에 나타난 응력에 대한 변위의 집중도와 시간차 대응 정도(즉 응력을 가했을 때 변형이 나타나는 미세한 시차의 정도)로 물리적인 개념이다.Q e is the inverse of the electrical loss (tanδ). On the other hand, Q m is a physical concept of a mechanical vibration absorption level concentration and the time difference corresponding to the displacement of the stress appeared because (damping) (i.e. the degree of subtle difference that appears when a strain is applied and the stress) of the oscillator.
표 1에는 본 발명에 따라 저온소결 첨가제 BC를 첨가한 후의 압전 특성, 즉 압전 세라믹의 전기기계 결합 계수와 기계적 품질 계수의 변화 및 소결온도를 기재하였다.Table 1 describes the piezoelectric properties after addition of the low temperature sintering additive BC according to the present invention, namely the change in the electromechanical coupling coefficient and mechanical quality coefficient of the piezoelectric ceramic and the sintering temperature.
[표 1] BC 첨가량에 따른 압전특성 및 적정 소결온도TABLE 1 Piezoelectric Properties and Optimum Sintering Temperature According to BC Addition
본 발명에 따른 Pb[(Zr1-xTix)1-y{(Mn1-zCoz)1/3Nb2/3}y]O3조성물에 BC 첨가량을 조성물의 전체 중량에 대하여 0.2 중량%에서 1.6중량%까지 단계적으로 증가시키면서 첨가하였다.The amount of BC added to the Pb [(Zr 1-x Ti x ) 1-y {(Mn 1-z Co z ) 1/3 Nb 2/3 } y ] O 3 compositions according to the present invention was 0.2 relative to the total weight of the composition. It was added in increments from 1% to 1.6% by weight.
표 1에서 보이는 바와 같이, 0.4 중량%까지의 BC 첨가량에서는 소결온도가1050℃까지 낮아져서 소결온도의 저하효과가 관찰되었다. 또한, 0.5 중량% 이상의 첨가량에서는 K값이나 Q 값은 저하되지 않으면서 소결온도가 900℃로 현저히 낮아진 것을 알 수 있으며, 5중량% 이상에서는 소결온도는 저하시키지만 압전특성인 K 값과 Q 값이 현저히 저하되었다.As shown in Table 1, in the BC addition amount up to 0.4 wt%, the sintering temperature was lowered to 1050 ° C, and the effect of lowering the sintering temperature was observed. In addition, at the addition amount of 0.5 wt% or more, the sintering temperature was significantly lowered to 900 ° C without decreasing the K value or the Q value. At 5 wt% or more, the sintering temperature was lowered, but the piezoelectric properties K and Q were Significantly lowered.
상기한 표에서 보이는 바와 같이, 본 발명에 따라 제조되는 압전 세라믹 조성물은 약 1000℃ 전후의 저온에서 압전특성의 변화없이 소결되었다.As shown in the above table, the piezoelectric ceramic composition prepared according to the present invention was sintered at low temperatures around 1000 ° C. without changing the piezoelectric properties.
또한, 도 1에는 본 발명에 따른 압전 세라믹 조성물의 소결온도에 따른 전기기계 결합 계수와 기계적 품질 계수의 변화를 나타내었다.In addition, Figure 1 shows the change of the electromechanical coupling coefficient and the mechanical quality coefficient according to the sintering temperature of the piezoelectric ceramic composition according to the present invention.
이하, 실시예에 의하여 본 발명을 더욱 상세히 설명하면 다음과 같다. 그러나, 하기한 실시예는 본 발명을 예시하기 위하여 기재된 것으로 각 제조단계의 변수, 예를 들면 온도, 시간, 압력, 바인더 양 등은 이 분야에 숙련된 사람들에 의해 본 발명의 범위 내에서 임의로 변화될 수 있다. 그러므로, 본 발명이 다음 실시예에 의하여 제한되지는 않는다.Hereinafter, the present invention will be described in more detail with reference to the following Examples. However, the following examples are set forth to illustrate the invention and the variables of each manufacturing step, such as temperature, time, pressure, binder amount, etc., are arbitrarily changed within the scope of the invention by those skilled in the art. Can be. Therefore, the present invention is not limited by the following examples.
실시예압전 세라믹의 제조 EXAMPLES Preparation of Piezoelectric Ceramics
먼저, Pb[(Zr1-xTix)1-y{(Mn1-zCoz)1/3Nb2/3}y]O3조성에서 x, y, z를 각각 x=0.5, y=0.1, z=0.3으로 하여 각 성분비 PbO:ZrO2:TiO2:MnCO3:CoO:Nb2O5=1:0.45:0.45:0.023:0.01:0.067를 정하고, 혼합 총 중량을 100g 으로 하여 중량비 PbO:ZrO2:TiO2:MnCO3:CoO:Nb2O5=66.47:16.51:10.71:0.79:0.22:5.30 로 상대적 양을결정하였다.First, x, y, and z are x = 0.5, y in the composition of Pb [(Zr 1-x Ti x ) 1-y {(Mn 1-z Co z ) 1/3 Nb 2/3 } y ] O 3 , respectively. = 0.1, z = 0.3, and each component ratio PbO: ZrO 2 : TiO 2 : MnCO 3 : CoO: Nb 2 O 5 = 1: 0.45: 0.45: 0.023: 0.01: 0.067 was determined, and the total weight of the mixture was 100 g. The relative amount was determined as PbO: ZrO 2 : TiO 2 : MnCO 3 : CoO: Nb 2 O 5 = 66.47: 16.51: 10.71: 0.79: 0.22: 5.30.
그리고, 결정된 양에 따라 PbO, ZrO2, TiO2, MnCO3, CoO, Nb2O5를 각각 전자 저울로 소수 둘째 자리 밀리그램 단위까지 정확히 취하여 혼합한 다음 여기에 저온에서 소결이 가능하도록 첨가제 BC를 첨가한 후 혼합하고 건조하는 각 성분의 혼합 건조단계를 수행한다.According to the determined amount, PbO, ZrO 2 , TiO 2 , MnCO 3 , CoO, and Nb 2 O 5 are each accurately weighed to the nearest two milligrams with an electronic balance and then mixed with additive BC to enable sintering at low temperature. After the addition, mixing and drying of each component to be mixed and dried are performed.
그리고, 상기 각 성분의 혼합 건조단계를 통해 혼합, 건조된 혼합 분말을 850℃에서 3시간 동안 하소시키는 하소 단계를 수행한다. 이때 승온 속도는 분당 5℃이며 알루미나 도가니를 사용한다. 상기와 같은 하소 공정을 거친 분체는 알루미나 유발로 잘게 부순 후 재분쇄를 위해 직경 1 mm의 ZrO2볼로 마모 밀을 실시하는 분쇄 단계를 수행한다.Then, a calcining step of calcining the mixed and dried mixed powder through the mixed drying step of each component at 850 ° C. for 3 hours is performed. At this time, the temperature increase rate is 5 ℃ per minute using an alumina crucible. The powder subjected to the calcination process as described above is subjected to a grinding step of performing a grinding mill with ZrO 2 balls having a diameter of 1 mm for regrind after crushing finely by alumina induction.
그리고, 상기 분쇄 단계를 통해 재분쇄된 분말은 건조기에서 건조되고, 결합제로 10% PVA 수용액 10 중량%를 첨가한 후, 100 메쉬 체로 체가름하여 과립화하는 과립화 단계를 수행한다.Then, the powder regrind through the grinding step is dried in a drier, and after the addition of 10% by weight of 10% PVA aqueous solution as a binder, a granulation step of sieving through a 100 mesh sieve to granulate.
그리고, 내경 10 mm의 실린더형 몰드를 사용하여 두께 1 mm 정도의 디스크 형태로 성형하였으며, 성형 시 유압 프레스로 1 톤의 압력을 가하여 성형단계를 수행한다.Then, using a cylindrical mold with an inner diameter of 10 mm was molded into a disk shape having a thickness of about 1 mm, a molding step is performed by applying a pressure of 1 ton by a hydraulic press during molding.
그리고, 상기 성형단계를 통해 성형체의 바인더를 제거하기 위해 시간당 2.5℃/분으로 승온하여 500℃에서 12시간 동안 실시하여 탈바인더 단계를 수행한다.Then, to remove the binder of the molded body through the molding step, the temperature is raised to 2.5 ℃ / min per hour and carried out at 500 ℃ for 12 hours to perform a binder removal step.
또한, 소결은 노에서 진행하였고, 별도의 분위기 조절을 위한 분말은 사용하지 않았다. 이때 시편 간의 접착을 막기 위해 자기분말을 사이에 뿌려 주었다. 승온 속도는 분당 2.5℃이며, 900 내지 1050℃ 소결온도에서는 50℃ 간격으로 2 시간씩 유지하는 소결 단계를 수행한다.In addition, sintering was carried out in the furnace, and no powder for controlling the atmosphere was used. At this time, in order to prevent the adhesion between the specimens were sprayed in between. The temperature increase rate is 2.5 ℃ per minute, at 900 to 1050 ℃ sintering temperature is performed for 2 hours at 50 ℃ intervals are carried out.
그리고, 외부 전극은 은전극을 스크린 프린팅하는 외부 전극도포 단계를 수행하고, 은 소부는 650℃에서 10분간 유지하고 상온까지 냉각시키는 은소부 단계를 수행한다.In addition, the external electrode performs an external electrode coating step of screen printing the silver electrode, and the silver baking part performs a silver baking step of maintaining at 650 ° C. for 10 minutes and cooling to room temperature.
마지막으로 분극은 양단자에 전압을 가하여 2 내지 3 KV/mm 의 전압에서 120 내지 130℃ 범위에서 15분간 유지하는 분극 단계를 수행한다.Finally, the polarization is performed by applying a voltage to both terminals to maintain the polarization step for 15 minutes in the range of 120 to 130 ℃ at a voltage of 2-3 KV / mm.
본 발명에 따른 압전 세라믹 조성물은 1000℃ 이하의 저온에서 소결되므로 PbO의 휘발을 방지하여 대량 생산이 가능하고 환경오염의 우려가 없으며 전기기계 결합 계수와 기계적 품질 계수 등의 압전 특성이 우수하다.Since the piezoelectric ceramic composition according to the present invention is sintered at a low temperature of 1000 ° C. or lower, it is possible to mass-produce by preventing volatilization of PbO, and there is no fear of environmental pollution, and has excellent piezoelectric properties such as electromechanical coupling coefficient and mechanical quality coefficient.
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| JPS5617089A (en) * | 1979-07-20 | 1981-02-18 | Matsushita Electric Ind Co Ltd | Manufacture of piezoelectric ceramic |
| JPH03201491A (en) * | 1989-12-28 | 1991-09-03 | Murata Mfg Co Ltd | Piezoelectric porcelain composition |
| JPH08310862A (en) * | 1995-05-12 | 1996-11-26 | Murata Mfg Co Ltd | Piezoelectric porcelain composition |
| JPH107458A (en) * | 1996-06-25 | 1998-01-13 | Tokin Corp | Piezoelectric porcelain material |
| JPH11228223A (en) * | 1998-02-10 | 1999-08-24 | Toto Ltd | Ceramic composition and piezoelectric transformer made thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5617089A (en) * | 1979-07-20 | 1981-02-18 | Matsushita Electric Ind Co Ltd | Manufacture of piezoelectric ceramic |
| JPH03201491A (en) * | 1989-12-28 | 1991-09-03 | Murata Mfg Co Ltd | Piezoelectric porcelain composition |
| JPH08310862A (en) * | 1995-05-12 | 1996-11-26 | Murata Mfg Co Ltd | Piezoelectric porcelain composition |
| JPH107458A (en) * | 1996-06-25 | 1998-01-13 | Tokin Corp | Piezoelectric porcelain material |
| JPH11228223A (en) * | 1998-02-10 | 1999-08-24 | Toto Ltd | Ceramic composition and piezoelectric transformer made thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110674570A (en) * | 2019-09-04 | 2020-01-10 | 山西大学 | Reverse distance model construction method for calculating contribution rates of different pollution sources to Pb pollution |
| CN110674570B (en) * | 2019-09-04 | 2023-05-30 | 山西大学 | Reverse distance model construction method for calculating Pb pollution contribution rate of different pollution sources |
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