KR101172797B1 - manufacturing process of composition and the composition thereby for advanced piezoelectricity including CeO2 addition - Google Patents
manufacturing process of composition and the composition thereby for advanced piezoelectricity including CeO2 addition Download PDFInfo
- Publication number
- KR101172797B1 KR101172797B1 KR1020100123659A KR20100123659A KR101172797B1 KR 101172797 B1 KR101172797 B1 KR 101172797B1 KR 1020100123659 A KR1020100123659 A KR 1020100123659A KR 20100123659 A KR20100123659 A KR 20100123659A KR 101172797 B1 KR101172797 B1 KR 101172797B1
- Authority
- KR
- South Korea
- Prior art keywords
- piezoelectric
- ceo
- composition
- present
- ceramic composition
- Prior art date
Links
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/093—Forming inorganic materials
- H10N30/097—Forming inorganic materials by sintering
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
본 발명은 산화세륨(CeO2)을 첨가하는 고기능성(high Q, high Kp를 갖는 의미로써 강압용 압전 변압기 제조를 위한 세라믹스 필요 조성임) 압전 세라믹스 제조방법 및 이에 의해 제조된 압전 세라믹스 조성물에 관한 것으로서, 높은 전기기계 결합계수(kp) 및 기계적 품질계수(Qm)를 동시에 수반하여 압전 역효과 및 정효과를 동시 응용가능한 강압형 압전 변압기용 압전세라믹스 조성물에 관한 발명을 나타낸다. 본 발명에 의한 압전 세라믹스 조성물은 Pb(Nb,Ni)O3, Pb(Mn,Nb)O3 및 Pb(Zr,Ti)O3로 이루어진 세라믹스 조성물에 첨가제로서 조성물 총 중량에 대해 0.1~0.5중량비의 산화세륨(CeO2)이 첨가되는 것을 특징으로 하며, 본 발명에 의한 고기능성 압전 세라믹스 조성물은 기존 압전재료에 비해 압전상수 및 유전상수가 크고, 기계적 품질계수와 전기기계 결합계수가 크게 향상되어 압전 역효과 및 정효과를 동시 응용 가능한 강압형 압전변압기용 압전 세라믹스로서 실용성이 매우 높은 이점이 있다The present invention relates to a method of manufacturing a piezoelectric ceramics and a piezoelectric ceramic composition prepared thereby, which have a high functionality of adding cerium oxide (CeO 2 ) (high Q, meaning Kp, which is a necessary composition for manufacturing piezoelectric transformers). The present invention relates to a piezoceramic composition for a piezoelectric transformer for a piezoelectric transformer having a high electromechanical coupling factor (kp) and a mechanical quality factor (Qm) at the same time. The piezoelectric ceramic composition according to the present invention is 0.1 to 0.5% by weight relative to the total weight of the composition as an additive to the ceramic composition consisting of Pb (Nb, Ni) O 3 , Pb (Mn, Nb) O 3 and Pb (Zr, Ti) O 3 . The cerium oxide of CeO 2 is added, the high-performance piezoelectric ceramic composition according to the present invention has a larger piezoelectric constant and dielectric constant than the conventional piezoelectric material, mechanical quality coefficient and electromechanical coupling coefficient is greatly improved Piezoelectric ceramics for piezoelectric transformers that can apply both piezoelectric and positive effects simultaneously.
Description
본 발명은 별도의 첨가제에 의한 압전 세라믹스 제조방법 및 이에 의해 제조된 압전 세라믹스 조성물에 관한 것으로서, 높은 전기기계결합계수 및 기계적 품질계수를 가지는 산화세륨(CeO2)을 첨가하는 고기능성 압전세라믹스 조성물의 제조방법 및 이에 의해 제조된 압전세라믹스 조성물에 관한 것이다.The present invention relates to a method for producing piezoelectric ceramics by a separate additive and a piezoelectric ceramic composition prepared by the present invention, and to a method of adding a high functional piezoceramic composition to which cerium oxide (CeO 2 ) having a high electromechanical It relates to a manufacturing method and a piezoceramic composition produced thereby.
최근들어 압전 변압기는 기업체나 연구소, 학계에서 많은 연구가 진행되어 왔고 많은 부분이 상용화가 되어있는 실정이다. 또한, 기기의 고성능화와 소형화, 고 신뢰성이 강하게 요구됨에 따라 제조공정 및 조성의 개선 및 기술의 진보가 계속되어 그 응용분야도 넓어지게 되었다.In recent years, piezoelectric transformers have been researched by companies, research institutes, and academia, and many of them have been commercialized. In addition, as the high performance, miniaturization, and high reliability of the device are strongly demanded, improvements in manufacturing processes and compositions, and advances in technology continue to widen the application fields.
압전 변압기는 에너지 변환 과정 중에 자기 에너지로의 변환이 없으므로 권선 변압기에서 나타나는 누설 자속이나 권선에서의 손실이 없어서 효율이 높다는 장점을 지니고 있으며, 권선 변압기에 비해 구조가 간단하고 소형이며 박형으로 제작이 가능하고 전기적 손실이 적다.Piezoelectric transformer has the advantage of high efficiency because there is no leakage flux in winding transformer or loss in winding because there is no conversion to magnetic energy during energy conversion process.The structure is simpler, smaller and thinner than winding transformer. And low electrical loss.
이러한 특성으로 압전 변압기는 음이온 발생기, 전자복사기, 고주파 변압기, 공기청정기 및 DC-DC 컨버터와 소형 AC-adaptor 등에 활용되고 있다.Due to these characteristics, piezoelectric transformers are used in anion generators, electron radiators, high frequency transformers, air cleaners, DC-DC converters and small AC-adaptors.
한편, 압전 변압기는 C.A.Rosen에 의해 기본적인 형태의 압전 변압기가 제안되어 이론적, 실용적 연구가 시작된 후, 최근까지 다양한 용도와 형태를 가진 압전 변압기가 제안되고 거기에 따른 분극 방향과 진동 방향에서의 압전 변압기의 전기적 기계적 특성 연구가 진행되고 있다.On the other hand, the piezoelectric transformer is proposed by the CARosen piezoelectric transformer of the basic form, the theoretical and practical research began, until recently, piezoelectric transformers having various uses and forms have been proposed and piezoelectric transformers in the polarization direction and vibration direction accordingly The study of electrical and mechanical properties of is ongoing.
압전 변압기는 압전 역효과와 압전 정효과를 동시에 응용하기 때문에 높은 전기기계결합계수(kp)와 기계적 품질계수(Qm)를 동시에 수반해야 한다. 하지만 압전 세라믹스의 기본적인 특성의 경우 전기기계결합계수와 기계적 품질계수를 동시에 수반하기에는 큰 어려움이 따르는 실정이다. 이에 따라 높은 압전상수 및 기계적 품질계수를 갖고, 장시간 연속 구동시 낮은 발열현상을 가지는 고품질, 고성능의 압전재료가 요구되고 있다.Piezoelectric transformers must be accompanied by a high electromechanical coupling factor (k p ) and a mechanical quality factor (Q m ) at the same time because they have both a piezoelectric adverse effect and a piezoelectric positive effect. However, in the case of the basic characteristics of piezoelectric ceramics, it is difficult to have both an electromechanical coupling factor and a mechanical quality factor at the same time. Accordingly, there is a demand for high quality and high performance piezoelectric materials having high piezoelectric constants and mechanical quality coefficients and low heat generation during continuous driving for a long time.
본 발명은 상기 문제점을 해결하기 위한 것으로, Pb(Nb,Ni)O3, Pb(Mn,Nb)O3 및 Pb(Zr,Ti)O3로 이루어진 세라믹스 조성물에 CeO2를 첨가하여 특성의 향상을 도모함으로써 에너지 변환효율을 높이기 위해 전기기계결합계수(Kp)가 크고, 승압비를 높이기 위해 기계적 품질계수(Qm)가 크며, 높은 전류를 발생하기 위해 유전상수가 큰 값을 가지는 우수한 유전 및 압전 특성을 가지는 산화세륨을 첨가하는 고기능성 압전세라믹스 조성물의 제조방법 및 이에 의해 제조된 압전세라믹스 조성물의 제공을 그 목적으로 한다.The present invention is to solve the above problems, in the ceramic composition consisting of Pb (Nb, Ni) O 3 , Pb (Mn, Nb) O 3 and Pb (Zr, Ti) O 3 By adding CeO 2 to improve the properties, the electromechanical coupling coefficient (K p ) is large to increase the energy conversion efficiency, the mechanical quality coefficient (Q m ) is large to increase the boost ratio, and the dielectric to generate high current. It is an object of the present invention to provide a method for producing a highly functional piezoceramic composition containing cerium oxide having excellent dielectric and piezoelectric properties having a large constant and a piezoceramic composition prepared thereby.
상기 목적을 달성하기 위해 본 발명은, PbO, ZrO2, TiO2, MnO2, NiO, Nb2O5 의 시료를 혼합, 분쇄하는 제1단계와; 상기 혼합, 분쇄된 시료를 75℃~100℃에서 건조하는 제2단계와; 상기 건조된 시료를 800℃~900℃에서 하소하는 제3단계와; 상기 하소된 시료에 CeO2를 첨가하고, 분산매를 투입하여 다시 혼합, 분쇄하고, 75℃~100℃에서 건조하는 제4단계와; 상기 건조된 시료를 성형하여 이를 소결하는 제5단계;를 포함하여 이루어지는 것을 특징으로 하는 산화세륨을 첨가하는 고기능성 압전세라믹스 조성물의 제조방법을 기술적 요지로 한다.The present invention to achieve the above object, the first step of mixing and grinding a sample of PbO, ZrO 2 , TiO 2 , MnO 2 , NiO, Nb 2 O 5 ; A second step of drying the mixed and ground sample at 75 ° C to 100 ° C; A third step of calcining the dried sample at 800 ° C to 900 ° C; Adding a CeO 2 to the calcined sample, adding a dispersion medium, mixing, pulverizing, and drying at 75 ° C. to 100 ° C .; The fifth step of molding the dried sample and sintering it; the manufacturing method of the high-performance piezoceramic composition to which the cerium oxide is added, comprising a.
또한, 상기 제5단계의 소결온도는 1200℃~1300℃에서 이루어지는 것이 바람직하다.In addition, the sintering temperature of the fifth step is preferably made at 1200 ℃ ~ 1300 ℃.
또한, 본 발명은, Pb(Nb,Ni)O3, Pb(Mn,Nb)O3 및 Pb(Zr,Ti)O3로 이루어진 세라믹스 조성물 또는 0.01Pb(Ni1 /3Nb2 /3)O3, 0.08Pb(Mn1 /3Nb2 /3)O3 및 0.91Pb(Zr0 .505Ti0 .485)O3로 이루어진 세라믹스 조성물에 CeO2가 첨가되는 것을 특징으로 하는 산화세륨이 첨가된 고기능성 압전세라믹스 조성물을 또 다른 기술적 요지로 한다.In addition, the present invention, Pb (Nb, Ni) O 3, Pb (Mn, Nb) O 3 and Pb (Zr, Ti) O 3 or the ceramic composition consisting of 0.01Pb (Ni 1/3 Nb 2 /3) O 3, 0.08Pb (Mn 1/3 Nb 2/3)
여기에서, 상기 CeO2는 상기 세라믹스 조성물 총 중량비에 대해 0.1~0.5중량비(wt%)로 첨가되는 것이 바람직하다.Here, the CeO 2 is preferably added in a 0.1 to 0.5 weight ratio (wt%) relative to the total weight ratio of the ceramic composition.
상기 과제 해결 수단에 의해 본 발명은 높은 전기기계결합계수 및 기계적 품질계수를 가지며, 압전상수 및 유전상수가 크고, 특히 기계적 품질계수가 크게 향상되어 압전 역효과 및 정효과를 동시 응용가능한 강압형 압전 변압기용 압전 세라믹스로서 실용성이 높은 소재의 조성물을 제공할 수 있는 효과가 있다.According to the above problem solving means, the present invention has a high electromechanical coupling coefficient and a mechanical quality coefficient, a piezoelectric constant and a dielectric constant are large, in particular, a piezoelectric transformer having a high piezoelectric reverse effect and a positive effect can be applied simultaneously with a significant improvement in the mechanical quality coefficient. As the piezoelectric ceramics, there is an effect capable of providing a composition of a material having high practicality.
따라서, 본 발명에 따른 고기능성 압전 세라믹스 조성물은 손실이 없고 효율이 높은 강압형 압전 변압기를 제작할 수 있으며, 권선 변압기에 비해 구조가 간단하고 소형이며 박형으로 제작이 가능한 고신뢰성 압전부품을 제조할 수 있는 효과가 있다.Therefore, the high-performance piezoelectric ceramic composition according to the present invention can produce a piezoelectric transformer having no loss and high efficiency, and can manufacture a high reliability piezoelectric component having a simpler structure, a smaller size, and a thinner structure than a winding transformer. It has an effect.
도 1은 본 발명에 따른 고기능성 압전 세라믹스 조성물의 제조과정을 간략하게 나타낸 흐름도.
도 2는 본 발명의 실시예에 따라 1250℃에서 소결되어진 고기능성 압전 세라믹스 조성물의 CeO2 첨가량에 따른 유전 및 압전특성을 나타낸 도.
도 3은 본 발명의 실시예에 따라 1250℃에서 소결되어진 고기능성 압전 세라믹스 조성물의 CeO2 첨가량에 따른 결정구조 분석도를 나타낸 도.
도 4는 본 발명의 실시예에 따라 1250℃에서 소결되어진 고기능성 압전 세라믹스 조성물의 CeO2 첨가량에 따른 미세구조를 나타낸 도((a)0wt%의 CeO2, (b)0.1wt%의 CeO2, (c)0.2wt%의 CeO2, (d)0.3wt%의 CeO2, (e)0.4wt%의 CeO2, (f) 0.5wt%의 CeO2).
도 5a는 본 발명의 실시예에 따라 1250℃에서 소결되어진 고기능성 압전 세라믹스 조성물의 CeO2 첨가량에 따른 전기기계결합계수(kp) 및 기계적품질계수(Qm) 그래프를 나타낸 도.
도 5b는 본 발명의 실시예에 따라 1250℃에서 소결되어진 고기능성 압전 세라믹스 조성물의 CeO2 첨가량에 따른 유전손실(tan δ) 및 밀도 그래프를 나타낸 도.
도 5c는 본 발명의 실시예에 따라 1250℃에서 소결되어진 고기능성 압전 세라믹스 조성물의 CeO2 첨가량에 따른 압전정수(d33) 및 유전율(εr) 그래프를 나타낸 도.1 is a flow chart briefly showing the manufacturing process of the high-performance piezoelectric ceramic composition according to the present invention.
Figure 2 is a diagram showing the dielectric and piezoelectric properties according to the CeO 2 addition amount of the high-performance piezoelectric ceramic composition sintered at 1250 ℃ according to an embodiment of the present invention.
Figure 3 is a view showing the crystal structure analysis according to the CeO 2 addition amount of the high-performance piezoelectric ceramic composition sintered at 1250 ℃ according to an embodiment of the present invention.
4 is a diagram showing the microstructure according to the amount of CeO 2 addition of the high-performance piezoelectric ceramic composition sintered at 1250 ℃ according to an embodiment of the present invention ((a) 0wt% CeO 2 , (b) 0.1wt% CeO 2 (c) 0.2 wt% CeO 2 , (d) 0.3 wt% CeO 2 , (e) 0.4 wt% CeO 2 , (f) 0.5 wt% CeO 2 ).
Figure 5a is a diagram showing the electromechanical coupling coefficient (k p ) and mechanical quality factor (Q m ) graph according to the CeO 2 addition amount of the high-performance piezoelectric ceramic composition sintered at 1250 ℃ according to an embodiment of the present invention.
Figure 5b is a graph showing the dielectric loss (tan δ) and density graph according to the CeO 2 addition amount of the high-performance piezoelectric ceramic composition sintered at 1250 ℃ according to an embodiment of the present invention.
Figure 5c is a graph showing the piezoelectric constant (d 33 ) and the dielectric constant (ε r ) graph according to the CeO 2 addition amount of the high-performance piezoelectric ceramic composition sintered at 1250 ℃ according to an embodiment of the present invention.
본 발명에 있어서는 소성온도를 1250℃로 고정하고 압전특성을 향상시키기 위하여 Pb(Nb,Ni)O3, Pb(Mn,Nb)O3 및 Pb(Zr,Ti)O3로 이루어진 세라믹스 조성물을 기본조성으로 하여 이에 CeO2를 첨가하고, 그 첨가량을 변화시키면서 각각의 시편을 제조하여 그에 따른 구조적 특성과 유전 및 압전특성을 조사하였다.In the present invention, in order to fix the firing temperature at 1250 ° C. and to improve piezoelectric properties, a ceramic composition composed of Pb (Nb, Ni) O 3 , Pb (Mn, Nb) O 3, and Pb (Zr, Ti) O 3 is used. CeO 2 was added to the composition, and each specimen was prepared while varying the amount thereof, and the structural properties, dielectric and piezoelectric properties thereof were investigated.
이하에서는 본 발명의 바람직한 실시예에 따른 산화세륨(CeO2)이 첨가된 압전 세라믹스 조성물 및 그 제조방법에 대하여 설명하고자 한다.Hereinafter, a piezoelectric ceramic composition to which cerium oxide (CeO 2 ) is added according to a preferred embodiment of the present invention and a manufacturing method thereof will be described.
우선 PbO, ZrO2, TiO2, MnO2, NiO, Nb2O5 를 출발원료로 사용하여 각 조성에 따라 칭량된 시료를 에탄올을 분산매로 하여 지르코니아볼을 사용하여 24시간 동안 혼합, 분쇄하였으며, 상기 볼밀한 시료를 80℃에서 24시간동안 건조하였다.First, PbO, ZrO 2 , TiO 2 , MnO 2 , NiO, and Nb 2 O 5 were used as starting materials, and the samples weighed according to each composition were mixed and ground for 24 hours using zirconia ball using ethanol as a dispersion medium. The ball mill sample was dried at 80 ° C. for 24 hours.
그리고, 상기 건조된 시료를 100mesh로 조립한 후, 알루미나 도가니에서 850℃에서 2시간 동안 하소하였다. 이렇게 하소된 시료에 CeO2를 첨가하여 다시 에탄올을 분산매로 지르코니아볼을 사용하여 24시간 동안 혼합, 분쇄하고, 80℃에서 24시간 동안 건조하였다.Then, the dried sample was assembled into 100mesh, and then calcined at 850 ° C. for 2 hours in an alumina crucible. CeO 2 was added to the calcined sample, and ethanol was further mixed and ground for 24 hours using zirconia ball as a dispersion medium, and dried at 80 ° C. for 24 hours.
그리고, 상기 건조된 시료에 PVA(Polyvinyl Alcohol: 5wt% 수용액)을 5wt% 첨가하여 18mm의 직경으로 1ton/cm2을 가하여 일축 성형하여 시편을 성형하였다. 상기 성형된 시편을 1250℃에서 4시간 동안 소결한 후, 두께를 0.95mm로 연마하였다.Then, 5 wt% of PVA (polyvinyl alcohol: 5 wt% aqueous solution) was added to the dried sample, and 1ton / cm 2 was added to a diameter of 18 mm to uniaxially shape the specimen. The molded specimen was sintered at 1250 ° C. for 4 hours and then ground to a thickness of 0.95 mm.
그리고, 상기 시편의 표면에 은전극을 부착시키고, 120℃의 실리콘유에 넣어서 30분간 3㎸/㎜의 전계를 가해 분극하였으며, 이로부터 24시간이 경과한 후에 제반 특성을 측정하였다.Then, a silver electrode was attached to the surface of the specimen, placed in a silicon oil at 120 ° C., and polarized by applying an electric field of 3 mA / mm for 30 minutes, and after 24 hours, various characteristics were measured.
최종분말 및 소결된 시편을 XRD분석을 통하여 상을 확인하였고, SEM을 이용하여 미세조직을 관찰하였다. 이후, 임피던스 해석기(HP4294A)로 압전 세라믹스의 공진주파수(fr), 반공진주파수(fa), 정전용량(C), 유전손실(tan δ)를 측정하였다. 그리고 경방향모드 전기기계결합계수(kp)와 유전율(εr) 그리고 기계적 품질계수(Qm)를 산출하였다.The final powder and the sintered specimens were identified by XRD analysis, and the microstructure was observed using SEM. Subsequently, the resonance frequency f r , the anti-resonant frequency f a , the capacitance C, and the dielectric loss tan δ of the piezoelectric ceramics were measured by an impedance analyzer HP4294A. The radial mode electromechanical coupling factor (k p ), permittivity (ε r ) and mechanical quality factor (Q m ) were calculated.
본 발명에 따른 고기능성 압전 세라믹스 조성물은 전술한 바와 같이, 0.01Pb(Ni1 /3Nb2 /3)O3-0.08Pb(Mn1 /3Nb2 /3)O3-0.91Pb(Zr0 .505Ti0 .485)O3 + χ wt% CeO2 의 조성을 가지며 χ = 0.1~0.5의 값을 가지며, 비교예로서 χ = 0인 경우를 추가하였다.
High functional piezoelectric ceramic composition according to the invention as described above, 0.01Pb (Ni 1/3 Nb 2/3) O 3 -0.08Pb (Mn 1/3
이와 같은 본 발명의 압전 세라믹스 조성물을 1200℃~1300℃ 범위에서 소결하였으며, 가장 소결 특성이 좋은 온도는 1250℃였다. 전반적인 세라믹스 합성공정을 도 1에, 그 물성을 측정한 결과를 도 2에 각각 나타내었다.The piezoelectric ceramic composition of the present invention was sintered in the range of 1200 ° C to 1300 ° C, and the temperature having the best sintering property was 1250 ° C. The overall ceramic synthesis process is shown in FIG. 1 and the results of measuring the physical properties thereof are shown in FIG. 2.
도 2에서 보는 바와 같이, 본 발명에 따른 압전 세라믹스 조성물은 0.2wt% CeO2의 첨가량에서 높은 유전 및 압전특성을 가짐을 알 수 있다.As shown in FIG. 2, it can be seen that the piezoelectric ceramic composition according to the present invention has high dielectric and piezoelectric properties at an amount of 0.2 wt% CeO 2 .
도 3은 1200℃~1300℃의 범위에서 실험한 결과 중 가장 양호한 소결 물성을 나타내는 1250℃ 소결체에 CeO2의 첨가량에 따른 시편의 결정구조 분석도를 나타낸 것이다. 이는 X-ray 회절분석에 의한 것으로, CeO2을 넣지 않은 시편을 제외하고, CeO2의 첨가량에 따른 시편의 결정구조는 모두 (002), (200) 피크를 나타내며 정방정상의 상특성을 나타내었고, 상전이는 나타나지 않았다. 그러나 CeO2의 첨가량이 증가함에 따라 0.5wt%의 첨가량에서는 미반응의 CeO2가 검출되었으며, 이는 유전 및 압전특성의 저하의 원인이 된다.Figure 3 shows the crystal structure analysis of the specimen according to the addition amount of CeO 2 to the 1250 ℃ sintered body showing the best sintered physical properties among the experiments in the range of 1200 ℃ to 1300 ℃ will be. This is due to the X-ray diffraction analysis, except for the specimen that does not contain CeO 2, and the crystal structure of the specimen according to the amount of CeO 2 represents both (002) and (200) peak showed a phase characteristic of the tetragonal phase , No phase change appeared. However, as the amount of CeO 2 increased, unreacted CeO 2 was detected at an amount of 0.5 wt%, which causes a decrease in dielectric and piezoelectric properties.
보다 자세히 살펴보기 위하여, 도 4의 a~f는 본 발명에 따른 고기능성 압전 세라믹스 조성물의 소결온도를 1250℃로 고정하고, CeO2의 첨가량에 다른 미세구조변화를 나타낸 것으로, a는 0wt% CeO2의 조성, b는 0.1wt% CeO2의 조성, c는 0.2 wt% CeO2의 조성, d는 0.3wt% CeO2의 조성, e는 0.4wt% CeO2의 조성, f는 0.5wt% CeO2의 조성일때의 각 미세구조를 나타낸 것이다.In order to examine in more detail, a to f of Figure 4 is fixed to the sintering temperature of the high-performance piezoelectric ceramic composition according to the present invention to 1250 ℃, showing a different microstructure change in the amount of CeO 2 added, a is 0wt% CeO 2. the composition of the, b is 0.1wt% composition of CeO 2, c is 0.2 wt% composition of CeO 2, d is a composition of 0.3wt% CeO 2, e is a composition of 0.4wt% CeO 2, f is 0.5wt% CeO Each microstructure in the composition of 2 is shown.
도시된 바와 같이, CeO2의 첨가량이 증가함에 따라 시편의 그레인(Grain)의 크기는 점차 감소하는 특성을 나타내었으며, CeO2의 첨가량이 0.2wt%일 때 그레인과 그레인 사이의 입계층이 치밀화되어 밀도는 증가하였으며, CeO2의 첨가량이 0.3wt% 일 때부터 그레인 사이즈가 점차 감소하였으며, CeO2의 첨가량이 0.5wt%일 때 그레인 사이즈의 감소와 함께 과잉첨가로 인해 오히려 밀도는 감소하였다.As shown, the size of the grain (Grain) of the specimen, as the addition amount of the increase is CeO 2 showed a property to gradually decrease, the amount of CeO 2 is a grain boundary layer between the grain and the grain densification when 0.2wt% The density increased and the amount of CeO 2 added Grain size gradually decreased from 0.3 wt%, and density was decreased due to over addition with decreasing grain size when the amount of CeO 2 added was 0.5 wt%.
도 5의 a~c 는 본 발명의 강압형 압전변압기용 압전 세라믹스 조성물의 1250℃ 소결온도에서 CeO2의 첨가량에 따른 유전 및 압전특성을 나타낸 것이다. 도 5a는 CeO2의 첨가량에 따른 전기기계결합계수(kp)와 기계적 품질계수(Qm)이며, 도 5b는 CeO2의 첨가량에 따른 밀도와 유전손실(tan δ)이며, 도 5c는 CeO2의 첨가량에 따른 유전율(εr)과 압전정수(d33)이다.5A to 5C show dielectric and piezoelectric characteristics of the piezoelectric transformer composition according to the present invention, depending on the amount of CeO 2 added at a sintering temperature of 1250 ° C. Figure 5a is an electromechanical coupling factor (k p) and mechanical quality factor (Q m), and Figure 5b is the density and the dielectric loss (tan δ) in accordance with the amount of CeO 2 in accordance with the amount of CeO 2, Figure 5c CeO Dielectric constant (ε r ) and piezoelectric constant (d 33 ) according to the amount of 2 added.
먼저 도 5a의 경우 CeO2의 첨가량이 0.2wt%일 때, 전기기계결합계수(kp)는 증가하였으며 기계적 품질계수는 감소하였다. 하지만 0.3wt% 이상의 첨가량에서부터 전기기계결합계수(kp)는 감소하였으며 기계적 품질계수는 감소하다가 증가하는 경향을 나타내었다. 도 5b의 경우 CeO2의 첨가량이 0.2wt%일 때, 입계층의 치밀화에 의해 밀도는 증가하였으며 그 이상의 첨가량에서는 급격히 감소하였다. 반면 유전손실(tan δ)은 미세하게 증가와 감소를 반복하였다. 도 5c의 경우 CeO2의 첨가량이 0.2wt%일 때 입계층의 치밀화에 의해 밀도가 증가함으로써 저유전율층인 기공이 감소하여 유전율(εr)이 증가하였으며, 압전정수(d33) 또한 CeO2의 첨가량이 0.2wt%일 때 증가하였으며, 그 이상의 첨가량에서는 과잉첨가로 인해 압전특성이 감소하였다.First, in the case of FIG. 5A, when the amount of CeO 2 added was 0.2 wt%, the electromechanical coefficient (kp) increased and the mechanical quality coefficient decreased. However, the electromechanical coefficient (kp) decreased and the mechanical quality coefficient decreased, but increased from 0.3 wt% or more. In the case of FIG. 5B, when the amount of CeO 2 added was 0.2 wt%, the density increased due to the densification of the grain boundary layer, and rapidly decreased at the added amount. On the other hand, the dielectric loss (tan δ) was slightly increased and decreased. By increasing the density by the densification of the grain boundary layer when the content of CeO 2 is also 0.2wt% for 5c it was to reduce the low-dielectric layer having a porosity increase the dielectric constant (ε r), the piezoelectric constant (d 33) also CeO 2 The addition amount of was increased at 0.2wt%, the piezoelectric properties were decreased due to the over addition at the addition amount.
Claims (5)
상기 혼합, 분쇄된 시료를 75℃~100℃에서 건조하는 제2단계와;
상기 건조된 시료를 800℃~900℃에서 하소하는 제3단계와;
상기 하소된 시료에 CeO2를 첨가하고, 분산매를 투입하여 다시 혼합, 분쇄하고, 75℃~100℃에서 건조하는 제4단계와;
상기 건조된 시료를 성형하여 이를 소결하는 제5단계;를 포함하여 이루어지는 것을 특징으로 하는 산화세륨이 첨가된 압전세라믹스 조성물의 제조방법.Mix and grind samples of PbO, ZrO 2 , TiO 2 , MnO 2 , NiO, and Nb 2 O 5 , but the composition ratio is 0.01Pb (Ni 1/3 Nb 2/3 ) O 3 -0.08Pb (Mn 1/3 Nb 2/3 ) mixing and grinding the sample to make O 3 -0.91 Pb (Zr 0.505 Ti 0.485 ) O 3 ;
A second step of drying the mixed and ground sample at 75 ° C to 100 ° C;
A third step of calcining the dried sample at 800 ° C to 900 ° C;
Adding a CeO 2 to the calcined sample, adding a dispersion medium, mixing, pulverizing, and drying at 75 ° C. to 100 ° C .;
And a fifth step of molding the dried sample and sintering it. The method of manufacturing a piezoceramic composition to which the cerium oxide is added is included.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100123659A KR101172797B1 (en) | 2010-12-06 | 2010-12-06 | manufacturing process of composition and the composition thereby for advanced piezoelectricity including CeO2 addition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100123659A KR101172797B1 (en) | 2010-12-06 | 2010-12-06 | manufacturing process of composition and the composition thereby for advanced piezoelectricity including CeO2 addition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20120062408A KR20120062408A (en) | 2012-06-14 |
| KR101172797B1 true KR101172797B1 (en) | 2012-08-09 |
Family
ID=46683358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020100123659A KR101172797B1 (en) | 2010-12-06 | 2010-12-06 | manufacturing process of composition and the composition thereby for advanced piezoelectricity including CeO2 addition |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101172797B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200002185A (en) | 2018-06-29 | 2020-01-08 | 윤호섭 | Eco-friendly bathtub |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003261377A (en) | 2002-03-05 | 2003-09-16 | Ngk Insulators Ltd | Dielectric/electrostrictive type element |
| KR100481718B1 (en) | 2001-12-27 | 2005-04-11 | 주식회사 에스세라 | Piezoelectric ceramic composition and piezoelectric device using the same |
-
2010
- 2010-12-06 KR KR1020100123659A patent/KR101172797B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100481718B1 (en) | 2001-12-27 | 2005-04-11 | 주식회사 에스세라 | Piezoelectric ceramic composition and piezoelectric device using the same |
| JP2003261377A (en) | 2002-03-05 | 2003-09-16 | Ngk Insulators Ltd | Dielectric/electrostrictive type element |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120062408A (en) | 2012-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | High performance Aurivillius-type bismuth titanate niobate (Bi3TiNbO9) piezoelectric ceramics for high temperature applications | |
| CN111302797B (en) | Potassium-sodium niobate-based leadless piezoelectric ceramic and preparation method thereof | |
| WO2010128647A1 (en) | Piezoelectric ceramic, method for producing same, and piezoelectric device | |
| US9105845B2 (en) | Piezoelectric ceramic comprising an oxide and piezoelectric device | |
| KR101260675B1 (en) | Method for preparation of piezoelectric element for low sintering and piezoelectric element using the same | |
| KR101099980B1 (en) | Lead-free piezoelectric ceramic composition | |
| KR20130086093A (en) | Lead-free piezoelectric ceramics composition | |
| KR101198298B1 (en) | Composition of lead-free piezoelectric ceramics for sensor and actuator and making method for the same | |
| KR101172797B1 (en) | manufacturing process of composition and the composition thereby for advanced piezoelectricity including CeO2 addition | |
| CN103524129B (en) | Piezoceramic material for ultrasonic emission-type transducers and preparation method | |
| JP4616544B2 (en) | Piezoelectric ceramic composition, production method thereof, and piezoelectric element | |
| KR101239275B1 (en) | Low temperature sintering piezoelectric ceramic composition, manufacturing method thereof, and piezoelectric ceramic device using the same ceramic composition | |
| CN103435346B (en) | Piezoceramic material for ultrasonic receiver-type transducer | |
| Tsai et al. | Doping effects of CuO additives on the properties of low-temperature-sintered PMnN-PZT-based piezoelectric ceramics and their applications on surface acoustic wave devices | |
| KR101299677B1 (en) | PZN-PZT Piezoelectric Ceramic and Method for manufactruing the Same | |
| Liu et al. | Effect of different MnO 2 phases (β-, γ-, and ε-) on the microstructure and piezoelectric properties of Pb (Zr 1/2 Ti 1/2) O 3–Pb (Zn 1/3 Nb 2/3) O 3–Pb (Ni 1/3 Nb 2/3) O 3 ceramics for energy harvesting | |
| KR100816039B1 (en) | Bnbt piezoelectric ceramics and the method for producing the same | |
| Kim et al. | Effects of Zn/Ni ratio and doping material on piezoelectric characteristics of Pb ((Zn, Ni) 1/3Nb2/3) O3–Pb (Zr, Ti) O3 ceramics | |
| CN117326866B (en) | Cerium-manganese co-doped lead zirconate titanate-based piezoelectric ceramic material and preparation method thereof | |
| KR101454341B1 (en) | Piezoelectric ceramic composite and method of fabricating the same | |
| Jaita et al. | Composition range and electrical properties of the morphotropic phase boundary in Bi 0.5 (Na 0.80 K 0.20) 0.5 TiO 3-(Ba 0.7 Sr 0.3) TiO 3 system | |
| JP5894222B2 (en) | Multilayer electronic component and manufacturing method thereof | |
| KR100649931B1 (en) | A method for manufacturing low temperature sintering ceramics | |
| Chen et al. | Piezoelectric and dielectric properties of (Na0. 5K0. 5) NbO3-Bi0. 5 (Na0. 8K0. 2) 0.5 TiO3 lead-free ceramics | |
| KR101792084B1 (en) | Pmw-pnn-pzt piezoelectric ceramics, manufacturing method thereof and ultrasonic transmitting/receiving sensor using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20160801 Year of fee payment: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20170801 Year of fee payment: 6 |
|
| FPAY | Annual fee payment |
Payment date: 20180802 Year of fee payment: 7 |