KR20050082803A - High power piezoelectric ceramic composition and device - Google Patents
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- 239000000919 ceramic Substances 0.000 title claims abstract description 46
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- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 5
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C01G33/006—Compounds containing, besides niobium, two or more other elements, with the exception of oxygen or hydrogen
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Abstract
본 발명은 압전 엑츄에이터나 압전 변압기, 압전 초음파 모터등에 사용될 수 있는 고출력 압전 세라믹 조성물 및 이를 이용하여 제조된 압전소자에 관한 것으로서, 우수한 압전특성 및 유전특성을 갖는 고출력 압전 세라믹 조성물 및 이를 이용하여 제조된 압전소자를 제공하고자 하는데, 그 목적이 있는 것이다. The present invention relates to a high output piezoelectric ceramic composition that can be used in piezoelectric actuators, piezoelectric transformers, piezoelectric ultrasonic motors, and the like, and to piezoelectric elements manufactured using the same, and to a high output piezoelectric ceramic composition having excellent piezoelectric properties and dielectric properties, and To provide a piezoelectric element, which is the purpose.
본 발명은 하기 조성식(1) 또는 조성식(2)와 같이 조성되는 고출력 압전 세라믹 조성물 및 이를 이용한 압전소자를 그 요지로 한다.The present invention has as its gist a high-power piezoelectric ceramic composition and a piezoelectric element using the same, which is formulated as the following Formula (1) or Formula (2).
[조성식 1]: Pb(Zn1/3Nb2/3)x(ZraTib)O3 + z(wt%)Mn 공급원(x= 0.1∼0.3, z=0.1∼2, a + b= 1, a/b = 0.4/0.6 ∼ 0.52/0.48 임)Formula 1: Pb (Zn 1/3 Nb 2/3 ) x (Zr a Ti b ) O 3 + z (wt%) Mn source (x = 0.1 to 0.3, z = 0.1 to 2, a + b = 1, a / b = 0.4 / 0.6-0.52 / 0.48
[조성식 2]: Pb(Zn1/3Nb2/3)x(BⅠ' 1/3BⅡ' 2/3)y(ZraTib)O3 + z(wt%)Mn 공급원(x + y = 0.1∼0.3, z=0.1∼2, a + b= 1, a/b = 0.4/0.6 ∼ 0.52/0.48, BⅠ'은 Ni, Sb, Sn, 및 Mg 로 이루어진 금속그룹으로부터 선택된 1종 또는 2종이상 이고, BⅡ'은 Nb, Ta, W, Yb, Y, 및 Eu로 이루어진 금속그룹으로부터 선택된 1종 또는 2종이상임)Formula 2: Pb (Zn 1/3 Nb 2/3 ) x (B I ′ 1/3 B II ′ 2/3 ) y (Zr a Ti b ) O 3 + z (wt%) Mn source (x + y = 0.1 to 0.3, z = 0.1 to 2, a + b = 1, a / b = 0.4 / 0.6 to 0.52 / 0.48, B I ' is 1 selected from a metal group consisting of Ni, Sb, Sn, and Mg Species or two or more, and B II ' is one or two or more selected from a metal group consisting of Nb, Ta, W, Yb, Y, and Eu)
Description
본 발명은 압전 엑츄에이터나 압전 변압기, 압전 초음파 모터등에 사용될 수 있는 고출력 압전 세라믹 조성물(High Power Piezoelectric Ceramic Composition)및 이를 이용하여 제조된 압전소자에 관한 것으로서, 보다 상세하게는 완화제(Softener) 및 강화제(Hardener)가 첨가된 고출력 압전 세라믹 조성물 및 이를 이용하여 제조된 압전소자에 관한 것이다.The present invention relates to a high power piezoelectric ceramic composition that can be used in piezoelectric actuators, piezoelectric transformers, piezoelectric ultrasonic motors, etc., and piezoelectric elements manufactured using the same, and more particularly, softeners and reinforcing agents ( The present invention relates to a high power piezoelectric ceramic composition to which a hardener is added, and a piezoelectric element manufactured using the same.
압전 초음파 모터, 변압기등의 전기-기계적 공진 (Electro-Mechanical Resonance)을 사용하는 압전소자의 경우, 압전소자에 공진 주파수의 전기적 에너지가 인가될 경우 압전체가 공진을 하게 되고, 그 공진을 이용하여 압전소자의 구동이 일어나게 된다. In the case of piezoelectric elements using electro-mechanical resonance such as piezoelectric ultrasonic motors and transformers, when the electrical energy of the resonant frequency is applied to the piezoelectric element, the piezoelectric element resonates, and the piezoelectric element is used by using the resonance. Driving of the device occurs.
이때, 압전 소자는 큰 기계적 진동으로 인하여, 온도의 상승, 압전특성의 저하를 가져오게 되고, 결론적으로 고출력을 얻을 수 없게 된다. At this time, the piezoelectric element causes an increase in temperature and a decrease in piezoelectric characteristics due to large mechanical vibration, and consequently, high output cannot be obtained.
이러한 고출력 달성에 방해가 되는 현상을 제거하여 고출력 압전 소자를 제작하기 위해서는 압전상수 (dij), 전기기계 변환계수 (kij), 기계적 품질계수 (Qm )이 높은 압전 재료가 사용되어야만 가능하다.The piezoelectric material having high piezoelectric constant (d ij ), electromechanical conversion coefficient (k ij ) and mechanical quality coefficient (Q m ) can be used to manufacture high-power piezoelectric elements by eliminating the phenomena that hinder such high output. .
상기 압전상수와 전기기계 변환계수와 압전상수의 향상은 PZT계의 압전조성에 Nb 등의 완화제 (Softener)를 페롭스카이트(Perovskite) 구조내의 B자리에 소량 첨가함으로써 가능하고, 기계적 품질계수의 향상은 Fe, Mn등의 강화제(Hardener)를 페롭스카이트 (Perovskite) 구조내의 B자리에 소량첨가함으로써 가능한 것으로 널리 알려져 있다. The improvement of the piezoelectric constant, the electromechanical conversion coefficient, and the piezoelectric constant can be achieved by adding a small amount of a softener such as Nb to the B site in the Perovskite structure to improve the piezoelectric composition of the PZT system. It is widely known that a small amount of a hardener such as Fe or Mn can be added to the B site in the Perovskite structure.
고출력 압전 세라믹 조성물의 일례가 미국특허출원 제2002-124619호( Penn State University)에 제시되어 있다.One example of a high power piezoelectric ceramic composition is presented in US Patent Application 2002-124619 to Penn State University.
이 미국 특허출원에는 (zPb(ZrwTi(1-w))O3-(1-z)Pb(Mn1/3Sb 2/3)O3 + REx) 를 기본조성으로 하는 압전 세라믹 조성물에 Eu, Yb등의 희토류 금속을 소량 첨가한 조성물이 제시되어 있다.This U.S. patent application includes a piezoelectric ceramic composition based on (zPb (Zr w Ti (1-w) ) O 3- (1-z) Pb (Mn 1/3 Sb 2/3 ) O 3 + RE x ) The composition which added the rare earth metals, such as Eu and Yb, in small amounts is shown.
상기 희토류 금속은 기본조성 zPb(ZrwTi(1-w))O3-(1-z)Pb(Mn1/3Sb 2/3)O3에 첨가될 시 “강화(hardening)”과 “완화(softening)”효과를 동시에 나타낸다.The rare earth metal is hardened and added to the basic composition zPb (Zr w Ti (1-w) ) O 3- (1-z) Pb (Mn 1/3 Sb 2/3 ) O 3 . Softening ”effect simultaneously.
상기와 같이 희토류 금속이 첨가된 zPb(ZrwTi(1-w))O3-(1-z)Pb(Mn1/3 Sb2/3)O3 압전세라믹은 일반 상업적으로 적용되고 있는 경한(Hard) PZT에 비하여 높은 진동 속도를 나타낸다.As described above, zPb (Zr w Ti (1-w) ) O 3- (1-z) Pb (Mn 1/3 Sb 2/3 ) O 3 piezoceramic to which rare earth metal is added is generally used in commercial applications. (Hard) It shows higher vibration speed than PZT.
그러나, 상기와 같이 희토류 금속이 첨가된 조성물은 희토류 금속이 고가이고, 기본조성의 압전 상수 및 전기기계 결함계수가 낮은 문제점이 있다.However, the rare earth metal is added as described above, the rare earth metal is expensive, there is a problem that the piezoelectric constant and electromechanical defect coefficient of the basic composition is low.
또한, 한국 특허공개공보 제2000-0054267호에는 고진폭 및 고출력 압전 디바이스로 응용하기 위한 xPb(Zr0.53Ti0.47)O3 + yPb(Mn1/3Nb1/3 Sb1/3)O3 + zCr2O3(0.85 ≤ x ≤ 0.95몰%, 0.05 ≤ y ≤ 0.15몰%, 0 < z ≤ 0.1중량%)로 이루어진 압전 세라믹 조성물이 제시되어 있다.In addition, Korean Patent Publication No. 2000-0054267 discloses xPb (Zr 0.53 Ti 0.47 ) O 3 + yPb (Mn 1/3 Nb 1/3 Sb 1/3 ) O 3 + for application as a high amplitude and high power piezoelectric device. A piezoelectric ceramic composition consisting of zCr 2 O 3 (0.85 ≦ x ≦ 0.95 mol%, 0.05 ≦ y ≦ 0.15 mol%, 0 <z ≦ 0.1 wt%) is shown.
상기 압전 세라믹 조성물은 높은 전기기계 결합계수(kp)와 기계적 품질계수(Qm), 높은 압전 정수(d)와 낮은 유전손실(tanδ)을 갖고 있으므로 압전 변압기, 초음파모터, 압전액츄에이터와 같은 고출력 압전 소자의 압전세라믹소재로의 응용이 가능하다는 장점이 있다.The piezoelectric ceramic composition has a high electromechanical coupling coefficient (k p ), a mechanical quality coefficient (Q m ), a high piezoelectric constant (d), and a low dielectric loss (tanδ), so that high power such as piezoelectric transformers, ultrasonic motors, and piezoelectric actuators may be used. There is an advantage that the piezoelectric element can be applied to piezoceramic materials.
그러나, 상기 압전 세라믹 조성물에는 중금속 Cr이 첨가되므로, 환경오염문제 및 공정시 엄격한 관리가 따라야 하는 문제점이 있다.However, since the heavy metal Cr is added to the piezoelectric ceramic composition, there is a problem that environmental pollution and strict management in the process should be followed.
또한, 한국특허공개공보 제2001-0102673호에는 Pb[Sn1/2Nb1/2)x(Zr0.495Ti 0.505 )1-x]O3 + yPbO + zMnO로 조성되고, x는 0.01∼0.05, y는 0.03∼0.6wt, z는 0.7wt이하로 이루어지는 고출력 압전세라믹 조성물이 제시되어 있다.In addition, Korean Patent Publication No. 2001-0102673 discloses Pb [Sn 1/2 Nb 1/2 ) x (Zr 0.495 Ti 0.505 ) 1-x ] O 3 + yPbO + zMnO, where x is 0.01 to 0.05, A high power piezoceramic composition consisting of y of 0.03 to 0.6 wt and z of 0.7 wt or less is presented.
상기 고출력 압전세라믹 조성물은 우수한 유전상수, 기계적품질계수(Qm), 및 전기기계 결합계수(Kp)를 갖는다.The high power piezoceramic composition has excellent dielectric constant, mechanical quality factor (Q m ), and electromechanical coupling coefficient (K p ).
그러나, 상기한 고출력 압전세라믹 조성물은 PbO가 추가로 첨가되므로, 휘발되는 Pb량이 상대적으로 많아져 환경문제가 야기될 우려가 있고, 또한 전기기계결함계수가 다소 낮아 압전소자의 효율이 떨어질 우려가 있다.However, in the high-power piezoceramic composition described above, since PbO is additionally added, the amount of Pb volatilized relatively increases, which may cause environmental problems, and the electromechanical defect coefficient may be slightly lower, which may lower the efficiency of the piezoelectric element. .
또한, 일본 특허공개공보2001-181033호에는 기본 조성식이 [Pba1Aa2][(B1B2)xTiyZrz]O 3(이 기본 조성식에서, A는 Ca, Sr, Ba 및 La로부터 선택된 적어도 1종의 원소이고, B1은 Sn, Zn, Cd, Mg, Ni, Co, Fe, Sc, Yb, Lu, In 또는 Mn이고; B2는 Sb, Nb, Ta, W 또는 Te이고; 또한 a1은 0은 아니지만, a2는 0이 될 수 있음)로 표현되는 산화물 조성물에 대하여 Pd, B2O3, MgO, Al2O3, Mn3O4등으로부터 선택된 적어도 1종의 금속 또는 산화물을 0.01-1중량% 첨가하여 이루어진 압전세라믹 조성물이 제시되어 있다.In addition, Japanese Patent Laid-Open No. 2001-181033 has a basic composition formula [Pb a1 A a2 ] [(B 1 B 2 ) x Ti y Zr z ] O 3 (wherein A is Ca, Sr, Ba, and La). At least one element selected from B 1 is Sn, Zn, Cd, Mg, Ni, Co, Fe, Sc, Yb, Lu, In or Mn; B 2 is Sb, Nb, Ta, W or Te At least one selected from Pd, B 2 O 3 , MgO, Al 2 O 3 , Mn 3 O 4, and the like, with respect to the oxide composition represented by a 1 is not 0, but a 2 may be 0). A piezoceramic composition made by adding 0.01-1% by weight of a metal or oxide is shown.
그러나, 상기 일본 특허공개공보2001-181033호에 제시된 압전세라믹 조성물은 완화특성은 우수하지만, 경화특성은 다소 떨어지는 문제점이 있다. However, the piezoceramic composition disclosed in Japanese Patent Application Laid-Open No. 2001-181033 has a problem of excellent relaxation characteristics, but poor curing characteristics.
본 발명은 기본성분 PZT (Pb(Zr,Ti)O3)에 적절한 완화형 강유전체 (relaxor ferroelectric) 및 강화제를 적정량으로 혼합함으로써 우수한 압전특성 및 유전특성을 갖는 고출력 압전 세라믹 조성물을 제공하고자 하는데, 그 목적이 있는 것이다.The present invention is to provide a high-power piezoelectric ceramic composition having excellent piezoelectric properties and dielectric properties by mixing an appropriate relaxed ferroelectric and a reinforcing agent in an appropriate amount to the basic component PZT (Pb (Zr, Ti) O 3 ). There is a purpose.
또한, 본 발명은 우수한 압전특성 및 유전특성을 갖는 고출력 압전 세라믹 조성물로 제조된 압전소자를 제공하고자 하는데, 그 목적이 있는 것이다. In addition, the present invention is to provide a piezoelectric element made of a high-power piezoelectric ceramic composition having excellent piezoelectric properties and dielectric properties, and an object thereof.
이하, 본 발명에 대하여 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated.
본 발명은 하기 조성식(1)과 같이 조성되는 고출력 압전 세라믹 조성물에 관한 것이다.The present invention relates to a high power piezoelectric ceramic composition which is formulated as in the following formula (1).
[조성식 1][Formula 1]
Pb(Zn1/3Nb2/3)x(ZraTib)O3 + z(wt%)Mn 공급원(x= 0.1∼0.3, z=0.1∼2, a + b= 1, a/b = 0.4/0.6 ∼ 0.52/0.48 임)Pb (Zn 1/3 Nb 2/3 ) x (Zr a Ti b ) O 3 + z (wt%) Mn source (x = 0.1-0.3, z = 0.1-2, a + b = 1, a / b = 0.4 / 0.6-0.52 / 0.48
또한, 본 발명은 하기 조성식(2)와 같이 조성되는 고출력 압전 세라믹 조성물에 관한 것이다.In addition, the present invention relates to a high-power piezoelectric ceramic composition which is formulated as the following formula (2).
[조성식 2][Formula 2]
Pb(Zn1/3Nb2/3)x(BⅠ' 1/3BⅡ' 2/3 )y(ZraTib)O3 + z(wt%)Mn 공급원(x + y = 0.1∼0.3, z=0.1∼2, a + b= 1, a/b = 0.4/0.6 ∼ 0.52/0.48, BⅠ'은 Ni, Sb, Sn, 및 Mg 로 이루어진 금속그룹으로부터 선택된 1종 또는 2종이상 이고, BⅡ'은 Nb, Ta, W, Yb, Y, 및 Eu로 이루어진 금속그룹으로부터 선택된 1종 또는 2종이상임)Pb (Zn 1/3 Nb 2/3 ) x (B I ' 1/3 B II' 2/3 ) y (Zr a Ti b ) O 3 + z (wt%) Mn source (x + y = 0.1 to 0.3, z = 0.1 to 2, a + b = 1, a / b = 0.4 / 0.6 to 0.52 / 0.48, B I ' is one or two or more selected from a metal group consisting of Ni, Sb, Sn, and Mg B II ' is one or two or more selected from a metal group consisting of Nb, Ta, W, Yb, Y, and Eu)
또한, 본 발명은 상기 조성식(1) 또는 조성식(2)와 같이 조성되는 고출력 압전 세라믹 조성물을 이용하여 제조된 압전소자에 관한 것이다.In addition, the present invention relates to a piezoelectric element manufactured using the high-power piezoelectric ceramic composition, which is formulated as the composition formula (1) or composition (2).
이하, 본 발명에 대하여 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
고출력 압전 세라믹 조성물은 압전 엑츄에이터나 압전 변압기, 압전 초음파 모터등에 사용되는 압전소자등의 재료로 사용되고 있다.The high power piezoelectric ceramic composition is used as a material such as piezoelectric elements used in piezoelectric actuators, piezoelectric transformers, piezoelectric ultrasonic motors, and the like.
보다 바람직한 고출력 압전 세라믹 조성물은 높은 출력을 낼수 있을 뿐만 아니라 열손실을 최소화할 수 있는 것이다.More preferred high power piezoelectric ceramic compositions are capable of producing high power as well as minimizing heat loss.
상기와 같이 높은 출력 및 낮은 열손실을 확보하기 위해서는 압전 세라믹 조성물은 완화(softening) 및 강화(Hardening)효과를 동시에 가져야 한다.In order to secure high output and low heat loss as described above, the piezoelectric ceramic composition should have both softening and hardening effects.
즉, 완화효과 즉, 우수한 압전상수, 전기기계결함계수 및 고변위등 뿐만 아니라 강화효과 즉, 우수한 기계적 품질계수(Qm) 및 저손실을 갖는 압전 세라믹 조성물이 요구되고 있다.That is, there is a need for a piezoelectric ceramic composition having a relieving effect, i.e., excellent piezoelectric constant, electromechanical defect coefficient and high displacement, as well as reinforcing effect, i.e., excellent mechanical quality factor (Qm) and low loss.
이러한 특성들이 우수하여야만 높은 전기기계 진동속도를 압전소자로부터 발생시킬 수 있고, 높은 효율을 가지는 고출력 압전소자를 제조할 수 있다.Only when these characteristics are excellent, a high electromechanical vibration speed can be generated from the piezoelectric element, and a high output piezoelectric element having high efficiency can be manufactured.
본 발명자는 완화(softening) 및 강화(Hardening)효과를 동시에 갖는 압전 세라믹 조성물에 대하여 연구 및 실험을 행하고, 그 결과에 근거하여 본 발명을 제안하게 이른 것이다. The inventors conducted research and experiments on piezoelectric ceramic compositions having both softening and hardening effects, and proposed the present invention based on the results.
즉, 본 발명의 고출력 압전 세라믹 조성물은 기본성분 PZT [Pb(Zr,Ti)O3]에 적절한 완화형 강유전체 (relaxor ferroelectric) 및 강화제를 적정량으로 혼합함으로써 완화(softening) 및 강화(Hardening)효과를 동시에 갖게 된다.In other words, the high-power piezoelectric ceramic composition of the present invention has a softening and hardening effect by mixing an appropriate relaxation ferroelectric and a reinforcing agent with the basic component PZT [Pb (Zr, Ti) O 3 ] in an appropriate amount. At the same time.
본 발명에 있어서 기본조성인 PZT[Pb(ZraTib)O3]는 Zr과 Ti가 a + b= 1, 및 a/b = 0.4/0.6 ∼ 0.52/0.48를 만족하는 조성비를 갖도록 조성되어야 한다.In the present invention, PZT [Pb (Zr a Ti b ) O 3 ], which is a basic composition, should be formulated such that Zr and Ti have a composition ratio satisfying a + b = 1 and a / b = 0.4 / 0.6 to 0.52 / 0.48. do.
기본조성인 PZT[Pb(ZraTib)O3]는 a/b가 0.4/0.6보다 작게 조성되는 경우에는 소결성이 저하되고, 압전상수 및 전기기계결합계수가 저감되는 문제점이 있고, a/b가 0.52/0.48보다 크게 조성되는 경우에는 기계적품질계수가 저감되는 문제점이 있다.PZT [Pb (Zr a Ti b ) O 3 ], which is the basic composition, has a problem in that when a / b is smaller than 0.4 / 0.6, the sintering property is lowered, the piezoelectric constant and the electromechanical coupling coefficient are reduced, and a / If b is larger than 0.52 / 0.48, there is a problem that the mechanical quality factor is reduced.
본 발명에서는 상기와 같이 조성되는 PZT 성분에 적정량의 완화형 강유전체및 강화제가 첨가되었을 때 우수한 특성을 얻을 수 있다. In the present invention, excellent properties can be obtained when an appropriate amount of a relaxed ferroelectric and a reinforcing agent are added to the PZT component formed as described above.
즉, 상기 완화형 강유전체 성분은 페롭스카이트 결정구조의 B자리에 위치되어 특히 저손실 고출력 특성을 현저히 향상시킬 수 있다.That is, the relaxed ferroelectric component is located at the B site of the perovskite crystal structure, and in particular, it is possible to remarkably improve low loss high power characteristics.
본 발명의 고출력 압전 세라믹 조성물은 하기 조성식(1)에서와 같이 PZT 성분에 완화형 강유전체인 Pb(Zn1/3Nb2/3)O3 및 강화제인 Mn 공급원을 함유한다.The high power piezoelectric ceramic composition of the present invention contains Pb (Zn 1/3 Nb 2/3 ) O 3 as a relaxed ferroelectric and Mn source as a reinforcing agent in the PZT component as in the following formula (1).
[조성식 1][Formula 1]
Pb(Zn1/3Nb2/3)x(ZraTib)O3 + z(wt%)Mn공급원(x= 0.1∼0.3, z=0.1∼2, a + b= 1, a/b = 0.4/0.6 ∼ 0.52/0.48 임)Pb (Zn 1/3 Nb 2/3 ) x (Zr a Ti b ) O 3 + z (wt%) Mn Source (x = 0.1 to 0.3, z = 0.1 to 2, a + b = 1, a / b = 0.4 / 0.6-0.52 / 0.48
상기 완화형 강유전체인 Pb(Zn1/3Nb2/3)O3는 Zn 및 Nb이 페롭스카이트 결정구조의 B자리에 위치되어 압전상수, 전기기계결함계수 및 고변위등 완화특성을 향상시킬 뿐만 아니라 강화특성인 기계적 품질계수(Qm)도 Mn과 함께 작용하여 증가시키는 역할을 한다.Pb (Zn 1/3 Nb 2/3 ) O 3 , the relaxed ferroelectric, has Zn and Nb positioned in B-position of the perovskite crystal structure to improve the relaxation characteristics such as piezoelectric constant, electromechanical defect coefficient, and high displacement. In addition, the mechanical quality factor (Q m ), which is a reinforcing property, acts together with Mn to increase.
상기 완화형 강유전체인 Pb(Zn1/3Nb2/3)O3가 너무 적게 함유되는 경우에는 충분한 첨가효과를 얻을 수 없고, 너무 많이 함유되는 경우에는 상전이 온도(큐리온도)가 200℃이하로 낮아서 사용온도가 좁아지는 문제점이 있다.When the Pb (Zn 1/3 Nb 2/3 ) O 3, which is the relaxed ferroelectric, is contained too little, a sufficient addition effect cannot be obtained, and when it contains too much, the phase transition temperature (Curie temperature) is 200 ° C. or less. There is a problem that the use temperature is narrowed low.
또한, 본 발명의 다른 고출력 압전 세라믹 조성물은 하기 조성식(2)에서와 같이 PZT 성분에 완화형 강유전체로서 Pb(Zn1/3Nb2/3)x(BⅠ' 1/3BⅡ' 2/3)yO3(x + y = 0.1∼0.3, a + b= 1, a/b = 0.4/0.6 ∼ 0.52/0.48, BⅠ'은 Ni, Sb, Sn, 및 Mg 로 이루어진 금속그룹으로부터 선택된 1종 또는 2종이상 이고, BⅡ'은 Nb, Ta, W, Yb, Y, 및 Eu로 이루어진 금속그룹으로부터 선택된 1종 또는 2종이상임)를 함유하고, 그리고 강화제로서 Mn 공급원을 함유한다.In addition, another high-power piezoelectric ceramic composition of the present invention is Pb (Zn 1/3 Nb 2/3 ) x (B I ' 1/3 B II' 2 / as a relaxed ferroelectric in the PZT component as shown in the following formula (2). 3 ) y O 3 (x + y = 0.1 to 0.3, a + b = 1, a / b = 0.4 / 0.6 to 0.52 / 0.48, B I ' is selected from a metal group consisting of Ni, Sb, Sn, and Mg One or two or more, and B II ' contains one or two or more selected from a metal group consisting of Nb, Ta, W, Yb, Y, and Eu), and contains an Mn source as a reinforcing agent.
[조성식 2][Formula 2]
Pb(Zn1/3Nb2/3)x(BⅠ' 1/3BⅡ' 2/3 )y(ZraTib)O3 + z(wt%)Mn 공급원(x + y = 0.1∼0.3, z=0.1∼2, a + b= 1, a/b = 0.4/0.6 ∼ 0.52/0.48, BⅠ'은 Ni, Sb, Sn, 및 Mg 로 이루어진 금속그룹으로부터 선택된 1종 또는 2종이상 이고, BⅡ'은 Nb, Ta, W, Yb, Y, 및 Eu로 이루어진 금속그룹으로부터 선택된 1종 또는 2종이상임)Pb (Zn 1/3 Nb 2/3 ) x (B I ' 1/3 B II' 2/3 ) y (Zr a Ti b ) O 3 + z (wt%) Mn source (x + y = 0.1 to 0.3, z = 0.1 to 2, a + b = 1, a / b = 0.4 / 0.6 to 0.52 / 0.48, B I ' is one or two or more selected from a metal group consisting of Ni, Sb, Sn, and Mg B II ' is one or two or more selected from a metal group consisting of Nb, Ta, W, Yb, Y, and Eu)
상기 Pb(Zn1/3Nb2/3)O3와 함께 함유될 수 있는 완화형 강유전체로는 Pb(Ni1/3Nb2/3)O3,및 Pb(Sb1/2Nb1/2)O3 등을 들수 있다.The relaxed ferroelectrics that may be contained together with Pb (Zn 1/3 Nb 2/3 ) O 3 include Pb (Ni 1/3 Nb 2/3 ) O 3 , and Pb (Sb 1/2 Nb 1/2). ) O 3 and the like.
본 발명의 다른 고출력 압전 세라믹 조성물은 완화형 강유전체로서 Pb(Zn1/3Nb2/3)O3를 반드시 함유하고, 여기에 Pb(Ni1/3 Nb2/3)O3 및 Pb(Sb1/2Nb1/2)O3 등을 추가로 1종 또는 2종을 함유한다.Another high power piezoelectric ceramic composition of the present invention necessarily contains Pb (Zn 1/3 Nb 2/3 ) O 3 as a relaxed ferroelectric, Pb (Ni 1/3 Nb 2/3 ) O 3 and Pb (Sb 1/2 Nb 1/2 ) O 3 and the like further contain one kind or two kinds.
상기 완화형 강유전체의 함량은 Pb(Zn1/3Nb2/3)x(BⅠ' 1/3 BⅡ' 2/3)y로 표시되는 조성식에서 x + y가 0.1∼0.3이 되도록 설정된다.The content of the relaxed ferroelectric is set such that x + y is 0.1 to 0.3 in the compositional formula represented by Pb (Zn 1/3 Nb 2/3 ) x (B I ' 1/3 B II' 2/3 ) y . .
상기 Pb(Ni1/3Nb2/3)O3 및 Pb(Sb1/2Nb1/2 )O3 등의 완화형 강유전체는 압전상수, 전기기계결합계수를 향상시키는 완화제의 역할을 한다.remind Relaxed ferroelectrics, such as Pb (Ni 1/3 Nb 2/3 ) O 3 and Pb (Sb 1/2 Nb 1/2 ) O 3 , act as a relaxing agent to improve the piezoelectric constant and electromechanical coupling coefficient.
상기 완화형 강유전체 성분이 너무 적게 함유되는 경우에는 충분한 첨가효과를 얻을 수 없고, 너무 많이 함유되는 경우에는 상전이 온도(큐리온도)가 200℃이하로 낮아서 사용온도 범위가 좁아지는 문제점이 있다.If the mild ferroelectric component is contained too little, sufficient addition effect may not be obtained. If the mild ferroelectric component is contained too much, the phase transition temperature (Curie temperature) may be lower than 200 ° C., resulting in a narrow use temperature range.
Mn은 페롭스카이트 결정구조의 B 자리를 치환하여 강화(hardening)효과를 부여할 수 있는 강화제(hardener)로서 첨가되는 성분이다.Mn is a component added as a hardener capable of imparting a hardening effect by substituting the B site of the perovskite crystal structure.
Mn이 첨가되는 경우에는 다른 압전특성의 저감없이 기계적 품질계수가 향상된다.When Mn is added, the mechanical quality factor is improved without reducing other piezoelectric properties.
상기 Mn 공급원으로는 MnO2, Mn2O3, MnCO3 등을 들수 있으며, 이들 Mn 공급원은 PZT 기본조성에 혼합되어 페롭스카이트 결정구조의 B 자리를 치환하게 된다.The Mn source may be MnO 2 , Mn 2 O 3 , MnCO 3 , and the like, and these Mn sources are mixed in the PZT basic composition to replace the B site of the perovskite crystal structure.
상기 Mn 공급원중 가장 바람직한 것은 MnO2이다.Most preferred of the Mn sources is MnO 2 .
페롭스카이트 결정구조의 B 자리에 치환되는 Mn을 공급하는 Mn 공급원의 첨가량은 0.1∼2wt%로 설정하는 것이 바람직하다.The amount of Mn source added to supply Mn substituted in the B site of the perovskite crystal structure is preferably set to 0.1 to 2 wt%.
상기 Mn 공급원의 함량이 0.1wt%미만인 경우에는 그 첨가효과 충분하지 않고, 2 wt%를 초과하는 경우에는 고용한계를 초과하여 압전조성체내에 고용되지 않고 석출되어 이차상을 형성할 수 있으며, 계획된 압전조성물을 얻을 수 없으므로, 압전특성을 저감시키는 문제점이 있기 때문에, 그 함량은 0.1 ~ 2 wt%로 설정하는 것이 바람직하다.If the content of the Mn source is less than 0.1wt%, its addition effect is not sufficient, and if it exceeds 2wt%, it may precipitate out of solid solution in the piezoelectric composition beyond the solid solution limit to form a secondary phase. Since the piezoelectric composition cannot be obtained, there is a problem of reducing the piezoelectric properties, so the content thereof is preferably set to 0.1 to 2 wt%.
본 발명의 바람직한 고출력 압전 세라믹 조성물로는 Pb(Zn1/3Nb2/3)0.2(Zr0.5Ti0.5)0.8O 3 + 0.5 wt% MnO2 조성물, Pb(Zn1/3Nb2/3)0.16(Ni1/3Nb2/3)0.04(Zr 0.5Ti0.5)0.8O3 + 0.5 wt% MnO2 조성물 및 Pb(Zn1/3Nb2/3)0.12(Ni1/3Nb2/3)0.04(Sb 1/2Nb1/2)0.04(Zr0.5Ti0.5)0.8O3 + 0.5 wt% MnO2 조성물등을들수 있다.Preferred high-power piezoelectric ceramic compositions of the present invention include Pb (Zn 1/3 Nb 2/3 ) 0.2 (Zr 0.5 Ti 0.5 ) 0.8 O 3 + 0.5 wt% MnO 2 composition, Pb (Zn 1/3 Nb 2/3 ) 0.16 (Ni 1/3 Nb 2/3 ) 0.04 (Zr 0.5 Ti 0.5 ) 0.8 O 3 + 0.5 wt% MnO 2 composition and Pb (Zn 1/3 Nb 2/3 ) 0.12 (Ni 1/3 Nb 2/3 ) 0.04 (Sb 1/2 Nb 1/2 ) 0.04 (Zr 0.5 Ti 0.5 ) 0.8 O 3 + 0.5 wt% MnO 2 composition.
종래의 압전체 세라믹 조성물에 있어서 완화형 강유전체가 첨가되는 경우에는 압전상수, 전기기계결함계수 및 고변위등의 완화특성은 향상되지만, 기계적 품질계수(Qm)와 같은 강화특성은 저하된다.In the conventional piezoelectric ceramic composition, when the relaxed ferroelectric is added, the relaxation characteristics such as the piezoelectric constant, the electromechanical defect coefficient, and the high displacement are improved, but the reinforcing characteristics such as the mechanical quality factor Q m are lowered.
그러나, 완화형 강유전체를 본 발명에 따라 첨가하는 경우에는 압전상수, 전기기계결함계수 및 고변위등 완화특성이 향상될 뿐만 아니라 강화특성인 기계적 품질계수(Qm)도 증가시키게 된다.However, when the relaxed ferroelectric is added according to the present invention, not only the relaxation characteristics such as the piezoelectric constant, the electromechanical defect coefficient, and the high displacement are improved, but also the mechanical quality factor Q m , which is a reinforcing characteristic, is also increased.
이에 대하여 설명하면 다음과 같다.This will be described as follows.
본 발명의 압전체 세라믹 조성물에 있어서는 완화형 강유전체로 첨가된 원소들 예를 들면, Zn과 Ni의 이온이 Zr, 또는 Ti의 자리를 차지하기 때문에 전하 균형을 맞추기 위하여 산소 공공을 발생시킨다. In the piezoelectric ceramic composition of the present invention, oxygen vacancies are generated in order to balance charges because elements added as a relaxed ferroelectric, for example, ions of Zn and Ni occupy the positions of Zr or Ti.
이렇게 발생된 산소 공공은 분극의 경계(도메인 바운더리)로 확산되고, 결과적으로 분극의 회전을 방해한다. The generated oxygen vacancies diffuse into the boundary of the polarization (domain boundary) and consequently interfere with the rotation of the polarization.
즉, 산소공공에 의한 분극 피닝(polarization pinning)현상이 일어난다. That is, polarization pinning due to oxygen vacancies occurs.
또한, +2가 또는 +3가 이온들이 B 자리를 차지할 경우 결함 쌍극자 (defect dipole)를 산소 공공과 함께 형성하게 된다.In addition, when the +2 or +3 ions occupy the B site, a defect dipole is formed together with the oxygen vacancies.
이렇게 형성된 결함 쌍극자는 내부 쌍극자 전기장 (internal dipolar field)을 형성하고, 분극의 회전을 방해하게 된다. The defective dipoles thus formed form an internal dipolar field and interfere with the rotation of the polarization.
상기한 두가지 이유에 의하여 본 발명의 압전체 세라믹 조성물의 기계적 품질계수 (Qm)가 증가되는 것으로 여겨진다.It is believed that the mechanical quality factor (Q m ) of the piezoelectric ceramic composition of the present invention is increased for two reasons described above.
한편, 본 발명의 고출력 압전 세라믹 조성물은 PZT와 같은 완벽한 강유전성 페롭스카이트 구조를 가지며, 이차상이 존재하지 않는다.On the other hand, the high power piezoelectric ceramic composition of the present invention has a perfect ferroelectric perovskite structure such as PZT, and there is no secondary phase.
또한, 본 발명의 고출력 압전 세라믹 조성물은 큐리온도가 300℃ 내외로 높아 고출력 소자용 압전재료로도 적합하다.In addition, the high-power piezoelectric ceramic composition of the present invention has a high Curie temperature of about 300 ° C. and is also suitable as a piezoelectric material for high power devices.
본 발명의 압전소자는 상기한 조성식(1) 또는 조성식(2)와 같이 조성되는 고출력 압전 세라믹 조성물을 이용하여 제조된다.The piezoelectric element of the present invention is manufactured by using a high power piezoelectric ceramic composition which is formulated as in the above formula (1) or (2).
이하, 본 발명의 고출력 압전세라믹 조성물을 제조하는 방법의 일례에 대하여 설명하면 다음과 같다.Hereinafter, an example of a method for producing the high output piezoceramic composition of the present invention will be described.
본 발명의 고출력 압전세라믹 조성물은 통상적인 방법에 의하여 제조될 수 있다.The high power piezoceramic composition of the present invention can be prepared by conventional methods.
본 발명에 따라 고출력 압전세라믹 조성물을 제조하기 위해서는 본 발명의 고출력 압전세라믹 조성물을 구성하는 성분들의 산화물 분말들을 칭량하여 이들 산화물과 Mn의 공급원으로서 MnO2, Mn2O3, MnCO3 등을 혼합한다.In order to prepare a high power piezoceramic composition according to the present invention, oxide powders of the components constituting the high power piezoceramic composition of the present invention are weighed to provide MnO 2 , as a source of these oxides and Mn. Mn 2 O 3 , MnCO 3 and the like are mixed.
조성물을 구성하는 Pb의 경우에는 PbO형태로, Zr의 경우에는 ZrO2형태로, Nb의 경우에는 Nb2O5 형태로, Ti의 경우에는 TiO2형태로, Zn의 경우에는 ZnO형태로, Ni의 경우에는 NiO형태로, Sb의 경우에는 Sb2O3형태로 혼합하는 것이 바람직하다.Pb constituting the composition is in the form of PbO, in the form of ZrO 2 in the case of Zr, in the form of Nb 2 O 5 in the case of Nb, in the form of TiO 2 in the case of Ti, in the form of ZnO in the case of Zn, In the case of NiO, in the case of Sb it is preferable to mix in the form of Sb 2 O 3 .
상기 산화물과 Mn 공급원의 슬러리의 혼합은 습식볼 밀링에 의하여 행하는 것이 바람직하며, 볼 밀링은 에탄올 용매와 고순도 3Y-TZP (Tetragonal Zirconia Polycrystalline)볼을 사용하여 행하는 것이 바람직하다.Mixing of the oxide and the slurry of the Mn source is preferably performed by wet ball milling, and ball milling is preferably performed using an ethanol solvent and a high purity 3Y-TZP (Tetragonal Zirconia Polycrystalline) ball.
상기 볼 밀링공정에서는 통상적으로 분쇄 및 혼합이 동시에 일어난다.In the ball milling process, grinding and mixing usually occur simultaneously.
상기와 같이 혼합하는 경우에는 산화물들은 슬러리 형태로 된다.In the case of mixing as described above, the oxides are in the form of a slurry.
다음에, 상기와 같이 혼합된 분말 슬러리를 충분히 건조한 후, 결정상 합성을 위해 하소한다.Next, the powder slurry mixed as above is sufficiently dried and then calcined for crystal phase synthesis.
상기 하소온도가 너무 높거나 하소시간이 너무 길어지면 입자간의 결합력이 커져 차후 행하는 분쇄공정이 어렵게 될 우려가 있고, 또한 입자성장이 일어나 소결성도 저하될 우려가 있다.If the calcination temperature is too high or the calcination time is too long, the bonding force between the particles may increase, and subsequent grinding may be difficult, and particle growth may occur, resulting in a decrease in sinterability.
따라서, 이러한 점을 고려하여 하소조건을 설정하는 것이 바람직하다. Therefore, it is desirable to set the calcination conditions in consideration of this point.
상기 하소온도 및 하소시간은 바람직하게는 800∼900℃에서 30분이상, 보다 바람직하게는 2∼5시간이다.The calcining temperature and the calcining time are preferably 30 minutes or more at 800 to 900 ° C, more preferably 2 to 5 hours.
다음에, 하소된 분말을 다시 미분쇄한다.Next, the calcined powder is pulverized again.
상기 미분쇄는 상기와 같이 에탄올과 3Y-TZP (Tetragonal Zirconia Polycrystalline)볼을 사용하여 행하는 것이 바람직하다.The fine grinding is preferably performed using ethanol and 3Y-TZP (Tetragonal Zirconia Polycrystalline) balls as described above.
상기와 같이 미분쇄된 하소 분말은 슬러리 형태로 된다.The pulverized calcined powder as described above is in the form of a slurry.
다음에, 미분쇄된 분말 슬러리를 건조 및 분쇄한다.Next, the finely ground powder slurry is dried and ground.
다음에, 상기와 같이 건조 및 분쇄된 하소분말을 소결한다.Next, the calcined powder dried and pulverized as above is sintered.
상기 소결온도가 너무 높거나 소결시간이 너무 길어지면, 결정립이 크게 성장하여 기계적으로 취약하고, 또한 PbO의 휘발이 과대히 발생하여 조성의 변화가 발생하여 압전특성 손실 및 유전손실이 커지게 된다.If the sintering temperature is too high or the sintering time is too long, the grains grow large and mechanically weak, and the volatilization of PbO is excessively generated, resulting in a change in composition, resulting in large piezoelectric property loss and dielectric loss.
따라서, 상기한 점을 고려하여 소결조건을 설정하는 것이 바람직하다.Therefore, it is preferable to set the sintering conditions in consideration of the above points.
상기 소결은 공기중 상압하에서 1000∼1200℃의 온도범위에서 30분이상 행하는 것이 바람직하고, 보다 바람직하게는 1100∼1200℃의 온도범위에서 1∼4시간동안 행하는 것이다.The sintering is preferably carried out for 30 minutes or more at a temperature range of 1000 to 1200 ° C under atmospheric pressure in air, and more preferably for 1 to 4 hours at a temperature range of 1100 to 1200 ° C.
상기와 소성하면 고출력 압전 세라믹 조성물이 얻어진다.When fired with the above, a high-power piezoelectric ceramic composition is obtained.
본 발명의 압전소자는 상기와 같이 제조된 고출력 압전 세라믹 조성물을 이용하여 제조된다.The piezoelectric element of the present invention is manufactured using the high output piezoelectric ceramic composition prepared as described above.
본 발명에 부합되는 압전소자를 제조하는 방법은 특별히 한정되는 것은 아니며, 본 발명이 속하는 기술분야에서 통상 사용되는 방법이면 어느 것이나 사용할 수 있다.The method of manufacturing the piezoelectric element according to the present invention is not particularly limited, and any method may be used as long as it is a method generally used in the art.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
(실시예 1)(Example 1)
하기 표 1의 압전 세라믹 조성물이 제조되도록 PbO, ZrO2, Nb2O5, TiO2 , MnO2, ZnO, NiO, Sb2O3 상화물 분말들을 칭량하여 이들 산화물과 MnO2 를 혼합하였다.PbO, ZrO 2 , Nb 2 O 5 , TiO 2 , MnO 2 , ZnO, NiO, and Sb 2 O 3 phase powders were weighed to prepare the piezoelectric ceramic compositions of Table 1, and these oxides and MnO 2 were mixed.
상기 산화물들은 99.9% 이상의 순도를 갖는 것을 사용하였다.The oxides were used having a purity of at least 99.9%.
이 때 혼합은 습식 볼 밀링에 의하여 행하였으며, 이 볼 밀링은 에탄올 용매와 고순도 3Y-TZP (Tetragonal Zirconia Polycrystalline)볼을 사용하여 24시간 동안 행하였다.At this time, mixing was performed by wet ball milling, which was performed for 24 hours using an ethanol solvent and a high purity 3Y-TZP (Tetragonal Zirconia Polycrystalline) ball.
다음에, 혼합된 분말 슬러리를 충분히 건조한 후, 결정상 합성을 위해 850℃에서 5시간동안 하소하였다.The mixed powder slurry was then dried sufficiently and then calcined at 850 ° C. for 5 hours for crystal phase synthesis.
하소된 결정상은 XRD분석으로 상합성을 확인한뒤, 미세한 분말로 분쇄하기 위하여 다시 24시간동안 에탄올과 3Y-TZP (Tetragonal Zirconia Polycrystalline)볼을 사용하여 미세하게 분쇄하였다.The calcined crystal phase was confirmed by XRD analysis, and then finely ground using ethanol and 3Y-TZP (Tetragonal Zirconia Polycrystalline) balls for 24 hours in order to grind into fine powder.
이 때, 미세하게 분쇄된 하소 분말은 슬리러 형태를 갖는다.At this time, the finely ground calcined powder has a slurry form.
다음에, 상기와 같이 미세하게 분쇄된 하소 분말 슬러리를 건조 및 분쇄한 후, 체가름을 하여 미세한 하소분말을 준비하였다.Next, the calcined powder slurry finely pulverized as described above was dried and pulverized, and then sieved to prepare a fine calcined powder.
상기와 같이 준비된 미세한 하소분말을 성형기로 성형하여 성형체(φ12.7 ×3 mm )들을 제조하였다.The fine calcined powder prepared as described above was molded by a molding machine to prepare molded bodies (φ12.7 × 3 mm).
상기와 같이 제조된 성형체들을 공기중에서 1100∼1200℃에서 소결하였다. The molded bodies prepared as above were sintered at 1100 to 1200 캜 in air.
상기 성형체들의 조성이 소결중 변화(주로 PbO의 휘발로 인한)하는 것을 방지하기 위하여 PbZrO3분위기 분말을 고순도 알루미나 도가니에 함께 장입하여 소결하였다.PbZrO 3 atmosphere powder was charged together in a high purity alumina crucible and sintered in order to prevent the composition of the molded bodies from changing during sintering (mainly due to volatilization of PbO).
또한, 성형체와 알루미나 도가니의 화학적 반응을 방지하기 위해 백금호일을 성형체의 바닥에 배치한 후, 소결하여 시편들을 제조하였다.In addition, in order to prevent chemical reaction between the molded body and the alumina crucible, the platinum foil was placed on the bottom of the molded body and then sintered to prepare specimens.
상기와 같이 제조된 시편들은 일정한 두께를 가지도록 연마한 후 은페이스트을 스크린 프린팅하였다.The specimens prepared as described above were polished to have a constant thickness and then screen printed with silver paste.
상기와 같이 스크린 프린팅한 은 페이스트는 600℃에서 10분간 소부하여 전극을 형성시켰다. The silver paste screen-printed as mentioned above was baked at 600 degreeC for 10 minutes, and the electrode was formed.
상기와 같이 전극이 형성된 은 130℃의 실리콘 오일내에서 3kV/mm의 고전압을 인가하여 30분간 분극처리를 행하였다.As described above, polarization treatment was performed for 30 minutes by applying a high voltage of 3 kV / mm in the silicon oil at 130 ° C. in which the electrode was formed.
상기와 같이 제조된 시편들에 대하여 Kp, Qm, d33, 유전상수, tanδ,Np (Hz,m), 및 Tc 측정하고, 그 결과를 하기 표 2에 나타내었다.K p , Q m , d 33 , dielectric constant, tanδ, N p (Hz, m), and T c were measured for the specimens prepared as above, and the results are shown in Table 2 below.
하기 표 2에서 Kp는 일반적인 압전 소자 측정에 사용되는 공진/반공진 법을 이용하여 측정하였다. 임피던스 분석기에 시편을 장착한후 1 Vp-p의 전압으로 주파수에 따른 임피던스 곡선을 측정한 후 공진주파수와 반공진 주파수의 차이에 의하여 다음 수식(1)로 구한 값이다.In Table 2, K p was measured using a resonance / antiresonance method used for general piezoelectric element measurement. After mounting the specimen in the impedance analyzer, measure the impedance curve according to frequency with the voltage of 1 Vp-p and calculate the value by the following equation (1) by the difference between the resonance frequency and the anti-resonance frequency.
[수식 1][Equation 1]
kp 2/(1-kp 2)=(π2/4)(Δf/fr), (Δf=f a-fr) k p 2 / (1-k p 2) = (π 2/4) (Δf / f r), (Δf = f a -f r)
(여기서 fa는 반공진 주파수이고, fr은 공진 주파수임)(Where f a is the anti-resonant frequency and f r is the resonant frequency)
Qm은 임피던스 곡선의 3dB법을 사용하여 측정하였으며, 다음의 수식(2)를 사용하였다.Q m was measured using the 3dB method of the impedance curve, the following equation (2) was used.
[수식 2][Formula 2]
Qm = fr / Δf3dBdown Q m = f r / Δf 3dBdown
(Δf3dBdown 는 공진주파수 진폭에서 3dB 낮은 부분의 주파수차이)(Δf 3dBdown is the frequency difference of 3dB lower part of the resonance frequency amplitude)
d33은 d33 meter를 사용하여 직접측정하였다.d33 was measured directly using a d33 meter.
유전상수와, tanδ는 LCR 메터로 1V전압인가시 1 kHz의 주파수에서의 측정값이다.The dielectric constant and tan δ are measured values at a frequency of 1 kHz when the LCR meter is applied with a 1 V voltage.
Np(Hz,m) 는 주파수 정수로써, 공진주파수와 샘플 직경의 곱으로 구한 값이다.N p (Hz, m) is a frequency constant, which is obtained by multiplying the resonance frequency and the sample diameter.
최대 진동속도는 전압이 인가되어 진동을 할 때, 얻을 수 있는 진동의 속도로써, 전체적인 고출력 압전세라믹의 평가기준이 될 수 있다. 이 진동속도는 전기기계결합계수, 압전상수, 기계적품질계수의 곱과 직접적인 관계를 가지며, 높은 진동속도를 얻기 위해서는 이 세가직 특성이 모두 우수하여야지만 가능하다. The maximum vibration speed is a speed of vibration that can be obtained when a voltage is applied and vibrates, and can be an evaluation criterion of the overall high output piezoceramic. This vibration speed is directly related to the product of the electromechanical coupling coefficient, piezoelectric constant, and mechanical quality coefficient, and it is possible to obtain all three segregation characteristics in order to obtain a high vibration speed.
일반적으로 최대 진동속도는 진동시 발생하는 시편의 온도상승이 20℃가 될때의 진동속도 (rms값)를 의미한다. In general, the maximum oscillation speed means the oscillation speed (rms value) when the temperature rise of the specimen during oscillation reaches 20 ℃.
진동속도는 Laser Doppler vibrometer를 시편의 끝에 초점을 맞춘 후, 시편에 공진주파수의 전압을 증가시켜가며 측정하였다. Vibration velocity was measured by focusing the Laser Doppler vibrometer at the end of the specimen and increasing the voltage at the resonant frequency.
온도변화를 확인하기 위하여 열전대를 시편의 표면에 설치하여 함께 측정하였다.In order to confirm the temperature change, a thermocouple was mounted on the surface of the specimen and measured together.
상기 표 2에 나타난 바와 같이, Pb(Zn1/3Nb2/3)(이하, "PZN"이라고도 함)이 함유되지 않은 PZT 1의 경우에는 낮은 전기기계결합계수 (kp), 압전 상수 (d33), 유전상수 (ε33/εo)와 적절한 기계적품질계수 (Qm)을 나타내고 있음을 알 수 있다.As shown in Table 2, in the case of PZT 1 not containing Pb (Zn 1/3 Nb 2/3 ) (hereinafter also referred to as "PZN"), the low electromechanical coefficient (k p ) and piezoelectric constant ( d 33 ), dielectric constant (ε 33 / ε o ) and appropriate mechanical quality factor (Q m ).
또한, PZT 1의 경우에는 압전특성을 잃는 상전이 온도 [Tc:큐리(Curie)온도)]는 367℃임을 알 수 있다.In addition, in the case of PZT 1, it can be seen that the phase transition temperature [T c : Curie temperature] that loses the piezoelectric characteristic is 367 ° C.
한편, PZN이 첨가된 PZT 2의 경우에는 원주방향 전기기계결합계수 (kp)는 0.588이고, 기계적 품질계수 (Qm)는 1405로 모두 높은 값을 나타내고 있음을 알 수 있다.On the other hand, in the case of PZT 2 to which PZN is added, it can be seen that the circumferential electromechanical coupling coefficient (k p ) is 0.588 and the mechanical quality coefficient (Q m ) is 1405.
이러한 특성은 압전 변압기나 초음파 모터등의 공진을 사용하는 압전소자로 적용하기에 매우 적합하게 해준다.This property makes it very suitable for application to piezoelectric elements using resonance of piezoelectric transformers or ultrasonic motors.
또한, PZT 2의 경우에는 유전손실은 감소됨을 알 수 있다.In addition, in the case of PZT 2 it can be seen that the dielectric loss is reduced.
또한, PZN과 Pb(Ni1/3Nb2/3)(이하, "PNN"이라고도 함)이 동시 첨가된 PZT 3의 경우에는 PZT 2와 비교하여 기계적품질계수와 유전상수는 소폭증가하고, 전기기계 결합계수, 압전상수,유전상수는 소폭 감소하였으나 그 차이는 크지 않음을 알 수 있다.In addition, in the case of PZT 3 to which PZN and Pb (Ni 1/3 Nb 2/3 ) (hereinafter also referred to as "PNN") are added simultaneously, the mechanical quality factor and dielectric constant increase slightly compared to PZT 2, and The mechanical coupling coefficient, piezoelectric constant, and dielectric constant decreased slightly, but the difference was not large.
상기 PZT 3에 Pb(Sb1/2Nb1/2)(이하, "PSN"이라 칭함)이 추가로 첨가된 PZT 4의 경우에는 기계적 품질계수는 소폭 감소하나, 압전상수, 전기기계결합계수 및 유전상수는 증가됨을 알 수 있다.In the case of PZT 4 in which Pb (Sb 1/2 Nb 1/2 ) (hereinafter referred to as "PSN") is additionally added to PZT 3, the mechanical quality coefficient is slightly reduced, but the piezoelectric constant, electromechanical coupling coefficient, It can be seen that the dielectric constant is increased.
더욱이, PZT 1, 2 및 3은 PZT 1에 비하여 최대진동속도가 우수함을 알 수 있다.Moreover, it can be seen that PZT 1, 2 and 3 have superior maximum vibration speeds compared to PZT 1.
(실시예 2)(Example 2)
상기 실시예 1과 동일한 방법으로 제조된 각각의 시편들에 대하여 온도변화에 따른 전기기계결합계수와 기계적 품질계수를 측정하고, 그 결과를 도 1에 나타내었다.For each of the specimens prepared in the same manner as in Example 1, the electromechanical coupling coefficient and the mechanical quality coefficient were measured according to the temperature change, and the results are shown in FIG. 1.
도 1(a)는 전기기계결합계수[Kp(%)]를 나타내고, 도 1(b)는 기계적 품질계수(Qm)를 나타낸다.Figure 1 (a) shows the electromechanical coupling coefficient [K p (%)], Figure 1 (b) shows the mechanical quality factor (Q m ).
도 1(a)에 나타난 바와 같이, 시편 PZT 2, 3 및 4는 -20∼120℃ 영역에서 전기기계결합계수[Kp(%)]가 높을 뿐만 아니라 또한 그 변화폭도 적음을 알 수 있다.As shown in Figure 1 (a), it can be seen that the specimens PZT 2, 3, and 4 not only have a high electromechanical coefficient [K p (%)] in the range of -20 to 120 ° C., but also have a small variation.
한편, PZT 1의 경우에는 -20∼120℃ 영역에서 전기기계결합계수[Kp(%)]의 변화폭은 적지만, 그 값이 시편 PZT 2, 3 및 4에 비하여 현저히 낮음을 알 수 있다.On the other hand, in the case of PZT 1, although the variation range of the electromechanical coupling coefficient [K p (%)] is small in the range of -20 to 120 ° C, the value is significantly lower than that of the specimens PZT 2, 3 and 4.
도 1(b)에 나타난 바와 같이, 시편 PZT 2 및 3의 경우에는 시편 PZT 1에 비하여 0∼120℃ 영역에서의 기계적 품질계수가 우수함을 알 수 있고, 또한 그 변화폭도 적음을 알 수 있다.As shown in FIG. 1 (b), it can be seen that, in the case of specimens PZT 2 and 3, the mechanical quality coefficient in the region of 0 to 120 ° C. is superior to that of the specimen PZT 1, and the change width is small.
다만, 시편 PZT 4의 경우에는 상온까지는 PZT 1에 비하여 기계적 품질계수가 우수하지만 상온 보다 높은 온도에서는 PZT 1에 비하여 기계적 품질계수가 떨어짐을 알 수 있다.However, in the case of specimen PZT 4, the mechanical quality factor is superior to PZT 1 at room temperature, but the mechanical quality factor is lower than PZT 1 at a temperature higher than room temperature.
(실시예 3)(Example 3)
상기 실시예 1과 동일한 방법으로 제조된 시편들의 각각에 대하여 XRD 분석을 행하고, 그 결과를 도 2에 나타내었다.XRD analysis was performed on each of the specimens prepared in the same manner as in Example 1, and the results are shown in FIG. 2.
도 2에 나타난 바와 같이, PZT 1의 경우에는 (200) 면과 (211)면의 회절 피크가 완벽히 분리되어 있음을 알 수 있다.As shown in FIG. 2, in the case of PZT 1, the diffraction peaks of the (200) plane and the (211) plane are completely separated.
따라서, PZT 1의 경우에는 MPB 구조와는 떨어진 정방정(Tetragonal)구조를 갖는다고 볼 수 있다. Therefore, PZT 1 may be regarded as having a tetragonal structure away from the MPB structure.
한편, 시편 PZT 2 및 3의 경우에는 (200) 면과 (211)면의 분리된 회절피크가 완전히 분리되어 있지 않음을 알 수 있다.On the other hand, in the case of specimens PZT 2 and 3, it can be seen that the separated diffraction peaks of the (200) plane and the (211) plane are not completely separated.
따라서, 시편 PZT 2 및 3의 경우에는 MPB 구조에 가까운 결정구조를 갖는다고 볼 수 있다.Therefore, the specimens PZT 2 and 3 can be said to have a crystal structure close to the MPB structure.
또한, 시편 PZT 4의 경우에는 (200) 면과 (211)면의 피크가 겹쳐져 하나의 피크로 나타남을 알 수 있다.In addition, in the case of the specimen PZT 4, it can be seen that the peaks of the (200) plane and the (211) plane overlap and appear as one peak.
따라서, 시편 PZT 4의 경우에는 MPB 구조를 갖는다.Thus, in the case of specimen PZT 4, it has an MPB structure.
(실시예 4)(Example 4)
상기 실시예 1과 동일한 방법으로 제조된 시편들의 각각에 대하여 온도에 따른 유전상수와 유전 손실을 측정하고, 그 결과를 도 3에 나타내었다.For each of the specimens prepared in the same manner as in Example 1, the dielectric constant and dielectric loss according to temperature were measured, and the results are shown in FIG. 3.
도 3에서의 유전상수 및 유전 손실의 측정은 주파수 1 kHz에서 분극처리된 것에 대하여 행하였다. The dielectric constant and dielectric loss in FIG. 3 were measured for polarization at a frequency of 1 kHz.
도 3에 나타난 바와 같이, PZT의 상전이 온도 (Tc; Curie 온도)는 완화형 강유전체가 첨가됨에 따라 감소함을 알 수 있다.As shown in FIG. 3, it can be seen that the phase transition temperature (T c ; Curie temperature) of PZT decreases as the relaxed ferroelectric is added.
즉, 시편 PZT 1의 경우에는 Tc가 367℃이고, 시편 PZT 2의 경우에는 Tc가 306℃이고, 시편 PZT 3의 경우에는 Tc가 298℃이고, 그리고 시편 PZT 4의 경우에는 Tc가 268℃임을 알 수 있다.That is, in the case of the specimen PZT 1 has a T c is 367 ℃, in the case of the specimen PZT 2 has a T c is 306 ℃, in the case of the specimen PZT 3 has a T c is 298 ℃, and in the case of the specimen PZT 4 has T c It can be seen that is 268 ℃.
시편 PZT 2와 3의 경우에는 유사한 Tc를 갖는데, 이는 시편 PZT 2와 3의 조성이 서로 상당히 유사하다는 것을 나타낸다.The specimens PZT 2 and 3 have similar T c , indicating that the compositions of specimens PZT 2 and 3 are quite similar to each other.
또한, 시편 PZT 1의 경우에는 높은 온도에서 유전손실의 증가가 크게 됨을 알 수 있는데, 이는 공간전하가 존재하기 때문이다.In addition, in the case of the specimen PZT 1, it can be seen that the increase of the dielectric loss at a high temperature is large because there is a space charge.
한편, 시편 PZT 2, 3 및 4에서와 같이 완화형 강유전체를 첨가함으로써, 공간전하가 상쇄될 수 있다. On the other hand, by adding a relaxed ferroelectric as in specimens PZT 2, 3 and 4, the space charge can be offset.
(실시예 5)(Example 5)
상기 실시예 1과 동일한 방법으로 제조된 시편 PZT 1 및 4에 대하여 강유전이력곡선(분극-전압, P-E 곡선) 및 변형 이력곡선(변형-전압, S-E 곡선)을 측정하고, 그 결과를 도 4에 나타내었다.Ferroelectric history curves (polarization-voltage, PE curve) and strain hysteresis curves (strain-voltage, SE curve) were measured on specimens PZT 1 and 4 prepared in the same manner as in Example 1, and the results are shown in FIG. Indicated.
도 4(a)는 강유전이력곡선 (분극-전압, P-E)을 나타내고, 그리고 도 4(b)는 변형 이력곡선(변형-전압, S-E)을 나타낸다.Fig. 4 (a) shows the ferroelectric history curve (polarization-voltage, P-E), and Fig. 4 (b) shows the deformation hysteresis curve (strain-voltage, S-E).
도 4에 나타난 바와 같이, 시편 PZT 1의 경우에는 비대칭적인 강유전이력곡선(P-E 곡선)을 나타내고 있음을 알 수 있는데, 이는 경한(하드) 압전체의 전형적 특성이다. As shown in FIG. 4, it can be seen that the specimen PZT 1 exhibits an asymmetric ferroelectric curve (P-E curve), which is a typical characteristic of a hard (hard) piezoelectric body.
순방향으로 전압을 인가할 시 역방향 전압인가시보다 선형적인 곡선을 보이고, 또한, 순방향 전압 인가 시 곡선을 주파수 경향성을 가지지 않는데 반하여 역방향 곡선은 주파수 경향성을 가진다. When the voltage is applied in the forward direction, the curve is more linear than when the reverse voltage is applied. Also, the curve has the frequency tendency while the curve has no frequency tendency when the forward voltage is applied.
시편 PZT 1의 곡선은 4 kV/mm의 전압이 인가되더라도 얇은 타원형을 가지고 둥근 열린 형태가 되지 않음을 알 수 있다.It can be seen that the curve of specimen PZT 1 has a thin oval shape and does not become round open even when a voltage of 4 kV / mm is applied.
시편 PZT 4의 경우에는 완화(softening)특성 및 강화(hardening)특성을 함께 가지고 있음을 알 수 있다.In the case of specimen PZT 4, it can be seen that it has both softening and hardening properties.
즉, 시편 PZT 4의 P-E 및 S-E 곡선은 순방향 전압인가 시 선형 영역을 가지고, 역방향 인가 시 비선형 영역을 나타내고 있음을 알 수 있다.That is, it can be seen that the P-E and S-E curves of the specimen PZT 4 have a linear region when the forward voltage is applied and a nonlinear region when the reverse voltage is applied.
이러한 특성은 자체 내재된 쌍극자 전기장(internal dipolar field)이 존재함을 보여주는 것이다.This property shows the presence of an internal dipolar field.
상기한 바와 같이, 본 발명은 압전상수, 전기기계결합계수, 기계적품질계수가 모두 높은 압전 세라믹 조성물을 제공함으로써 낮은 공진 전압하에서도 높은 출력을 얻을 수 있는 압전소자(압전 초음파 모터, 엑츄에이터, 압전변압기)를 제작할 수 있는 효과가 있는 것이다. As described above, the present invention provides a piezoelectric ceramic composition having a high piezoelectric constant, an electromechanical coupling coefficient, and a mechanical quality coefficient all to provide a piezoelectric element (a piezoelectric ultrasonic motor, an actuator, and a piezoelectric transformer) to obtain a high output even at a low resonance voltage. ) Is the effect that can be produced.
도 1은 본 발명의 압전 세라믹 조성물 및 종래의 압전 세라믹 조성물에 대한 온도변화에 따른 전기기계결합계수와 기계적 품질계수를 나타내는 그래프로서,1 is a graph showing the electromechanical coupling coefficient and the mechanical quality coefficient according to the temperature change of the piezoelectric ceramic composition and the conventional piezoelectric ceramic composition of the present invention.
도 1(a)는 전기기계결합계수[Kp(%)]를 나타내고, 그리고 도 1(b)는 기계적 품질계수(Qm)를 나타냄Figure 1 (a) shows the electromechanical coupling coefficient [K p (%)], and Figure 1 (b) shows the mechanical quality factor (Q m ).
도 2는 본 발명의 압전 세라믹 조성물 및 종래의 압전 세라믹 조성물에 대한 XRD 분석 결과도2 is an XRD analysis result of the piezoelectric ceramic composition and the conventional piezoelectric ceramic composition of the present invention.
도 3은 본 발명의 압전 세라믹 조성물 및 종래의 압전 세라믹 조성물에 대한온도에 따른 유전상수와 유전 손실을 나타내는 그래프Figure 3 is a graph showing the dielectric constant and dielectric loss with temperature for the piezoelectric ceramic composition of the present invention and the conventional piezoelectric ceramic composition
도 4는 강유전이력곡선(분극-전압, P-E 곡선) 및 변형 이력곡선(변형-전압, S-E 곡선)을 나타내는 것으로서, 4 shows the ferroelectric history curve (polarization-voltage, P-E curve) and strain hysteresis curve (strain-voltage, S-E curve),
도 4(a)는 강유전이력곡선 (분극-전압, P-E)을 나타내고, 그리고 도 4(b)는 변형 이력곡선(변형-전압, S-E)을 나타냄4 (a) shows the ferroelectric history curve (polarization-voltage, P-E), and FIG. 4 (b) shows the strain hysteresis curve (strain-voltage, S-E).
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