WO2015163685A1 - Matériau piézoélectrique sans plomb pour capteur de cliquetis de véhicule, son procédé de fabrication, capteur de cliquetis de véhicule le comprenant - Google Patents

Matériau piézoélectrique sans plomb pour capteur de cliquetis de véhicule, son procédé de fabrication, capteur de cliquetis de véhicule le comprenant Download PDF

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Publication number
WO2015163685A1
WO2015163685A1 PCT/KR2015/004011 KR2015004011W WO2015163685A1 WO 2015163685 A1 WO2015163685 A1 WO 2015163685A1 KR 2015004011 W KR2015004011 W KR 2015004011W WO 2015163685 A1 WO2015163685 A1 WO 2015163685A1
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Prior art keywords
piezoelectric
powder
cuo
piezoelectric material
mixture
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PCT/KR2015/004011
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English (en)
Korean (ko)
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남산
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고려대학교 산학협력단
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Publication of WO2015163685A1 publication Critical patent/WO2015163685A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L5/00—Apparatus for, or methods of, measuring force, work, mechanical power, or torque, specially adapted for specific purposes
    • 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
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials

Definitions

  • the present invention relates to a non-connected piezoelectric material for a vehicle knocking sensor, a method of manufacturing the same, and a vehicle knocking sensor including the same, and more particularly, to a non-linked piezoelectric material which does not include lead (Pb) and converts mechanical energy and electrical energy.
  • the present invention relates to a method of manufacturing the non-connected piezoelectric body and a vehicle knocking sensor.
  • Piezoelectric materials are widely used as materials for ultrasonic vibrators, electromechanical transducers, and actuator components used in a wide range of fields such as ultrasonic devices, imaging devices, audio devices, communication devices, and sensors.
  • PZT Pb (Zr, Ti) O 3
  • lead (Pb) is a highly toxic material, and volatilized during the sintering process, causing serious environmental pollution. Therefore, research and development on non-connected piezoelectric elements to replace PZT is being actively conducted.
  • the non-piezoelectric material has excellent characteristics that can be applied as a vibration sensor for a vehicle knocking sensor. Therefore, if only a suitable composition for a non-piezoelectric material is developed, it may be possible to substitute PZT. In addition, through the development of the composition of the non-piezoelectric material, not only vibration sensors such as automobile knocking sensors, but also piezoelectric acoustic components and actuators can be sufficiently utilized.
  • BaTiO 3 , (Bi 1/2 Na 1/2 ) TiO 3 and Alkali-Niobate-based ceramics are materials that form a non-connected piezoelectric material.
  • the alkali-based ceramics have excellent piezoelectric properties and have a high phase transition temperature (T c ) of 400 ° C. or higher.
  • NKN NbO 3
  • KN KNbO 3
  • KN KN ceramics
  • NKN-LNTS has been researched as a non-linked piezoelectric material that can replace PZT.
  • NKN ceramics are sintered due to volatilization of sodium (Na) at high temperatures of 1,000 ° C or higher. This volatilization of sodium makes it difficult to fully sinter NKN ceramics and lowers the insulation resistance of the ceramic itself. The decrease in the insulation resistance may affect the polarization process of the piezoelectric ceramics, which may lead to deterioration of the piezoelectric properties.
  • the NKN ceramics are sintered at low temperature to suppress volatilization of sodium and at the same time, research for improvement of piezoelectric properties is needed.
  • KN piezoelectric material has a higher phase transition temperature (T c ) than conventional non-lead piezoelectric materials, and thus, many studies have been conducted since it has been recognized as a possibility as a non-connected piezoelectric material that can replace PZT.
  • T c phase transition temperature
  • the present invention has been made in view of such a problem, and an object of the present invention is to provide a non-connected piezoelectric material for an automobile knock sensor having improved piezoelectric properties.
  • Another object of the present invention is to provide a method for producing a non-connected piezoelectric material for an automotive knock sensor having excellent piezoelectric properties which can be produced at a reduced sintering temperature through a relatively simple manufacturing process.
  • the non-connected piezoelectric material for a vehicle knocking sensor (Na 1-x K x ) NbO 3 ; And z mol% of additive CuO, and is formed at a sintering temperature of 940 to 980 ° C.
  • (Na 2 CO 3 or K 2 CO 3 ) and Nb 2 O 5 are mixed as raw materials to form a first mixture, and the first mixture is formed using a first milling process and a second drying process using the first mixture.
  • the first powder was calcined to form (Na 1-x K x ) NbO 3 powder, where x is 0.5 or 1, and z mol% of additives to the (Na 1-x K x ) NbO 3 powder CuO, where 0.5 ⁇ z ⁇ 2.0, is added to form a second mixture.
  • a second powder is formed through the second milling process and the second drying process using the second mixture, and the second powder is sintered at a temperature of 940 to 980 ° C to form a sintered body.
  • the first milling process may be put in a nylon jar (nylon jar) with anhydrous alcoholic solvent can be crushed for 2 to 24 hours using a zirconia ball.
  • the second milling process may be put into a nylon jar (nylon jar) with anhydrous alcoholic solvent and pulverized for 48 to 72 hours using a zirconia ball.
  • the process of sintering the second powder to form a sintered body may be performed for 2 to 20 hours.
  • the non-connected piezoelectric piezoelectric sensor for automobile knocking sensor and the manufacturing method thereof according to the embodiments of the present invention described above CuO is added and lead (Pb) is not added, thereby preventing environmental problems. Furthermore, the non-connected piezoelectric body can be manufactured through a relatively simple process. In particular, as the low-temperature sintering process is possible at a temperature lower than 1,000 ° C., volatilization of Na 2 O and K 2 O is suppressed, thereby making a non-connected piezoelectric body having a uniform composition. Furthermore, the non-connected piezoelectric element to which CuO is added can implement excellent piezoelectric and dielectric properties.
  • the non-connected piezoelectric body according to the embodiments of the present invention described above has a relatively high piezoelectric voltage constant (g 33 ) value, quality coefficient (Q m ) value, and high phase transition temperature to be suitable for various vibration sensors including a knocking sensor for a vehicle.
  • (T c ) value it can be used for non-connected piezoelectric sensor.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a non-connected piezoelectric material for a vehicle knocking sensor according to embodiments of the present invention.
  • FIG. 2 is a graph showing changes in relative density, dielectric properties, and piezoelectric properties of CuO-added NKN piezoelectric bodies with sintering temperature.
  • FIG. 4 is a graph showing changes in relative density, dielectric properties, and piezoelectric properties of a KN piezoelectric body added with CuO sintered at 960 ° C. for 2.0 hours.
  • Example 5 is a sensor sensitivity characteristics of a knocking sensor manufactured using an NKN piezoelectric material (Example 1) added with CuO sintered at 960 ° C. for 2.0 hours and a vehicle knocking sensor using PZT (existing commercially available, comparative example). This is a graph.
  • Non-connected piezoelectric for automotive knock sensor according to an embodiment of the present invention (Na 1-x K x ) NbO 3 ; And z mol% of additive CuO, and is formed at a sintering temperature of 940 to 980 ° C.
  • first and second may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.
  • the first component may be referred to as the second component, and similarly, the second component may also be referred to as the first component.
  • Non-connected piezoelectric for automotive knocking sensor includes (Na 1-x K x ) NbO 3 and z mol% of additive CuO.
  • x is 0.5 or 1 and has a range of 0.5 ⁇ z ⁇ 2.0. That is, when x is 0.5, the non-connected piezoelectric material includes (Na 0.5 K 0.5 ) NbO 3, and thus, corresponds to the NKN-based piezoelectric material.
  • x is 1, KNbO 3 is included, so the non-connected piezoelectric material includes (N 0.5 K 0.5 ) NbO 3 . do.
  • the additive includes CuO.
  • the additive reacts with (Na 1-x K x ) NbO 3 to form an intermediate in the sintering process of manufacturing the non-connected piezoelectric body, and the intermediate has a relatively low melting point, thereby liquid phase sintering at a reduced sintering temperature. Allow this to proceed. That is, the sintering process may be performed at a sintering temperature of 940 to 980 ° C. Thus, as the sintering process proceeds at the reduced sintering temperature, volatilization of Na 2 O and K 2 O is suppressed, thereby making a non-connected piezoelectric body having a uniform composition.
  • the non-connected piezoelectric element to which CuO is added may implement excellent piezoelectric and dielectric properties.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a non-connected piezoelectric material for a vehicle knocking sensor according to embodiments of the present invention.
  • the composition of the first mixture of purity of 99% or more (Na 2 CO 3 K 2 CO 3 ) and Nb 2 O 5 are subjected to a batch process for calculating the mass ratio, and then a basis weight process for weighing each weight according to the batch results is performed. Then, according to the batch process and basis weight process according to the amount (Na 2 CO 3 or K 2 CO 3 ) and Nb 2 O 5 are mixed to form a first mixture. That is, when Na 2 CO 3, K 2 CO 3 and Nb 2 O 5 are mixed to form a first mixture, an NKN series piezoelectric body is formed, while K 2 CO 3 and Nb 2 O 5 are mixed to form a first mixture. When forming a mixture, a KN series piezoelectric body may be formed.
  • the first mixture is used to form a first powder through a first milling process and a second drying process (S120).
  • a first ball-milling process of wet mixing using anhydrous alcohol solvent for 2 to 24 hours with a zirconia ball in a nylon jar and grinding it into powder This can be done.
  • a drying process of removing the mixed anhydrous alcohol in the first ball-milling process is performed to form a first powder in powder form.
  • the non-connected piezoelectric material includes (Na 0.5 K 0.5 ) NbO 3, and thus, corresponds to the NKN-based piezoelectric material, and when x is 1, KNbO 3 is included and thus corresponds to the KN-based piezoelectric material. do.
  • the calcination process may be performed at 800 to 1000 ° C. for 2 to 10 hours.
  • the additive reacts with (Na 1-x K x ) NbO 3 to form an intermediate during the subsequent sintering process and allows the liquid phase sintering process to proceed at a reduced sintering temperature as the intermediate has a relatively low melting point. . That is, the sintering process may be performed at a sintering temperature of 940 to 980 ° C.
  • the sintering process proceeds at the reduced sintering temperature, volatilization of Na 2 O and K 2 O is suppressed, thereby making a non-connected piezoelectric body having a uniform composition.
  • the non-connected piezoelectric element to which CuO is added may implement excellent piezoelectric and dielectric properties.
  • a second powder is formed through the second milling process and the second drying process using the second mixture.
  • the second powder is wet-mixed for 48 to 72 hours with anhydrous alcohol solvent to the second powder consisting of (Na 1-x K x ) NbO 3 and CuO, and crushed using a zirconia ball -Second ball-milling process can be performed.
  • a drying process may be performed to remove the anhydrous alcoholic solvent used in the second ball-milling process.
  • NKN and KN-based second powder to which CuO was added as an additive is formed.
  • the sintered body may be a piezoelectric material used in a sound wave device, an imaging device, an audio device, a communication device, a sensor, an ultrasonic vibrator, an electromechanical transducer, or an actuator, and may have various shapes and sizes.
  • a sieving process for filtering the second powder into a homogeneous size and a pressing process for performing the filtered powder to have a specific shape are performed in advance.
  • the sintered body may be press-molded to have a cylinder shape or a ring shape.
  • a post-treatment process may be additionally performed on the sintered body.
  • an electrode material is applied to the surface of the sintered body and immersed in silicon oil, and a 3 to 5 kV / mm DC bias may be applied for 1 hour at a temperature of 120 to 150 ° C.
  • the first mixture by mixing Na 2 CO 3 , K 2 CO 3 and Nb 2 O 5 , which is an initial raw material with a purity of 99.9%, and wet mixing with zirconia balls in a nylon jar using anhydrous alcoholic solvent for 24 hours. Formed.
  • the first mixture was dried and then calcined at 950 ° C. for 3 hours to synthesize (Na 0.5 K 0.5 ) NbO 3 (Example 1) and KNbO 3 (Example 2) powders to prepare a first powder.
  • 0.5-5.0 mol% of CuO was added to the first powder, wet mixed and pulverized with anhydrous alcoholic solvent for 72 hours, and then dried to form a second mixture.
  • the dried powder was sintered at 960 ° C. for 2 hours after pressure molding into a cylindrical shaped body having a diameter of 18 mm and a height of about 1.3 to 1.5 mm to form a sintered body.
  • the characteristics were measured after 24 hours after applying a 3-5 kV / mm DC bias for 1 hour at 120-150 ° C. in a silicone oil.
  • FIG. 2 is a graph showing changes in relative density, dielectric properties, and piezoelectric properties of NKN piezoelectric material (Example 1) to which CuO is added according to a change in sintering temperature.
  • Example 3 are electron scanning micrographs showing the microstructure of the KN piezoelectric body (Example 2) added with CuO sintered at 960 ° C. for 2.0 hours according to the change of CuO addition amount.
  • Example 4 is a graph showing changes in relative density, dielectric properties, and piezoelectric properties of a KN piezoelectric body (Example 2) added with CuO sintered at 960 ° C. for 2.0 hours.
  • the sample without CuO at 960 ° C. is not sintered so that the relative density is very low.
  • the liquid phase sintering of the KN piezoelectric body generates a relative density of theoretical density. 95.5%.
  • the piezoelectric strain constant (d 33 ), piezoelectric voltage constant (g 33 ), and dielectric constant and electromechanical coupling constant (K p ) of the KN piezoelectric tend to decrease gradually with the addition amount of CuO.
  • the mechanical quality factor (Q m ) increases rapidly with the addition of CuO. This can be explained by the hardening effect caused by the solid solution of Cu as KN. Particularly, the specimen with 1.5 mol% CuO showed high Q m of 2,300.
  • the piezoelectric voltage constant g 33 has a high value of 44 Vm / N.
  • the piezoelectric voltage constant is the highest value of the non-lead ceramic piezoelectric material known so far, and it can be understood that the piezoelectric voltage constant can be sufficiently applied to a knocking sensor for a vehicle, which is a type of vibration sensor.
  • Example 5 is a sensor sensitivity characteristics of a knocking sensor using a vehicle knocking sensor prepared using NKN piezoelectric material (Example 1) added CuO sintered at 960 ° C. for 2.0 hours and PZT (existing commercially available, comparative example). This is a graph.
  • Example 1 (Na 0.5 K 0.5 ) NbO 3 [NKN] + 1.5 mol% CuO), Example 2 (KNbO 3 [KN] + 1.0 mol% CuO) and Comparative Example (P-6C TM , Murata Co., Ltd.) Dielectric properties and piezoelectric properties for) are summarized in the table below.
  • Example 1 and Example 2 it can be seen that it has superior piezoelectric properties suitable for the vibration sensor than the comparative example. In particular, it can be seen that the piezoelectric voltage constant which directly affects the sensitivity of the vibration sensor is high.
  • the non-connected piezoelectric body according to the embodiments of the present invention can be directly applied to the production of vibration sensors, particularly knocking sensors for automobiles by adjusting the amount of additive (CuO).

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  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
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  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention concerne un matériau piézoélectrique sans plomb pour un capteur de cliquetis de véhicule formé à une température de frittage comprise entre 940 et 980 °C, et qui comporte : (Na1-xKx)NbO3; et un additif CuO de z % en moles, dans lequel x est 0,5 ou 1, et 0,5 ≤ z ≤ 2,0.
PCT/KR2015/004011 2014-04-23 2015-04-22 Matériau piézoélectrique sans plomb pour capteur de cliquetis de véhicule, son procédé de fabrication, capteur de cliquetis de véhicule le comprenant WO2015163685A1 (fr)

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KR10-2014-0048629 2014-04-23
KR1020140048629A KR101616181B1 (ko) 2014-04-23 2014-04-23 자동차 노킹 센서용 비연계 압전체의 제조 방법

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117362034A (zh) * 2023-11-10 2024-01-09 成都信息工程大学 一种高机械品质因数铌酸钾钠基压电陶瓷及低温制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090040089A (ko) * 2007-10-19 2009-04-23 주식회사 이노칩테크놀로지 압전 재료 및 그 제조 방법
KR20100033002A (ko) * 2008-09-19 2010-03-29 (재)울산테크노파크 초음파 진동자용 무연 압전세라믹스 조성물
KR20100089651A (ko) * 2009-02-04 2010-08-12 고려대학교 산학협력단 비연계 압전재료 조성물 및 이를 제조하는 방법
KR20130008804A (ko) * 2011-07-13 2013-01-23 한국기계연구원 고상합성법을 이용하여 제조된 (Ｎａ,Ｋ)ＮｂＯ３계 단결정 무연 압전재료 및 이의 제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090040089A (ko) * 2007-10-19 2009-04-23 주식회사 이노칩테크놀로지 압전 재료 및 그 제조 방법
KR20100033002A (ko) * 2008-09-19 2010-03-29 (재)울산테크노파크 초음파 진동자용 무연 압전세라믹스 조성물
KR20100089651A (ko) * 2009-02-04 2010-08-12 고려대학교 산학협력단 비연계 압전재료 조성물 및 이를 제조하는 방법
KR20130008804A (ko) * 2011-07-13 2013-01-23 한국기계연구원 고상합성법을 이용하여 제조된 (Ｎａ,Ｋ)ＮｂＯ３계 단결정 무연 압전재료 및 이의 제조방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117362034A (zh) * 2023-11-10 2024-01-09 成都信息工程大学 一种高机械品质因数铌酸钾钠基压电陶瓷及低温制备方法

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KR20150122418A (ko) 2015-11-02

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