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CN-118026680-B - Relaxation lead-based textured ceramic material with low texture temperature and high electrical property, and preparation method and application thereof

CN118026680BCN 118026680 BCN118026680 BCN 118026680BCN-118026680-B

Abstract

A relaxation lead-based textured ceramic material with low texture temperature and high electrical property and a preparation method and application thereof relate to a relaxation lead-based textured ceramic material and a preparation method and application thereof. Solves the problems that the high-voltage electrical property and the low texture temperature of the ceramic can not be obtained due to the high texture temperature of the low-Zr-content ceramic and the fact that the oriented crystal grains are in a core-shell structure and the high-Zr-content ceramic is difficult to texture with high quality. The preparation of Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 with chemical formula of (1-x-y) at 850-1095 ℃ can reach a texture Zr content of over 50%, the orientation degree of [001] c is more than 96%, the crystal grain misplacement degree is less than 0.20, the structure has no core-shell structure, the Curie temperature is more than or equal to 200 ℃, the quasi-static piezoelectric coefficient is more than 1000pC/N, and the electromechanical coupling coefficient is more than 0.85. The method comprises the steps of preparing parent fine powder, preparing ceramic green bodies by casting lamination and pressurizing, and preparing textured ceramics. Used in multilayer piezoelectric devices.

Inventors

  • CHANG YUNFEI
  • LIU LINJING
  • XIE HANG
  • Kou qiangwei
  • LV RUI

Assignees

  • 哈尔滨工业大学

Dates

Publication Date
20260505
Application Date
20240206

Claims (6)

  1. 1. A relaxation lead-based textured ceramic material with low texture temperature and high electrical property is characterized by having a chemical formula of (1-x-y) Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 , wherein A is one or a combination of several of Mg, zn, sc and In, x is more than or equal to 0.15 and less than or equal to 0.55,0.15 and y is more than or equal to 0.55, and 0.10 and less than or equal to 1-x-y is more than or equal to 0.50; The relaxation lead-based texture ceramic material with low texture temperature and high electrical property is prepared by combining matrix fine powder or reactive matrix fine powder, a template and a growth auxiliary agent through a liquid phase auxiliary texture technology and a passivation template texture technology, wherein the template is flaky Ba (Zr m Ti 1-m )O 3 microcrystal, m is more than or equal to 0 and less than or equal to 0.1, the volume of the template is a percent of the volume of the matrix fine powder or reactive matrix fine powder, a is more than or equal to 3.0 and less than or equal to 5.0, when x is more than or equal to 0.15 and less than or equal to 0.35, the growth auxiliary agent is a mixture of Li 2 CO 3 and PbO, the mass of the growth auxiliary agent is b percent of the mass of the matrix fine powder, b is more than or equal to 0.1 and less than or equal to 1.2, when x is more than or equal to 0.35 and less than or equal to 0.55, the mass of the growth auxiliary agent is a mixture of Li 2 CO 3 and CuO, and the mass of the growth auxiliary agent is b percent of the mass of the reactive matrix fine powder is more than or equal to 0.1 and less than or equal to 0.48. The relaxation lead-based textured ceramic material with low texture temperature and high electrical property is prepared at a low sintering temperature of 850-1095 ℃, the Zr content of the texture can be up to more than 50%, the orientation degree along [001] c is more than or equal to 98%, the misplacement degree r of crystal grains is less than 0.20 as measured by using a March-Dollase method, the elements in the crystal grains are uniformly distributed, a core-shell-free structure is adopted, the Curie temperature T c is more than or equal to 200 ℃, the quasi-static piezoelectric coefficient d 33 is higher than 1000 pC/N, and the electromechanical coupling coefficient k 33 is higher than 0.85; the preparation method of the relaxation lead-based textured ceramic material with low texture temperature and high electrical property is completed according to the following steps: 1. Preparing parent fine powder: ① Synthesizing an A-containing niobate precursor powder by adopting a solid phase method, wherein the A-containing niobate precursor powder is one or more of MgNb 2 O 6 、ZnNb 2 O 6 、ScNbO 4 and InNbO 4 , and the A-containing niobate precursor powder is pure phase and fine crystal, and has the particle size smaller than 200 nm; ② Preparing parent fine powder or reaction parent fine powder respectively according to different values of x: When x is more than or equal to 0.15 and less than or equal to 0.35, weighing Pb source powder, A niobate-containing precursor powder, zrO 2 powder and TiO 2 powder according to the stoichiometric ratio of (1-x-y) Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 , ball-milling and drying the Pb source powder, the A niobate-containing precursor powder, the ZrO 2 powder and the TiO 2 powder by taking absolute ethyl alcohol as a medium, presintering the mixture for 1-6 hours at 600-900 ℃, and finally ball-milling and drying the mixture for the second time to obtain (1-x-y) Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 parent fine powder, wherein the (1-x-y) Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 parent fine powder is pure perovskite phase and fine crystals, the particle size is less than 300 nm, wherein y is more than or equal to 0.15 and less than or equal to 0.55, and 0.10 and less than or equal to 1-x-y is less than or equal to 0.50, and the Pb source powder is PbO, pb 3 O 4 or basic lead carbonate; When x is less than or equal to 0.35 and less than or equal to 0.55, weighing Pb source powder, A niobate-containing precursor powder, zrO 2 powder and TiO 2 powder according to the stoichiometric ratio of (1-x-y) Pb (A, nb) O 3 -0.35PbZrO 3 -yPbTiO 3 , ball milling and drying by taking absolute ethyl alcohol as a medium, presintering for 1-6 h at 600-900 ℃, finally ball milling and drying for the second time to obtain (1-x-y) Pb (A, nb) O 3 -0.35PbZrO 3 -yPbTiO 3 reaction matrix fine powder, wherein the (1-x-y) Pb (A, nb) O 3 -0.35PbZrO 3 -yPbTiO 3 reaction matrix fine powder is pure perovskite phase and fine crystal, the grain size is less than 300 nm, wherein y is less than or equal to 0.55 and is less than or equal to 0.10 and less than or equal to 0.50, weighing Pb source powder and ZrO 2 powder according to the stoichiometric ratio of PbZrO 3 , presintering for 1-6 h by taking absolute ethyl alcohol as a medium, ball milling and drying at 600-900 ℃, and finally ball milling for the second time to obtain Pb (A, nb) O 3 -0.35PbZrO 3 -yPbTiO 3 reaction matrix fine powder, wherein the grain size is less than 300-0.15 and less than or equal to 1-200 ℃ Pb (B) 3, and the fine crystal phase fine powder is equal to or equal to 60-200 ℃ fine crystal powder after ball milling; 2. Pressurizing and preparing a ceramic green body by casting and laminating: ① Preparing casting slurry according to the different values of x: When x is more than or equal to 0.15 and less than or equal to 0.35, mixing (1-x-y) Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 parent fine powder, flaky Ba (Zr m Ti 1-m )O 3 microcrystal, a growth aid, a solvent, a dispersing agent, a binder and a plasticizer, and then vacuum foaming to obtain (1-x-y) Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 casting slurry containing template seed crystals, wherein the volume of the flaky Ba (Zr m Ti 1-m )O 3 microcrystal is a% of the volume of the (1-x-y) Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 parent fine powder, a is more than or equal to 3.0 and less than or equal to 5.0, the growth aid is a mixture of Li 2 CO 3 and PbO, and the mass of the growth aid is b% of the mass of the (1-x-y) Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 parent fine powder, and b is more than or equal to 0.1 and less than or equal to 1.2; Mixing (1-x-y) Pb (A, nb) O 3 -0.35PbZrO 3 -yPbTiO 3 reactive matrix fine powder, flaky Ba (Zr m Ti 1-m )O 3 microcrystal, a growth aid, a solvent, a dispersing agent, a binder and a plasticizer when x is less than or equal to 0.35, and then vacuum-foaming to obtain a reactive casting slurry of (1-x-y) Pb (A, nb) O 3 -0.35PbZrO 3 -yPbTiO 3 containing template seed crystals, mixing PbZrO 3 reactive matrix fine powder, a solvent, a dispersing agent, a binder and a plasticizer, and then vacuum-foaming to obtain a reactive casting slurry of PbZrO 3 without template seed crystals, wherein the volume of flaky Ba (Zr m Ti 1-m )O 3 microcrystal is a% of the total volume of (1-x-y) Pb (A, nb) O 3 -0.35PbZrO 3 -yPbTiO 3 reactive matrix fine powder and PbZrO 3 reactive matrix fine powder, wherein a is less than or equal to 3.0 and less than or equal to 5.0, the growth aid is a mixture of Li 2 CO 3 and CuO, and the mass of (1-x-y) Pb (A, nb) O 3 -0.35PbZrO 3 -yPbTiO 3 reactive matrix fine powder and Pb 3 % of total fine powder is less than or equal to 0.48 and less than or equal to 0.48% of total mass of the reactive matrix fine powder of PbZrO; ② Casting: casting (1-x-y) Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 containing template seed crystals on a casting machine at the speed of 1.5 cm/s-2 cm/s, drying and cutting to obtain a (1-x-y) Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 membrane containing the template seed crystals; Or under the condition of the speed of 1.5 cm/s-2 cm/s, respectively casting the reaction casting slurry of (1-x-y) Pb (A, nb) O 3 -0.35PbZrO 3 -yPbTiO 3 containing the template seed crystal and the PbZrO 3 reaction casting slurry without the template seed crystal on a casting machine, and then drying and cutting to obtain a (1-x-y) Pb (A, nb) O 3 -0.35PbZrO 3 -yPbTiO 3 reaction membrane containing the template seed crystal and a PbZrO 3 reaction membrane without the template seed crystal; ③ Different stacks according to the value of x: When x is more than or equal to 0.15 and less than or equal to 0.35, laminating (1-x-y) Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 films containing template seed crystals to obtain a laminated sample; When x is less than or equal to 0.35 and less than or equal to 0.55, according to the stoichiometric ratio of Pb (A, nb) O 3 -xPbZrO 3 -yPbTiO 3 in the chemical general formula (1-x-y), the (1-x-y) Pb (A, nb) O 3 -0.35PbZrO 3 -yPbTiO 3 reaction membrane containing the template seed crystal and the PbZrO 3 reaction membrane without the template seed crystal are staggered and laminated to obtain a laminated sample; ④ Pressurizing: Carrying out hot pressing on the stacked samples for 10 min and hot water uniform pressing for 30min to obtain a ceramic green body; 3. preparation of textured ceramics: ① Discharging glue and cold isostatic pressing: Discharging the ceramic green body for 1-6 h at the temperature of 500-700 ℃, and then performing cold isostatic pressing for 1-10 min at the pressure of 150-250 MPa to obtain a ceramic biscuit; ② Sintering: Sintering the ceramic biscuit for 5-600 min at the low sintering temperature of 850-1095 ℃ to obtain textured ceramic; ③ Polarization: Polishing, cleaning and drying two surfaces of the textured ceramic perpendicular to the texture direction, and then carrying out electric polarization and polarization to obtain a relaxation lead-based textured ceramic material with low texture temperature and high electrical property; The electric polarization is specifically carried out by coating silver paste on a polished surface, burning and infiltrating the electrode for 30-90 min under the condition that the temperature is 450-650 ℃, and the polarization is specifically carried out under a direct current field of 30 kV/cm.
  2. 2. The relaxed lead-based textured ceramic material with low texture temperature and high electrical properties of claim 1, wherein in step one ②, ball milling is performed for 24-96 hours with absolute ethyl alcohol as a medium.
  3. 3. The relaxed lead-based textured ceramic material with low texture temperature and high electrical properties of claim 1, wherein the secondary ball milling time of step one ② is 12-72 hours.
  4. 4. The relaxed lead-based textured ceramic material with low texture temperature and high electrical properties of claim 1, wherein the solvent in step two ① is a mixed solution of xylene and ethanol, the dispersant in step two ① is menhaden oil, the binder in step two ① is polyvinyl butyral, and the plasticizer in step two ① is a mixture of polyalkylene glycol and butyl benzyl phthalate.
  5. 5. The relaxed lead-based textured ceramic material with low texture temperature and high electrical properties according to claim 1, wherein the hot pressing in step two ④ is specifically hot pressing 10min under the conditions of 10 MPa-50 MPa and 60-95 ℃, and the hot water homogenizing in step two ④ is specifically hot water homogenizing 30min under the conditions of 20 MPa-50 MPa and 70-95 ℃.
  6. 6. Use of a relaxed lead-based textured ceramic material with low texture temperature and high electrical properties according to claim 1, in a multi-layer piezoelectric device with high performance, wide temperature range, high power, high electric field drive comprising a high-side ultrasonic transducer, a high-side piezoelectric driver, a high-side piezoelectric sensor and a high-side energy collector.

Description

Relaxation lead-based textured ceramic material with low texture temperature and high electrical property, and preparation method and application thereof Technical Field The invention relates to a relaxation lead-based textured ceramic material, a preparation method and application thereof. Background The relaxation lead-based ferroelectric material containing zirconium has wide demands in important fields such as medical ultrasonic diagnosis, industrial nondestructive inspection, deep sea communication, precise driving control, energy collection and the like due to the outstanding electromechanical conversion performance. The relaxation lead-based ceramic is a core material of a plurality of piezoelectric devices, and the enhancement of the electrical property of the relaxation lead-based ceramic is of great significance for promoting the upgrading and updating of related devices and systems. The improvement of the piezoelectric performance of the ceramic can be realized by introducing solid solution components, ion substitution, doping modification, liquid phase preparation and the like, but the improvement of the piezoelectric performance is often obtained at the cost of reducing the Curie temperature due to the mutual restriction relation between the piezoelectric performance and the Curie temperature, so that the temperature stability of the material performance is further deteriorated and the actual use temperature area of the material is shortened. The crystal orientation texture can exert the anisotropic characteristic of the crystal grain performance, and is expected to greatly improve the piezoelectric performance of the ceramic material on the premise of keeping the Curie temperature of the ceramic material. For relaxation lead-based ceramics (1-x-y) Pb (A, B) O 3-xPbZrO3-yPbTiO3 (x is less than or equal to 0.35, and the coefficient of ternary composition is not zero) with low zirconium content, related texture research is reported. However, the sintering temperature of the high texture quality ceramics reported so far is high, usually up to 1200 ℃, which means that high temperature resistant Pd or Pt expensive electrodes are required to be used in the preparation of the multilayer structure, thus increasing the production cost and limiting the expansion of the production and application range of the ceramics. In addition, the template of the relaxed lead-based textured ceramic with low zirconium content is usually stably stored in textured grains, in other words, the textured grains of the ceramic are usually provided with a core-shell structure, and the residual stress exists near a core-shell interface of the structure, so that the ceramic has a clamping effect on polarization turnover, and the effective improvement range of piezoelectric performance is reduced. For a relaxation lead-based ceramic (1-x-y) Pb (A, B) O 3-xPbZrO3-yPbTiO3 (x is more than 0.35) system with high zirconium content, the coefficient of ternary composition is not zero, and the ceramic with high texture quality is difficult to prepare by the conventional texture technology, so that the improvement range of the electrical performance of the system is limited. Specifically, before ceramic texture, the powder can react with a microcrystalline template in a serious solid phase, so that the template cannot complete the task of guiding grain oriented growth. Therefore, the high-quality texturing and low-temperature sintering of the relaxation lead-based ferroelectric ceramic containing Zr are explored, and the core-shell structure of textured grains is eliminated, so that the electric performance is greatly improved on the premise of keeping high Curie temperature, the application range of devices of the material is remarkably widened, the promotion of upgrading and updating of piezoelectric devices and related instrument systems is assisted, and the relaxation lead-based ferroelectric ceramic containing Zr has important scientific significance and engineering application value. Disclosure of Invention The invention aims to solve the problems that the existing low-Zr-content ceramic has high texture temperature, the template is not dissolved in the texture process to cause oriented grains to take a core-shell structure, the electrical property of the high-Zr-content ceramic is difficult to texture and cannot be greatly improved, and the high-voltage electrical property and the low texture temperature cannot be obtained simultaneously, and further provides a relaxation lead-based textured ceramic material with low texture temperature and high electrical property, and a preparation method and application thereof. A relaxation lead-based textured ceramic material with low texture temperature and high electrical property has a chemical general formula of (1-x-y) Pb (A, nb) O 3-xPbZrO3-yPbTiO3, wherein A is one or a combination of more than one of Mg, zn, sc and In, x is more than or equal to 0.15 and less than or equal to 0.55,0.1