阅读说明：本技术 一种锑酸铋-镱酸铋-钛酸铅系压电陶瓷材料及制备方法 (Bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material and preparation method thereof ) 是由 余洋 丁忆 姜旭宇 王海圣 柯银鸿 翁新全 刘瑞林 许静玲 于 2021-11-08 设计创作，主要内容包括：本发明公开了一种锑酸铋-镱酸铋-钛酸铅系压电陶瓷材料及制备方法,它涉及压电陶瓷技术领域,其配方分子式为：xBiSbO-(3)-(1-x-y)BiYbO-(3)-yPbTiO-(3)-z wt％In-(2)O-(3),其中0≤x≤0.1,0.4≤y≤0.8,0≤z≤0.5。采用上述技术方案后,本发明兼具高居里点和高压电性,能够节约成本。(The invention discloses a bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material and a preparation method thereof, relating to the technical field of piezoelectric ceramic, wherein the formula molecular formula is as follows: xBiSbO 3 ‑(1‑x‑y)BiYbO 3 ‑yPbTiO 3 ‑z wt％In 2 O 3 Wherein x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0.4 and less than or equal to 0.8, and z is more than or equal to 0 and less than or equal to 0.5. By adopting the technical scheme, the high-voltage cable has high Curie point and high piezoelectricity, and the cost can be saved.)

1. A bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material is characterized in that: the formula molecular formula is as follows:

xBiSbO₃-(1-x-y)BiYbO₃-yPbTiO₃-z wt％In₂O₃。

2. the bismuth antimonate-bismuth ytterbium titanate lead-based piezoelectric ceramic material of claim 1, which is characterized in that: x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0.4 and less than or equal to 0.8, and z is more than or equal to 0 and less than or equal to 0.5.

3. A preparation method of a bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material is characterized by comprising the following steps: which comprises the following steps:

the method comprises the following steps: with Sb₂O₃、Bi₂O₃、Yb₂O₃、PbO、TiO₂、In₂O₃The raw materials are mixed according to the stoichiometric ratio of Sb, Bi, Yb, Pb, Ti and In the formula;

step two: adding a NaCl/KCl salt mixture into the ingredients in the step one, and then putting the mixture into a ball milling tank of a ball mill for mixing and ball milling to obtain powder after ball milling;

step three: presintering the ball-milled powder to obtain presintered powder;

step four: repeatedly cleaning the pre-sintered powder by using deionized water until no Cl ions are detected in the filtrate;

step five: performing secondary ball milling on the powder cleaned by the deionized water, taking the material and drying to obtain dried powder;

step six: adding a PVA solution into the dried powder, grinding and pressing the powder into a thin round blank, and performing plastic removal treatment on the thin round blank to obtain a thin round blank subjected to plastic removal treatment;

step seven: sintering the thin round blank subjected to plastic removal to obtain a sintered ceramic round piece;

step eight: polishing two surfaces of the sintered ceramic wafer, coating Ag electrodes on the two surfaces of the ceramic wafer, carrying out silver firing, and carrying out polarization treatment on the ceramic wafer after silver firing to obtain the piezoelectric ceramic.

4. The method for preparing a bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material according to claim 3, wherein the method comprises the following steps: in the third step, the presintering temperature is 600 ℃, and the presintering time is 3 hours.

5. The method for preparing a bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material according to claim 3, wherein the method comprises the following steps: in the fourth step, the temperature of the deionized water is 90 ℃.

6. The method for preparing a bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material according to claim 3, wherein the method comprises the following steps: in the fifth step, the time of the secondary ball milling is 24 hours, and the rotating speed of the ball mill is 250 r/min.

7. The method for preparing a bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material according to claim 3, wherein the method comprises the following steps: in the sixth step, the diameter of the thin round billet is 14mm, and the plastic discharge temperature is 600 ℃.

8. The method for preparing a bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material according to claim 3, wherein the method comprises the following steps: in the seventh step, the sintering temperature is 1020 ℃ and the sintering time is 2 h.

9. The method for preparing a bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material according to claim 3, wherein the method comprises the following steps: and step eight, applying a direct current electric field of 4kV/mm in 160 ℃ silicone oil, keeping for 20min, and carrying out polarization treatment.

Technical Field

The invention relates to the technical field, in particular to a bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material and a preparation method thereof.

Background

Piezoelectric ceramics are a class of functional materials that achieve the mutual coupling and conversion (transduction) of mechanical energy and electrical energy. The piezoelectric ceramic material has very wide application in the fields of advanced manufacturing, electronic information, energy detection, national defense and the like, such as a piezoelectric driver, an ultrasonic motor, sound wave detection in a deep well, a transducer, a vibration sensor and the like, and the piezoelectric ceramic material is a sensitive element and a core component of the whole system. Therefore, the performance parameters of the piezoceramic material, particularly the piezoelectric performance and the Curie temperature of the material, directly determine the quality of the system performance. A higher piezoelectric constant generally means that the primary function of the system or device is more excellent. The high Curie temperature can ensure the stable work at high temperature.

Lead-based system ceramics, such as lead zirconate titanate (PZT), are most commonly used with low curie temperatures and high lead contents. Lead-free systems such as bismuth layered ceramics have a high curie point but not a high piezoelectric constant. The bismuth scandate lead titanate system has high Curie point and high piezoelectric constant, but the rare earth element scandium is expensive. The bismuth ferrite lead titanate system has high Curie point, but large leakage current during polarization and low piezoelectric constant.

In view of the above, the present invention is designed based on the various defects and inconveniences caused by the perfection of the above piezoelectric ceramic material, and the present invention is further conceived and developed through active research and improvement.

Disclosure of Invention

The invention aims to provide a bismuth antimonate-bismuth ytterbium titanate lead system piezoelectric ceramic material which has high Curie point and high piezoelectricity and can save cost and a preparation method thereof aiming at the defects and the defects of the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

the formula of the bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material is as follows:

xBiSbO₃-(1-x-y)BiYbO₃-yPbTiO₃-z wt％In₂O₃

wherein x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0.4 and less than or equal to 0.8, and z is more than or equal to 0 and less than or equal to 0.5.

Another object of the present invention is to provide a bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material and a method for preparing the same, which comprises the following steps:

the method comprises the following steps: with Sb₂O₃、Bi₂O₃、Yb₂O₃、PbO、TiO₂、In₂O₃The raw materials are mixed according to the stoichiometric ratio of Sb, Bi, Yb, Pb, Ti and In the formula;

step two: adding a NaCl/KCl mixture with the same mass ratio into the ingredients in the step one, and then putting the mixture into a ball milling tank of a ball mill for mixing and ball milling to obtain powder after ball milling;

step three: presintering the ball-milled powder to obtain presintered powder;

step four: repeatedly cleaning the pre-sintered powder by using deionized water until no Cl ions are detected in the filtrate;

step five: performing secondary ball milling on the powder cleaned by the deionized water, taking the material and drying to obtain dried powder;

step six: adding a PVA solution into the dried powder, grinding and pressing the powder into a thin round blank, and performing plastic removal treatment on the thin round blank to obtain a thin round blank subjected to plastic removal treatment;

step seven: sintering the thin round blank subjected to plastic removal to obtain a sintered ceramic round piece;

step eight: polishing two surfaces of the sintered ceramic wafer, coating Ag electrodes on the two surfaces of the ceramic wafer, carrying out silver firing, and carrying out polarization treatment on the ceramic wafer after silver firing to obtain the piezoelectric ceramic.

Further, in the second step, the mass ratio of NaCl to KCl is 1, the ball milling time is 12h, and the rotating speed of the ball mill is 150 r/min.

Further, in the third step, the presintering temperature is 600 ℃, and the presintering time is 3 hours.

Further, in the fourth step, the temperature of the deionized water is 90 ℃.

Further, in the fifth step, the time of the secondary ball milling is 24 hours, and the rotating speed of the ball mill is 250 r/min.

Further, in the sixth step, the diameter of the thin round billet is 14mm, and the plastic discharge temperature is 600 ℃.

Further, in the seventh step, the sintering temperature is 1020 ℃ and the sintering time is 2 h.

Further, in the eighth step, a direct current electric field of 4kV/mm is applied to the silicone oil at 160 ℃ for 20min to carry out polarization treatment.

By adopting the technical scheme, the bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material has the advantages of high Curie point and high piezoelectricity, the performance can be guaranteed while the cost is saved by replacing noble metal scandium with metal antimony and metal ytterbium, the lead content is low, the material is environment-friendly, the preparation is simple, the pre-sintering and sintering temperatures are low, and the process is stable.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a dielectric thermogram of a piezoelectric ceramic of bismuth antimonate-bismuth ytterbium acid-lead titanate system according to the present invention.

FIG. 2 is an XRD pattern of the bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic of the present invention.

FIG. 3 is an SEM image of the bismuth antimonate-bismuth ytterbium-lead titanate piezoelectric ceramic of the present invention.

Detailed Description

In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.

In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are used merely for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, are not to be construed as limiting the present invention. In the description of the present invention, "a plurality" means two or more unless otherwise specified.

The formula of the bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material is as follows:

xBiSbO₃-(1-x-y)BiYbO₃-yPbTiO₃-z wt％In₂O₃

wherein x is more than or equal to 0 and less than or equal to 0.1, y is more than or equal to 0.4 and less than or equal to 0.8, and z is more than or equal to 0 and less than or equal to 0.5.

The following are some specific examples of the components of the bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material of the present invention:

example 1

The molecular formula of the preparation formula is as follows:

xBiSbO₃-(1-x-y)BiYbO₃-yPbTiO₃-z wt％In₂O₃x is 0.02, y is 0.63, and z is 0.2.

Namely: 0.02BiSbO₃-0.35BiYbO₃-0.63PbTiO₃-0.2wt％In₂O₃

The preparation method comprises the following steps:

the method comprises the following steps: with Sb₂O₃、Bi₂O₃、Yb₂O₃、PbO、TiO₂、In₂O₃The raw materials are mixed according to the stoichiometric ratio of Sb, Bi, Yb, Pb, Ti and In the formula;

step two: adding a NaCl/KCl salt mixture with the same mass ratio to the ingredients in the step one, wherein the mass ratio of NaCl to KCl is 1, then putting the mixture into a ball milling tank of a ball mill for mixing and ball milling for 12 hours, and the rotating speed of the ball mill is 150r/min to obtain powder after ball milling;

step three: presintering the ball-milled powder for 3 hours at 600 ℃ to obtain presintered powder;

step four: repeatedly washing the pre-sintered powder with deionized water at 90 ℃ until no Cl ions are detected in the filtrate in order to remove NaCl/KCl;

step five: performing secondary ball milling on the powder cleaned by the deionized water for 24 hours at the rotating speed of 250r/min, and then taking the material and drying to obtain dried powder;

step six: adding PVA solution into the dried powder, grinding and pressing the powder into a thin round blank with the diameter of 14mm, and performing plastic removal treatment on the thin round blank at the temperature of 600 ℃ to obtain a thin round blank after the plastic removal treatment;

step seven: sintering the thin round blank subjected to plastic removal at 1020 ℃ for 2h to obtain a sintered ceramic round piece;

step eight: polishing two surfaces of the sintered ceramic wafer, coating Ag electrodes on the two surfaces of the ceramic wafer, burning silver, applying a direct current electric field of 4kV/mm in 160 ℃ silicon oil, keeping for 20min, and carrying out polarization treatment to obtain the formula:

0.02BiSbO₃-0.35BiYbO₃-0.63PbTiO₃-0.2wt％In₂O₃the piezoelectric ceramic of (1).

The performance parameters are as follows: d33 ═ 420pC/N, k_p＝0.52，εr＝1848，tanδ＝1.4％，T_C＝395℃。

Example 2

The molecular formula of the preparation formula is as follows:

xBiSbO₃-(1-x-y)BiYbO₃-yPbTiO₃-z wt％In₂O₃x is 0.02, y is 0.64, and z is 0.2.

The preparation method comprises the following steps:

the method comprises the following steps: with Sb₂O₃、Bi₂O₃、Yb₂O₃、PbO、TiO₂、In₂O₃The raw materials are mixed according to the stoichiometric ratio of Sb, Bi, Yb, Pb, Ti and In the formula;

step two: adding a NaCl/KCl salt mixture with the same mass ratio to the ingredients in the step one, wherein the mass ratio of NaCl to KCl is 1, then putting the mixture into a ball milling tank of a ball mill for mixing and ball milling for 12 hours, and the rotating speed of the ball mill is 150r/min to obtain powder after ball milling;

step three: presintering the ball-milled powder for 3 hours at 600 ℃ to obtain presintered powder;

step four: repeatedly washing the pre-sintered powder with deionized water at 90 ℃ until no Cl ions are detected in the filtrate in order to remove NaCl/KCl;

step five: performing secondary ball milling on the powder cleaned by the deionized water for 24 hours at the rotating speed of 250r/min, and then taking the material and drying to obtain dried powder;

step six: adding PVA solution into the dried powder, grinding and pressing the powder into a thin round blank with the diameter of 14mm, and performing plastic removal treatment on the thin round blank at the temperature of 600 ℃ to obtain a thin round blank after the plastic removal treatment;

step seven: sintering the thin round blank subjected to plastic removal at 1020 ℃ for 2h to obtain a sintered ceramic round piece;

step eight: polishing two surfaces of the sintered ceramic wafer, coating Ag electrodes on the two surfaces of the ceramic wafer, burning silver, applying a direct current electric field of 4kV/mm in 160 ℃ silicon oil, keeping for 20min, and carrying out polarization treatment to obtain the formula:

0.02BiSbO₃-0.34BiYbO₃-0.64PbTiO₃-0.2wt％In₂O₃the piezoelectric ceramic of (1).

The performance parameters are as follows: d 33-450 pC/N, k_p＝0.52，εr＝1966，tanδ＝1.8％，T_C＝401℃。

Example 3

The molecular formula of the preparation formula is as follows:

xBiSbO₃-(1-x-y)BiYbO₃-yPbTiO₃-z wt％In₂O₃x is 0.02, y is 0.65, and z is 0.2.

The preparation method comprises the following steps:

the method comprises the following steps: with Sb₂O₃、Bi₂O₃、Yb₂O₃、PbO、TiO₂、In₂O₃The raw materials are mixed according to the stoichiometric ratio of Sb, Bi, Yb, Pb, Ti and In the formula;

step two: adding a NaCl/KCl salt mixture with the same mass ratio to the ingredients in the step one, wherein the mass ratio of NaCl to KCl is 1, then putting the mixture into a ball milling tank of a ball mill for mixing and ball milling for 12 hours, and the rotating speed of the ball mill is 150r/min to obtain powder after ball milling;

step three: presintering the ball-milled powder for 3 hours at 600 ℃ to obtain presintered powder;

step four: repeatedly washing the pre-sintered powder with deionized water at 90 ℃ until no Cl ions are detected in the filtrate in order to remove NaCl/KCl;

step five: performing secondary ball milling on the powder cleaned by the deionized water for 24 hours at the rotating speed of 250r/min, and then taking the material and drying to obtain dried powder;

step six: adding PVA solution into the dried powder, grinding and pressing the powder into a thin round blank with the diameter of 14mm, and performing plastic removal treatment on the thin round blank at the temperature of 600 ℃ to obtain a thin round blank after the plastic removal treatment;

step seven: sintering the thin round blank subjected to plastic removal at 1020 ℃ for 2h to obtain a sintered ceramic round piece;

step eight: polishing two surfaces of the sintered ceramic wafer, coating Ag electrodes on the two surfaces of the ceramic wafer, burning silver, applying a direct current electric field of 4kV/mm in 160 ℃ silicon oil, keeping for 20min, and carrying out polarization treatment to obtain the formula:

0.02BiSbO₃-0.33BiYbO₃-0.65PbTiO₃-0.2wt％In₂O₃the piezoelectric ceramic of (1).

The performance parameters are as follows: d33 ═ 400pC/N, k_p＝0.52，εr＝1672，tanδ＝1.5％，T_C＝408℃。

The bismuth antimonate-bismuth ytterbium acid-lead titanate piezoelectric ceramic material has the advantages of high Curie point and high piezoelectricity, can save cost and ensure performance by replacing noble metal scandium with metal antimony and metal ytterbium, and is low in lead content, friendly to environment, simple to prepare, low in pre-sintering and sintering temperatures and stable in process.

The above description is only for the purpose of illustrating the technical solutions of the present invention and not for the purpose of limiting the same, and other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.