CN114075073A

CN114075073A - PZT-Pb (Sb)1/2Nb1/2) Ternary system piezoelectric ceramic material and preparation method and application thereof

Info

Publication number: CN114075073A
Application number: CN202010825952.2A
Authority: CN
Inventors: 李玉臣; 周志勇; 梁瑞虹; 董显林
Original assignee: Shanghai Institute of Ceramics of CAS
Current assignee: Shanghai Institute of Ceramics of CAS
Priority date: 2020-08-17
Filing date: 2020-08-17
Publication date: 2022-02-22
Anticipated expiration: 2040-08-17
Also published as: CN114075073B

Abstract

The invention relates to PZT-Pb (Sb)_1/2Nb_1/2) Ternary system piezoelectric ceramic material, preparation method and application thereof, and PZT-Pb (Sb)_1/2Nb_1/2) The ternary system piezoelectric ceramic material comprises: lead zirconate titanate and lead antimonite solid solution are taken as main components, and SiO is taken as₂、Sm₂O₃、MnO₂、Cr₂O₃And CeO₂At least 3 of which act as dopants.

Description

PZT-Pb (Sb)1/2Nb1/2) Ternary system piezoelectric ceramic material and preparation method and application thereof

Technical Field

The invention relates to PZT-Pb (Sb)_1/2Nb_1/2) A ternary system piezoceramic material, a preparation method and application thereof, in particular to PZT-Pb (Sb) which can be stably used at 260 DEG C_1/2Nb_1/2) IIIA component system piezoelectric ceramic material, a preparation method and an application thereof belong to the field of piezoelectric ceramics.

Background

The vibration quantity reflects the operation conditions of objects and equipment, and the detection of the vibration quantity almost relates to each engineering field. A vibration measuring instrument is required to detect the vibration, and a vibration sensor is not needed. Piezoelectric acceleration sensors capable of working normally at a certain temperature have been widely applied to a plurality of important scientific research and industrial departments such as aerospace, nuclear energy, power generation, automobiles, ships, submarines and the like to realize system monitoring. Particularly in the field of aviation, accidents of machine damage and people death caused by faults of aircraft engines often occur, particularly military machines.

Rocket, satellite and airship in China are continuously subjected to simulation tests, and piezoelectric acceleration sensors are needed on oxyhydrogen engines (such as bases and thrust chambers of the engines) to monitor and control the vibration of the engines in the ground test bed and the launching process. At present, many piezoelectric acceleration sensors used in Shanghai and Beijing aerospace systems are imported from foreign countries. Vibration detection of a rolling mill and a steel plate rolling mill in a metallurgical system, vibration detection of a thermal power generating set, vibration monitoring of high-speed diesel engines on various ships and warships, and monitoring of the operation condition of large-scale operation equipment in large and medium-scale enterprises all need piezoelectric acceleration sensors.

The helicopter has incomparable functions in the ground attack of modern war and the prevention of various natural disasters such as forest fire, flood and the like. Because the lift force, the pulling force and the control force for changing the flight state required by the helicopter are all provided by the propeller, and the high-speed rotation of the propeller can cause the vibration of a rotor wing, a fuselage and the like, acceleration sensors with different specifications are monitored in the processes of strength test on the ground, test run on the ground or test flight, vibration measurement and analysis are carried out, and data are provided for implementing vibration reduction, vibration isolation or active vibration suppression. Vibration is reported in the literature to be one of the main failures common to turbine engines. The faults of leaf damage, rotor imbalance, transmission gear accessory failure and the like can be detected by selecting a proper acceleration sensor and an intervention signal analysis device, an early warning is sent, secondary damage can be avoided, and accidents are prevented.

In the detection of object vibration, the piezoelectric acceleration sensor is often carried out in a high-temperature environment (more than 260 ℃), so that the use temperature and the high-temperature stability of the piezoelectric ceramic are key factors. The piezoelectric ceramic element is a core component of the piezoelectric acceleration sensor, and the performance of the piezoelectric ceramic material directly influences the detection effect of the piezoelectric acceleration sensor. At present, a large number of low-end piezoelectric acceleration sensors are abundant in China, and the high-temperature stability is poor. Most of high-temperature piezoelectric acceleration sensors are imported, and one main reason is lack of piezoelectric ceramic materials with high use temperature and good stability. Therefore, the development of the piezoelectric ceramic material with good comprehensive performance has fundamental significance.

In the field of petroleum logging, a new generation of multipolar array acoustic logging instrument is the latest technology of acoustic logging, and can measure the wave velocity and the attenuation of various fluctuation modes of longitudinal waves, transverse waves and Stoneley waves in liquid-filled well bores in soft and hard formations. In order to meet the requirements of complex oil and gas exploration and development in China, China repulses huge capital and directly requests the China's services of the Spirobeck well logging company in recent years, more than 30 sets of imaging well logging systems including multipole array acoustic wave imaging instruments (MAC, XMAC) and low-frequency dipole transverse wave well logging instruments (LFD) are introduced, but strict security measures are taken for China abroad for high-end and advanced well logging technologies. Therefore, the development of a new generation of multipole array acoustic logging instrument with the independent intellectual property rights in China is of great significance to breaking monopoly of western developed countries on the logging technology, greatly reducing the exploration cost and keeping up with the advanced level of the world logging technology.

At present, medium and medium sea oil is dedicated to the development of a new generation of multi-pole array acoustic logging instruments. Monopole receiving transducer, digital sound wave transmitting transducer, receiving transducer and the like are core components of a new generation of multi-pole array sound wave logging instrument. Due to the special environment of logging operation, the transducer not only needs to meet the requirements of acoustic logging on acoustic characteristics, but also needs to stably work under high temperature and high pressure. In recent years, although a few domestic units also actively explore the piezoelectric transducers, the piezoelectric transducers developed so far have the outstanding problems of low sensitivity, low resolution, unstable performance at high temperature and the like, cannot really meet the use requirements of underground exploration, and the key point is the lack of piezoelectric ceramic materials capable of stably working for a long time at high temperature and high pressure, so that the development of the high-temperature piezoelectric ceramic materials becomes an important technical bottleneck in the development process of a new generation of multi-pole array acoustic logging instruments.

Lead zirconate titanate (PZT) piezoelectric ceramic is an important piezoelectric ceramic material with the most extensive application, and belongs to ABO₃The perovskite structure is a structure, and the substitution modification and additive modification of A site or B site are commonly carried out to change different properties of the material. When the A, B site is doped with potassium, iron, manganese, magnesium or other "hard" dopant, the performance is characterized by a "hard" side, commonly referred to as a "hard" type piezoelectric ceramic, with improved mechanical quality factor (Qm), dielectric loss (tg δ), electromechanical coupling coefficient (kp), and dielectric constant (ε₃₃ ^T/ε₀) And decreases. When doped with lanthanum, bismuth, niobium and antimony donors at A, B, the performance of the piezoelectric ceramic is converted to soft, and the piezoelectric ceramic is called soft type, and the performance characteristic of the piezoelectric ceramic is dielectric constant (epsilon)₃₃ ^T/ε₀) Dielectric loss (tg δ), and electromechanical coupling coefficient (kp) increase. The use temperature of either hard or soft materials is generally below about 175 c, with some higher temperatures being used at 200 c.

As described above, PZT-Pb (Sb)_1/2Nb_1/2) As an important material related to the national civilization, the ternary system piezoelectric ceramic material is urgently required by a plurality of scientific research and industrial departments.

Disclosure of Invention

Accordingly, it is an object of the present invention to provide a novel PZT-Pb (Sb)_1/2Nb_1/2) The ternary system piezoelectric ceramic material, the preparation method and the application thereof meet the requirement of stable use at 260 ℃.

In one aspect, the present invention provides PZT-Pb (Sb)_1/2Nb_1/2) A ternary system piezoceramic material, said PZT-Pb (Sb)_1/2Nb_1/2) The ternary system piezoelectric ceramic material comprises: lead zirconate titanate and lead antimonite solid solution are taken as main components, and Si O is taken as a main component₂、MnO₂、Sm₂O₃、Cr₂O₃And CeO₂At least 3 of which act as dopants.

In the method, lead zirconate titanate (PZT) piezoelectric ceramics are selected, wherein the ratio of Zr to Ti is on one side of a tetragonal phase rich in Ti but does not deviate from a phase boundary too much (the piezoelectric activity is low due to the fact that the Zr deviates from the phase boundary too much); lead niobium antimonate (Pb (Sb)_1/2Nb_1/2)) Lead zirconate titanate which deviates from the phase boundary is dissolved in solid to form PZT-Pb (Sb)_1/2Nb_1/2) Ternary system piezoelectric ceramics; doped SiO₂、MnO₂、Sm₂O₃、Cr₂O₃And CeO₂At least 3 of the additives modify the material. The invention is aligned with the A-position Pb²⁺Using a trace amount of Sr²⁺And Ba²⁺The composite substitution is beneficial to sintering on one hand and can improve the piezoelectric activity of the material on the other hand; doped with soft additive Sm₂O₃And neutral additive CeO₂And adding SiO₂Adding glassy phase to improve grain boundary structure, MnO₂The doping can strengthen the combination between crystal grains, improve the density and form a pinning effect on an electric domain; the content of various additives is accurately controlled during design, so that a new material with high stability and excellent comprehensive performance is obtained. The composite doping has a unique mechanism, lead vacancy is caused to make the motion of a domain wall easy to carry out, simultaneously, a small amount of oxygen vacancy restricts the motion of an electric domain wall, and the balance is achieved on the basis of a certain amount, namely SiO₂The crystal grains are introduced and arranged outside the crystal lattices and concentrated near the grain boundaries, so that the density of the material crystal grains is improved. Cr (chromium) component₂O₃The addition of (2) is special, and valence change Cr of chromium can occur³⁺And Cr⁶⁺The materials coexist, so that the materials are soft and hard, the domain wall motion is mutually constrained, a balance is achieved, and the temperature stability of the materials is greatly improved; CeO (CeO)₂The addition of (2) increases the bulk resistivity of the material, thereby increasing the polarization voltageThe potential piezoelectric performance is fully exerted, and the temperature stability is greatly improved.

Preferably, the PZT-Pb (Sb)_1/2Nb_1/2) The ternary system piezoelectric ceramic material comprises the following chemical components: pb_1-xM_x(Zr_1- _yTi_y)_1-z(Sb_1/2Nb_1/2)_zO₃+awt.％SiO₂+bwt.％Sm₂O₃+cwt.％Cr₂O₃+dwt.％CeO₂+ewt.％MnO₂(ii) a Wherein M is Sr²⁺And Ba²⁺Wherein x is 0.01 to 0.1, y is 0.4 to 0.6, z is 0.01 to 0.10, a is 0 to 0.2, b is 0.02 to 0.5, c is 0.02 to 0.5, d is 0.01 to 0.6, and e is 0 to 0.8.

Preferably, M is Sr²⁺And Ba²⁺Then, Sr²⁺And Ba²⁺In a molar ratio of 1: 3.

preferably, x is 0.01 to 0.1, y is 0.4 to 0.6, z is 0.01 to 0.10, a is 0.02 to 0.2, b is 0.02 to 0.5, c is 0.02 to 0.5, d is 0.02 to 0.6, and e is 0.02 to 0.8.

In another aspect, the present invention provides a PZT-Pb (Sb) as described above_1/2Nb_1/2) The preparation method of ternary system piezoelectric ceramic material selects Pb₃O₄、ZrO₂、TiO₂、SrCO₃、BaCO₃、Cr₂O₃、Sm₂O₃、Sb₂O₃、Nb₂O₅、CeO₂、MnCO₃And SiO₂The PZT-Pb (Sb) is obtained by mixing, synthesizing, crushing, fine grinding, compression molding, plastic removal, sintering and polarization as raw materials_1/2Nb_1/2) A ternary system piezoelectric ceramic material.

Preferably, the sintering temperature is 1260-1320 ℃, and the time is 1-3 hours.

Preferably, the temperature of the polarization is 120-180 ℃, the voltage is 3-5 kV/mm, and the time is 10-20 minutes.

Preferably, the synthesis comprises: firstly, the synthesis is carried out for 1 to 4 hours at the temperature of 600 to 750 ℃, and then the synthesis is carried out for 1 to 4 hours at the temperature of 800 to 900 ℃.

Preferably, the temperature of the plastic discharge is 700-800 ℃, and the time is 0.5-1 hour.

Preferably, the obtained PZT-Pb (Sb)_1/2Nb_1/2) Carrying out high-low temperature cyclic aging on the ternary system piezoelectric ceramic material; the high-low temperature cyclic aging system comprises the following steps: starting from the normal temperature (20-30 ℃), firstly cooling to-40 ℃, then preserving heat for 0.5-2 hours, then heating to 260 ℃, preserving heat for 0.5-2 hours, and finally cooling to the normal temperature, wherein 1 cycle is counted; the number of the circulation is 5-10; preferably, the rate of temperature reduction is 2-10 ℃/min, and the rate of temperature rise is 2-10 ℃/min.

In still another aspect, the present invention also provides a PZT-Pb (Sb) as described above_1/2Nb_1/2) The ternary system piezoelectric ceramic material is applied to the preparation of high-temperature acceleration sensors and acoustic logging equipment.

Has the advantages that:

the invention prepares a piezoelectric ceramic material which can be stably used at a high temperature (260 ℃) or above. The standard piezoelectric ceramic material sheet obtained by the invention has the following main properties: d₃₃＝295pC/N，ε₃₃ ^T/ε₀＝1400，tgδ＝1.2％，Kp＝0.53，Qm＝60，Tc＝362℃，ρ_v(260℃)＝7.8×10⁹Ω·cm；

The piezoelectric acceleration sensor is assembled by using the ceramic elements made of the piezoelectric ceramic material, and can be used for vibration monitoring and monitoring in the aspects of aerospace, nuclear energy, power generation, automobiles, ships, submarines and the like; in the field of petroleum logging, the piezoelectric ceramic material can meet the application requirement under the extreme environment of more than 260 ℃;

compared with common PZT piezoelectric ceramics, the ceramic material of the invention has high service temperature (260 ℃) and higher piezoelectric constant d₃₃It is a piezoelectric ceramic material with excellent performance.

Detailed Description

The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.

In the method, the characteristics of the ternary system piezoelectric ceramic that the piezoelectric performance can be widely adjusted are utilized, the performance of the material is greatly changed by changing different proportions of three components, and meanwhile, some modification additives are added on the basis of the ternary system main components, so that the performance of the material is further improved. Specifically, the PZT-Pb (Sb)_1/2Nb_1/2) The ternary piezoelectric ceramic material is prepared with lead zirconate titanate and lead niobate antimonate solid solution as main components and through doping SiO₂、MnO₂、Sm₂O₃、Cr₂O₃And CeO₂At least 3 additives.

In an alternative embodiment, PZT-Pb (Sb)_1/2Nb_1/2) The ternary system piezoelectric ceramic material comprises the following components: pb_1-xM_x(Zr_1-yTi_y)_1-z(Sb_1/2Nb_1/2)_zO₃+awt.％SiO₂+bwt.％Sm₂O₃+cwt.％Cr₂O₃+dwt.％CeO₂+ewt.％MnO₂. Wherein M is selected from Sr²⁺And Ba²⁺One or a combination of both; and x is 0.01 to 0.1, y is 0.4 to 0.6, z is 0.01 to 0.10, a is 0 to 0.2, b is 0.02 to 0.5, c is 0.02 to 0.5, d is 0.01 to 0.6, and e is 0 to 0.8. Wherein x, y and z represent molar ratios; a. b, c, d and e represent mass ratios (see examples for specific effects).

Further preferably, PZT-Pb (Sb)_1/2Nb_1/2) In the ternary system piezoelectric ceramic material, when M is Sr²⁺And Ba²⁺In combination of two kinds of above, Sr²⁺And Ba²⁺In a molar ratio of Sr²⁺：Ba²⁺1: 3 (the piezoelectricity was improved, and the specific effect was shown in the comparative examples).

More preferably, the PZT-Pb (Sb)_1/2Nb_1/2) The ternary system piezoelectric ceramic material comprises the following materials: pb_1-xM_x(Zr_1-yTi_y)_1-z(Sb_1/2Nb_1/2)_zO₃+awt.％SiO₂+bwt.％Sm₂O₃+cwt.％Cr₂O₃+dwt.％CeO₂+ewt.％MnO₂. Wherein M is selected from Sr²⁺And Ba²⁺One or a combination of both; and x is 0.01 to 0.1, y is 0.4 to 0.6, z is 0.01 to 0.10, a is 0.02 to 0.2, b is 0.02 to 0.5, c is 0.02 to 0.5, d is 0.02 to 0.6, and e is 0.02 to 0.5 (specific effects are shown in the examples).

For example, PZT-Pb (Sb)_1/2Nb_1/2) The ternary system piezoelectric ceramic material comprises the following materials: pb_0.98Sr_0.02(Zr_0.50Ti_0.50)0_.98(Sb_1/2Nb_1/2)_0.02O₃+0.04wt.％SiO₂+0.1wt.％Sm₂O₃+0.1wt.％Cr₂O₃+0.05wt.％CeO₂，Pb_0.98Sr_0.005Ba_0.015(Zr_0.50Ti_0.50)_0.98(Sb_1/2Nb_1/2)_0.02O₃+0.04wt.％SiO₂+0.1wt.％Sm₂O₃+0.1wt.％Cr₂O₃+0.05wt.％CeO₂Etc. (formulations can be adjusted widely within the limits set, and are given here by way of example only and in particular in the examples below).

PZT-Pb (Sb) is exemplarily explained below_1/2Nb_1/2) A preparation method of ternary system piezoelectric ceramic material.

And (4) batching. According to said PZT-Pb (Sb)_1/2Nb_1/2) The composition of the ternary system piezoelectric ceramic material is calculated and weighed, various element raw materials are weighed and mixed, and the mixed raw material is obtained. The raw material is selected from Pb₃O₄、ZrO₂、TiO₂、SrCO₃、BaCO₃、Cr₂O₃、Sm₂O₃、Sb₂O₃、Nb₂O₅、CeO₂、MnCO₃And SiO₂. Preferably, said Pb is₃O₄、ZrO₂、TiO₂、SrCO₃、BaCO₃、MnCO₃And Sb₂O₃Are all industrial pure grade; the Cr is₂O₃、Sm₂O₃、CeO₂And SiO₂All are chemical pure grades.

And (3) mixing materials. Further ball milling and mixing the mixed raw materials to obtain mixed powder. Specifically, deionized water and agate balls are used as media, and the raw materials are mixed according to the following ratio: agate ball: deionized water 1: 1.2: mixing according to the proportion of 0.8, ball-milling and mixing for 6-10 hours by using a roller, pouring the mixed powder into a container, and drying in an oven.

And (4) pre-burning and synthesizing. And (3) dry-pressing the mixed powder into blocks at 80-100 MPa, and then presintering and synthesizing in a box type electric furnace. Wherein, the synthesis is divided into two sections: the parameters for the synthesis of the first stage are: synthesizing for 1-4 hours at 600-750 deg.C (preferably 650-700 deg.C) to produce PbTiO₃. The synthesis parameters for the second stage were: synthesizing at 800-900 deg.C (preferably 850-870 deg.C) for 1-4 hr to obtain Pb (ZrbTi) O₃And Pb (Sb)_1/2Nb_1/2) Fusion is performed. The pre-sintering temperature is too low, the synthesis is insufficient, and the performance is reduced; the lead oxide is easy to volatilize due to too high pre-sintering temperature, and the blocks are too hard and difficult to crush. The reasonable control of the presintering temperature and the heat preservation time has certain influence on the performance.

And (5) fine grinding. And (4) crushing and finely grinding the pre-sintered and synthesized material blocks. Specifically, the prepared synthesized material block is mechanically pulverized and then finely ground. Wherein, the fine grinding adopts deionized water and agate balls as media, and the mass ratio of the powder is as follows: agate ball: deionized water 1: 1.5: mixing the raw materials according to the proportion of 0.6, and ball-milling the mixture for 12 to 48 hours by using a roller.

And (6) granulating and forming. Discharging and drying the finely ground powder, adding a binder, granulating and molding to obtain a blank. The binder can be selected by those skilled in the art according to the prior art, and preferably is a PVA (polyvinyl alcohol) binder. The addition amount of the binder can be 3-6 wt% of the raw material powder. The molding pressure can be 150MPa to 200 MPa.

And (6) plastic removal. And performing plastic removal on the blank body at 700-800 ℃ for 0.5-1 hour to remove the glue in the blank body, wherein the blank body has certain hardness. The unclean glue discharge can affect the sintering quality in the subsequent sintering because of the reducing atmosphere. The plastic discharging is generally carried out in an open oven, and the oven door is kept at a certain clearance so as to fully discharge the glue in the blank.

And (5) firing. Sintering the green body after plastic removal to obtain PZT-Pb (Sb)_1/2Nb_1/2) A ternary system piezoelectric ceramic material. Wherein the sintering temperature can be 1260-1320 ℃ (preferably 1260-1300 ℃), and the time can be 1-3 hours.

And (5) cold working. And machining the sintered sample according to the specification requirement.

And carrying out ultrasonic cleaning, oxidation and electrode mounting on the cold-processed sample. Wherein, the oxidation procedure can be 800-900 ℃ (temperature)/1-3 hours (time), the introduction of soft additives can cause certain lead vacancy and cause insufficient oxygen in the sample in the sintering machine, in order to maintain electroneutrality, high-temperature oxidation treatment is usually adopted, and the electromechanical coupling coefficient of the material can be improved after the high-temperature treatment. For example, the oxidation procedure is 850 deg.C/2 h. And (4) after oxidation, applying a silver electrode, and putting into a box-type electric furnace for silver burning. The silver firing temperature can be 650-750 ℃, and the time can be 0.5-1 hour.

And (6) polarization. The sample with the electrode is placed in silicon oil, and a high-voltage electric field is added for polarization treatment, so that electric domains in the ceramic are oriented and arranged along the direction of the electric field, and the piezoelectric effect can be displayed. Whether the ceramic is perfectly polarized or not is related to the polarized electric field, the temperature and the heat preservation time. The conditions for polarization were: the temperature is 120-180 ℃, the voltage is 3-5 kV/mm, and the time is 10-20 min.

In an optional embodiment, after the polarized sample is placed for at least one day, high-low temperature cyclic aging is carried out, the temperature stability and the time stability of the material are improved, the electric engineering movement inside the ceramic is accelerated under the temperature cycle, the release of the internal stress is accelerated, and the stable effect is achieved in a short period. Setting the high-low temperature cyclic aging temperature range to be-40-260 ℃, the temperature rising and falling rate to be 2-10 ℃ per minute, and carrying out heat preservation for 30 minutes to 2 hours when the temperature reaches-40 ℃ and 260 ℃ for 5-10 temperature cycles. Wherein, the high-low temperature cyclic aging generally starts from normal temperature, and then is carried out by cooling and then heating.

The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. Unless otherwise specified in the following examples, the purity of the industrial grade is at least 95% and the purity of the chemical grade is at least 98%.

Example 1

The raw material is selected from Pb₃O₄、ZrO₂、TiO₂、SrCO₃、BaCO₃、MnCO₃And Sb₂O₃Are all industrial pure grade; the Cr is₂O₃、Sm₂O₃、CeO₂And SiO₂All are chemical pure grades. The raw materials are used as raw materials for blending;

according to Pb_0.98Sr_0.005Ba_0.015(Zr_0.50Ti_0.50)_0.98(Sb_1/2Nb_1/2)_0.02O₃+0.04wt.％SiO₂+0.1wt.％Sm₂O₃+0.15wt.％Cr₂O₃+0.05wt.％CeO₂+0.06wt.％MnO₂The method comprises the following steps of (1) weighing by using the stoichiometric proportion, taking deionized water and agate balls as media, and mixing the raw materials: agate ball: deionized water 1: 1.2: mixing according to the proportion of 0.8, and ball-milling and mixing for 8 hours by a roller; pouring the mixed raw materials into a container, putting the container into an oven for drying, and then briquetting, wherein the synthesis comprises two sections: the first stage synthesis: synthesizing for 1h at the temperature of 650 ℃, and synthesizing a second-stage briquette: synthesizing for 2 hours at the temperature of 850 ℃; the prepared synthesized powder is ground and then finely ground, deionized water and agate balls are used as media in the fine grinding, and the raw materials are as follows: agate ball: deionized water 1: 1.5: mixing at a ratio of 0.6, and making into roller ballGrinding for 24 hours; then discharging, drying, adding a binder, granulating and forming (the forming pressure is 200 MPa); placing the molded sample in a box-type electric furnace for plastic removal (800 ℃/1h), placing the sample in an alumina crucible for closed sintering, wherein the sintering system is sintering for 2h at the temperature of 1280 ℃; machining the sintered sample according to the specification requirement; carrying out ultrasonic cleaning and oxidation on the processed sample, wherein the oxidation procedure is 850 ℃/2 h; after oxidation, a silver electrode is coated, and the silver electrode is placed into a box type electric furnace for silver burning; then, a sample with electrodes is placed in silicon oil, and a high-voltage electric field is applied at a certain temperature, wherein the polarization condition is that the temperature is 180 ℃, the voltage is 5kv/mm, and the time is 20 min. And (3) placing the polarized sample for one day, then carrying out high-low temperature cyclic aging, wherein the normal temperature is 20-30 ℃, the high-low temperature aging temperature range is-40 ℃ -260 ℃, the temperature rising and falling rate is 5 ℃ per minute, and the temperature is respectively kept for 2 hours from-40 ℃ to 260 ℃ for 5 temperature cycles.

The main properties of the standard sheet of the material obtained in example 1 at room temperature (25 ℃) are: d₃₃＝295pC/N，ε₃₃ ^T/ε₀＝1400，tgδ＝1.2％，Kp＝0.53，Qm＝65，Tc＝362℃，ρ_v(260℃)＝7.8×10⁹Ω·cm。

Example 2

The raw material is selected from Pb₃O₄、ZrO₂、TiO₂、SrCO₃、BaCO₃And Sb₂O₃Are all industrial pure grade; the Cr is₂O₃、Sm₂O₃、CeO₂And SiO₂All are chemical pure grades. The raw materials are used as raw materials for blending;

according to Pb_0.98Sr_0.005Ba_0.015(Zr_0.50Ti_0.50)_0.98(Sb_1/2Nb_1/2)_0.02O₃+0.04wt.％SiO₂+0.1wt.％Sm₂O₃+0.15wt.％Cr₂O₃+0.05wt.％CeO₂The method comprises the following steps of (1) weighing by using the stoichiometric proportion, taking deionized water and agate balls as media, and mixing the raw materials: agate ball: deionized water 1: 1.2: mixing according to the proportion of 0.8, and ball-milling and mixing for 8 hours by a roller; will be mixed withPouring the good raw materials into a container, putting the container into an oven for drying, and then briquetting, wherein the synthesis comprises two sections: the first stage synthesis: synthesizing for 1h at the temperature of 650 ℃, and synthesizing a second-stage briquette: synthesizing for 2 hours at the temperature of 850 ℃; the prepared synthesized powder is ground and then finely ground, deionized water and agate balls are used as media in the fine grinding, and the raw materials are as follows: agate ball: deionized water 1: 1.5: mixing according to the proportion of 0.6, and ball-milling for 24 hours by a roller; then discharging, drying, adding a binder, granulating and forming (the forming pressure is 200 MPa); placing the molded sample in a box-type electric furnace for plastic removal (800 ℃/1h), placing the sample in an alumina crucible for closed sintering, wherein the sintering system is sintering for 2h at the temperature of 1300 ℃; machining the sintered sample according to the specification requirement; carrying out ultrasonic cleaning and oxidation on the processed sample, wherein the oxidation procedure is 850 ℃/2 h; after oxidation, a silver electrode is coated, and the silver electrode is placed into a box type electric furnace for silver burning; then, a sample with electrodes is placed in silicon oil, and a high-voltage electric field is applied at a certain temperature under the polarization condition that the temperature is 170 ℃, the voltage is 5kv/mm, and the time is 20 min. And (3) placing the polarized sample for one day, then carrying out high-low temperature cyclic aging, wherein the normal temperature is 20-30 ℃, the high-low temperature aging temperature range is-40 ℃ -260 ℃, the temperature rising and falling rate is 5 ℃ per minute, and the temperature is respectively kept for 2 hours from-40 ℃ to 260 ℃ for 5 temperature cycles.

The main properties of the standard sheet of the material obtained in example 2 at room temperature (25 ℃) are: d₃₃＝292pC/N，ε₃₃ ^T/εo＝1421，tgδ＝1.5％，Kp＝0.525，Qm＝62，Tc＝363℃，ρ_v(260℃)＝6.4×10⁹Ω·cm。

Example 3

The raw material is selected from Pb₃O₄、ZrO₂、TiO₂、SrCO₃、BaCO₃And Sb₂O₃Are all industrial pure grade; the Cr is₂O₃、Sm₂O₃、CeO₂And SiO₂All are chemical pure grades. The raw materials are used as raw materials for blending. According to Pb_0.98Sr_0.005Ba_0.015(Zr_0.50Ti_0.50)_0.975(Sb_1/2Nb_1/2)_0.025O₃+0.04wt.％SiO₂+0.1wt.％Sm₂O₃+0.15wt.％Cr₂O₃+0.05wt.％CeO₂The preparation process is the same as example 1.

The main properties of the standard sheet of material obtained in this example 3 are: d₃₃＝298pC/N，ε₃₃ ^T/εo＝1485，tgδ＝1.58％，Kp＝0.532，Qm＝61，Tc＝358℃，ρ_v(260℃)＝7.2×10⁹Ω·cm。

Example 4

according to Pb_0.98Sr_0.005Ba_0.015(Zr_0.51Ti_0.49)_0.98(Sb_1/2Nb_1/2)_0.02O₃+0.04wt.％SiO₂+0.1wt.％Sm₂O₃+0.15wt.％Cr₂O₃+0.05wt.％CeO₂The preparation process is the same as example 1.

The main properties of the standard sheet of the material obtained in this example 4 at room temperature (25 ℃) are: d₃₃＝305pC/N，ε₃₃ ^T/ε₀＝1590，tgδ＝1.60％，Kp＝0.54，Qm＝59，Tc＝352℃，ρ_v(260℃)＝4.1×10⁹Ω·cm。

Example 5

according to Pb_0.98Sr_0.005Ba_0.015(Zr_0.49Ti_0.51)_0.98(Sb_1/2Nb_1/2)_0.02O₃+0.04wt.％SiO₂+0.1wt.％Sm₂O₃+0.15wt.％Cr₂O₃+0.05wt.％CeO₂The preparation process is the same as example 1.

The main properties of the standard sheet of the material obtained in this example 5 at room temperature (25 ℃) are: d₃₃＝282pC/N，ε₃₃ ^T/ε₀＝1386，tgδ＝1.25％，Kp＝0.52，Qm＝65，Tc＝364℃，ρ_v(260℃)＝5.8×10⁹Ω·cm。

Example 6

according to Pb_0.98Sr_0.005Ba_0.015(Zr_0.50Ti_0.50)_0.98(Sb_1/2Nb_1/2)_0.02O₃+0.04wt.％SiO₂+0.1wt.％Sm₂O₃+0.15wt.％Cr₂O₃The preparation process is the same as example 1.

The main properties of the standard sheet of the material obtained in this example 6 at room temperature (25 ℃) are: d₃₃＝285pC/N，ε₃₃ ^T/ε₀＝1396，tgδ＝1.25％，Kp＝0.525，Qm＝64，Tc＝363℃，ρ_v(260℃)＝1.2×10⁹Ω·cm。

Example 7

The raw material is selected from Pb₃O₄、ZrO₂、TiO₂、SrCO₃、BaCO₃、MnCO₃And Sb₂O₃Are all industrial pure grade; the Sm is₂O₃、CeO₂And SiO₂All are chemical pure grades. The raw materials are used as raw materialsAnd (5) batching the materials. According to Pb_0.98Sr_0.005Ba_0.015(Zr_0.50Ti_0.50)_0.98(Sb_1/2Nb_1/2)_0.02O₃+0.04wt.％SiO₂+0.1wt.％Sm₂O₃+0.05wt.％CeO₂+0.06wt.％MnO₂The preparation process is the same as example 1.

The main properties of the standard sheet of the material obtained in this example 7 at room temperature (25 ℃) are: d₃₃＝286pC/N，ε₃₃ ^T/ε₀＝1369，tgδ＝1.28％，Kp＝0.528，Qm＝62，Tc＝361℃，ρ_v(260℃)＝2.1×10⁹Ω·cm。

Comparative example 1

The raw material is selected from Pb₃O₄、ZrO₂、TiO₂、SrCO₃、MnCO₃And Sb₂O₃Are all industrial pure grade; the Cr is₂O₃、Sm₂O₃、CeO₂And SiO₂All are chemical pure grades. The raw materials are used as raw materials for blending. According to Pb_0.98Sr_0.02(Zr_0.50Ti_0.50)_0.98(Sb_1/2Nb_1/2)_0.02O₃+0.04wt.％SiO₂+0.1wt.％Sm₂O₃+0.15wt.％Cr₂O₃+0.05wt.％CeO₂+0.06wt.％MnO₂The preparation process is the same as that of example 1;

the main properties at room temperature (25 ℃) of the standard sheet of the material obtained in comparative example 1 are: d₃₃＝278pC/N，ε₃₃ ^T/ε₀＝1396，tgδ＝1.25％，Kp＝0.528，Qm＝65，Tc＝361℃，ρ_v(260℃)＝4.8×10⁹Omega cm. When M is Sr alone²⁺In this case, the piezoelectric property is lowered and the resistivity is lowered.

Comparative example 2

The raw material is selected from Pb₃O₄、ZrO₂、TiO₂、SrCO₃、BaCO₃、MnCO₃And Sb₂O₃Are all goodThe industrial grade is pure; the Cr is₂O₃、Sm₂O₃、CeO₂And SiO₂All are chemical pure grades. The raw materials are used as raw materials for blending. According to Pb_0.98Sr_0.01Ba_0.01(Zr_0.50Ti_0.50)_0.98(Sb_1/2Nb_1/2)_0.02O₃+0.04wt.％SiO₂+0.1wt.％Sm₂O₃+0.15wt.％Cr₂O₃+0.05wt.％CeO₂+0.06wt.％MnO₂The preparation process is the same as that of example 1;

the main property at room temperature (25 ℃ C.) of the standard sheet of the material obtained in comparative example 2 was d₃₃＝276pC/N，ε₃₃ ^T/ε₀＝1394，tgδ＝1.27％，Kp＝0.527，Qm＝65，Tc＝361℃，ρ_v(260℃)＝3.4×10⁹Omega cm. When M is selected from Sr²⁺And Ba²⁺And a ratio of 1: 1, the piezoelectric property is lowered and the resistivity is lowered.

Comparative example 3

The raw material is selected from Pb₃O₄、ZrO₂、TiO₂、SrCO₃、BaCO₃、MnCO₃And Sb₂O₃Are all industrial pure grade; the Cr is₂O₃、Sm₂O₃、CeO₂And SiO₂All are chemical pure grades. The raw materials are used as raw materials for blending. According to Pb_0.98Sr_0.005Ba_0.015(Zr_0.50Ti_0.50)_0.98(Sb_1/2Nb_1/2)_0.02O₃+0.04wt.％SiO₂+0.1wt.％Sm₂O₃+0.5wt.％Cr₂O₃+0.05wt.％CeO₂+0.06wt.％MnO₂The preparation process is the same as that of example 1;

the main property at room temperature (25 ℃ C.) of the standard sheet of the material obtained in comparative example 2 was d₃₃＝267pC/N，ε₃₃ ^T/ε₀＝1394，tgδ＝1.27％，Kp＝0.505，Qm＝65，Tc＝349℃，ρ_v(260℃)＝3.4×10⁸Omega cm. When Cr is present₂O₃When the additive is added by more than 0.5 wt%, the piezoelectric performance is obviously reduced, so that the control of the proportion of the additive in a certain range is important.

Table 1 shows Kp and piezoelectric coefficient d of the ceramic element prepared according to the present invention after heat treatment₃₃The change of (2):

。

as can be seen from Table 1, the electromechanical coupling coefficient Kp and the piezoelectric coefficient d of the ceramic element of the present invention were subjected to high temperature treatment for a long period of time₃₃Hardly changes, and the volume resistivity of the ceramic material of the invention reaches 7.8 multiplied by 10 at high temperature (260℃)⁹Omega cm, a highly stable piezoelectric ceramic material with excellent properties. In Table 1, samples 1 to 2 are ceramic elements which were not subjected to high-low temperature cyclic aging in examples 1 to 2, respectively.

Claims

1. PZT-Pb (Sb)_1/2Nb_1/2) A ternary system piezoceramic material, characterized in that said PZT-Pb (Sb)_1/2Nb_1/2) The ternary system piezoelectric ceramic material comprises: lead zirconate titanate and lead antimonite solid solution are taken as main components, and SiO is taken as₂、Sm₂O₃、MnO₂、Cr₂O₃And CeO₂At least 3 of which act as dopants.

2. PZT-Pb (Sb) according to claim 1_1/2Nb_1/2) A ternary system piezoceramic material, characterized in that said PZT-Pb (Sb)_1/2Nb_1/2) The ternary system piezoelectric ceramic material comprises the following chemical components: pb_1-xM_x(Zr_1-yTi_y)_1-z(Sb_1/2Nb_1/2)_zO₃+ awt.%SiO₂+bwt.%Sm₂O₃+ cwt.%Cr₂O₃+ dwt.%CeO₂+ewt.%MnO₂(ii) a (ii) a Wherein M is Sr²⁺And Ba²⁺X =0.01 to 0.1, y=0.4～0.6，z=0.01～0.10，a=0～0.2，b=0.02～0.5，c=0.02～0.5，d=0.01～0.6，e=0～0.8。

3. PZT-Pb (Sb) according to claim 2_1/2Nb_1/2) The ternary system piezoelectric ceramic material is characterized in that M is Sr²⁺And Ba²⁺Then, Sr²⁺And Ba²⁺In a molar ratio of 1: 3.

4. PZT-Pb (Sb) according to claim 2 or 3_1/2Nb_1/2) The ternary piezoelectric ceramic material is characterized in that x = 0.01-0.1, y = 0.4-0.6, z = 0.01-0.10, a = 0.02-0.2, b = 0.02-0.5, c = 0.02-0.5, d = 0.02-0.6, and e = 0.02-0.8.

5. PZT-Pb (Sb) according to any one of claims 1 to 4_1/2Nb_1/2) The preparation method of the ternary system piezoelectric ceramic material is characterized in that Pb is selected₃O₄、ZrO₂、TiO₂、SrCO₃、BaCO₃、Cr₂O₃、Sm₂O₃、Sb₂O₃、Nb₂O₅、CeO₂、MnCO₃And SiO₂The PZT-Pb (Sb) is obtained by mixing, synthesizing, crushing, fine grinding, compression molding, plastic removal, sintering and polarization as raw materials_1/2Nb_1/2) A ternary system piezoelectric ceramic material.

6. The preparation method according to claim 5, wherein the firing temperature is 1260 to 1320 ℃ and the time is 1 to 3 hours; the temperature of the polarization is 120-180 ℃, the voltage is 3-5 kV/mm, and the time is 10-20 minutes.

7. The method of claim 5 or 6, wherein the synthesizing comprises: the temperature is preserved for 1 to 4 hours at 600 to 750 ℃ and then preserved for 1 to 4 hours at 800 to 900 ℃.

8. The preparation method according to any one of claims 5 to 7, wherein the temperature of the plastic discharge is 700 to 800 ℃ and the time is 0.5 to 1 hour.

9. The production method according to any one of claims 5 to 8, wherein the obtained PZT-Pb (Sb)_1/2Nb_1/2) Carrying out high-low temperature cyclic aging on the ternary system piezoelectric ceramic material; the high-low temperature cyclic aging system comprises the following steps: from the normal temperature, firstly cooling to-40 ℃, then preserving heat for 0.5-2 hours, then heating to 260 ℃, preserving heat for 0.5-2 hours, and finally cooling to the normal temperature, wherein 1 cycle is counted; the number of the circulation is 5-10;

preferably, the rate of temperature reduction is 2-10 ℃/min, and the rate of temperature rise is 2-10 ℃/min.

10. PZT-Pb (Sb) according to any one of claims 1 to 4_1/2Nb_1/2) The ternary system piezoelectric ceramic material is applied to the preparation of high-temperature acceleration sensors and acoustic logging equipment.