CN111548155B - High-voltage high-Curie-point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic and preparation method thereof - Google Patents

High-voltage high-Curie-point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic and preparation method thereof Download PDF

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CN111548155B
CN111548155B CN202010246687.2A CN202010246687A CN111548155B CN 111548155 B CN111548155 B CN 111548155B CN 202010246687 A CN202010246687 A CN 202010246687A CN 111548155 B CN111548155 B CN 111548155B
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吴波
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Chengdu Dimace Technology Co ltd
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Abstract

The invention discloses a high-voltage high-Curie point potassium-sodium niobate-potassium-sodium antimonate leadless piezoelectric ceramic and a preparation method thereof, wherein the leadless piezoelectric ceramic is prepared by a general formula of 0.965[ (1-x) K)0.54Na0.476NbO3‑xK0.54Na0.476SbO3]–0.01Bi2O3‑0.0025Fe2O3‑0.03ZrO2Expressed in the formula, x is more than or equal to 0.01 and less than or equal to 0.03. The invention adopts a two-step method to prepare the high-voltage high-Curie-point potassium-sodium niobate-potassium-sodium antimonate leadless piezoelectric ceramic by the traditional ceramic preparation technology, the high-voltage high-Curie-point potassium-sodium niobate-potassium-sodium antimonate leadless piezoelectric ceramic has the advantages of mixed grain size, compact microstructure, high tetragonal phase content of more than 70 percent, good piezoelectric property, temperature stability and higher Curie temperature, has wide applicability in the field of piezoelectric sensors, and can be used in the field of high-temperature sensing.

Description

High-voltage high-Curie-point potassium-sodium niobate-potassium-sodium antimonate lead-free piezoelectric ceramic and preparation method thereof
Technical Field
The invention belongs to the field of lead-free piezoelectric ceramics, relates to preparation of perovskite type alkali metal niobate-based lead-free piezoelectric ceramics, and particularly relates to high-voltage high-Curie point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramics and a preparation method thereof.
Background
The piezoelectric ceramics have excellent performances of ferroelectricity, piezoelectricity, dielectricity and the like, and have wide application in the aspects of detection, conversion and storage of information such as electricity, magnetism, light, sound, heat, force and the like, and have been deeply applied to various fields of national safety and national economy. However, most of piezoelectric ceramics in the current market are lead-based piezoelectric ceramics, lead oxide in production raw materials of the piezoelectric ceramics is toxic, the content of the lead oxide is more than 60%, and lead is a heavy metal element and has extremely high toxicity, so that serious harm is brought to the environment and human health in large-scale production, use and waste processes. With the improvement of consciousness of human beings on ecological environment protection and the requirement of social sustainable development strategy, many countries have issued relevant laws to limit the use of lead in electronic and electric products. Therefore, research and development of lead-free piezoelectric ceramics which are environment-friendly have become an urgent and significant research task.
At present, in the research of lead-free piezoelectric ceramics, three types of piezoelectric ceramics have been developedLead-free piezoelectric ceramics of perovskite structure, i.e. barium titanate (BaTiO)3: BT) series, sodium bismuth titanate (Bi)0.5Na0.5TiO3: BNT) series and alkali metal niobate (K)0.5Na0.5NbO3: KNN) system, which has been widely studied because of its superior performance and the expectation of being fabricated by a conventional preparation process capable of realizing mass production. Among them, perovskite type alkali metal niobate based lead-free piezoelectric ceramics have attracted attention for their relatively high piezoelectric performance and curie temperature, and are considered as one of lead-free piezoelectric ceramic systems that are most promising substitutes for lead-based piezoelectric ceramics. The phase boundary construction mode is reported to be a more effective means for improving the piezoelectric performance of the KNN series ceramic, namely reducing the orthorhombic-tetragonal phase transition temperature TO-TConstructing an orthogonal-tetragonal phase boundary around room temperature; increasing the trigonal-orthorhombic phase transition temperature TR-OConstructing a three-way-orthogonal phase boundary in a room temperature area; simultaneously reducing the orthorhombic-tetragonal phase transition temperature TO-TAnd increasing the trigonal-orthorhombic phase transition temperature TR-OAnd building a trigonal-orthogonal-tetragonal or trigonal-tetragonal phase boundary near room temperature. The piezoelectric coefficient of the KNN ceramic prepared by the idea is improved to a certain extent, and particularly the piezoelectric coefficient can be greatly improved when a trigonal-orthogonal-tetragonal or trigonal-tetragonal phase boundary is constructed near room temperature. Although the KNN-based ceramic obtained in this way has a high piezoelectric constant, the increase in the piezoelectric constant is accompanied by a decrease in the curie temperature, and the application temperature range is narrowed, thereby limiting the application range. Therefore, it becomes important how to obtain a KNN-based ceramic system having both high piezoelectric properties and high curie temperature.
Disclosure of Invention
Aiming at the technical problem that the conventional KNN series ceramic system is difficult to have high piezoelectric property and high Curie point temperature at the same time, the invention aims to provide the high-voltage high-Curie point potassium-sodium niobate-potassium-sodium antimonate lead-free piezoelectric ceramic and the preparation method thereof.
The above object of the present invention can be achieved by a high-voltage high curie point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic having the following general formula:
0.965[(1-x)K0.54Na0.476NbO3-xK0.54Na0.476SbO3]-0.01Bi2O3-0.0025Fe2O3-0.03ZrO2x in the general formula is: x is more than or equal to 0.01 and less than or equal to 0.03; preferably, x is 0.03.
The preparation method of the high-voltage high-Curie point potassium-sodium niobate-potassium-sodium antimonate lead-free piezoelectric ceramic provided by the invention adopts a two-step method to prepare the lead-free piezoelectric ceramic, namely, K is synthesized firstly0.54Na0.476NbO3And K0.54Na0.476SbO3Compound according to the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]-0.01Bi2O3-0.0025Fe2O3-0.03ZrO2Weighing and proportioning the materials according to a chemical formula determined by the set value of the medium x, and introducing Bi2O3、Fe2O3、Zr O2The method specifically comprises the following steps:
(1) compounding with K2CO3、Na2CO3、Nb2O5、Sb2O3As a raw material, according to the general formula K0.54Na0.476NbO3And K0.54Na0.476SbO3The chemical formulas are respectively weighed and proportioned;
(2) pre-sintering, namely respectively grinding and drying the raw materials prepared in the step (1), and then respectively pre-sintering at 800-900 ℃ for 4-6 h for K0.54Na0.476NbO3And K0.54Na0.476SbO3Synthesizing;
(3) compounding with K0.54Na0.476NbO3、K0.54Na0.476SbO3、Bi2O3、Fe2O3、ZrO2Weighing and proportioning raw materials according to a chemical formula determined by a set value of x in the general formula of the leadless piezoelectric ceramic;
(4) pre-sintering, namely grinding and drying the raw materials prepared in the step (3), and then pre-sintering at 750-900 ℃ for 4-8 h to synthesize niobate compounds to obtain pre-sintered powder;
(5) molding, namely adding a polyvinyl alcohol aqueous solution with the mass concentration of 5-7% into the obtained pre-sintered powder for granulation, and pressing and molding the obtained granules by using a mold;
(6) calcining, namely sintering the ceramic blank subjected to compression molding at 1060-1080 ℃ for 2-6 h to obtain sintered ceramic;
(7) and (3) polarizing, namely plating an electrode on the obtained sintered ceramic, putting the sintered ceramic into silicon oil, applying a direct current electric field of 2-3 kV/mm for polarization, and polarizing for 15-30 min to obtain the high-voltage high-Curie point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic.
In the preparation method of the high-voltage high-curie-point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic, the raw materials prepared in the steps (2) and (4) are preferably ground by using absolute ethyl alcohol as a ball milling medium, and are further preferably ground by using a rolling ball milling method.
The inventor finds that K is added to perovskite KNN-based lead-free piezoelectric ceramics in the research of the piezoelectric ceramics0.54Na0.476SbO3Can simultaneously reduce the orthorhombic-tetragonal phase transition temperature and increase the orthorhombic-orthorhombic phase transition temperature to be near the room temperature, but the Curie temperature of the system can also follow K0.54Na0.476SbO3The content is increased and greatly reduced. The inventor also found that Bi is added in the research2O3、Fe2O3、ZrO2Its effect on the orthorhombic-tetragonal and orthorhombic transformation temperatures of the system and K0.54Na0.476SbO3Similarly, but with less Curie temperature reduction for the system. The inventors have found that K can be adjusted by adjusting K0.54Na0.476SbO3And Bi2O3、Fe2O3、ZrO2The addition amount of the compound is increased, on one hand, the construction and optimization of a three-square phase boundary of a KNN system are realized, and the piezoelectric performance of the compound is improved; on the other hand, by introducing Bi2O3、Fe2O3、ZrO2Reducing K when building a trigonal-tetragonal phase boundary0.54Na0.476SbO3The content is controlled to keep higher Curie temperature, and the technical scheme of the invention is completed through repeated experiments.
Compared with the prior art, the high-voltage high-Curie point potassium-sodium niobate-potassium-sodium antimonate lead-free piezoelectric ceramic and the preparation method thereof provided by the invention have the following beneficial effects:
1. the potassium-sodium niobate-potassium-sodium antimonate lead-free piezoelectric ceramic provided by the invention has small and compact crystal grain size inclusion and compact microstructure, and K is introduced at the same time0.54Na0.476SbO3And Bi2O3、Fe2O3、ZrO2The construction and optimization of the trigonal-tetragonal phase boundary of the KNN system are realized, and the lead-free piezoelectric ceramic has good piezoelectric property, temperature stability, higher Curie temperature and piezoelectric constant d33The maximum temperature can reach about 505pC/N, and the Curie temperature TCThe temperature is kept above 285 ℃, the temperature application range of the ceramic is widened, the piezoelectric sensor has wide applicability in the field of piezoelectric sensors, and the piezoelectric sensor can be used in the field of high-temperature sensing.
2. The potassium-sodium niobate-potassium-sodium antimonate lead-free piezoelectric ceramic prepared by the invention benefits from Bi2O3、Fe2O3、ZrO2The crystal grains are mixed, the microstructure is compact, and the electrical property is favorably improved; especially by Fe2O3The introduction of (2) can reduce the sintering temperature on one hand, and has great influence on the microstructure on the other hand, such as grains with large and small impurities, and improves the structural density;
3. the potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic provided by the invention can be obtained by adopting industrial raw materials through the traditional ceramic preparation technology, has a low sintering temperature (1060-1080 ℃), and is easy to realize;
4. the preparation method of the potassium-sodium niobate-potassium-sodium antimonate lead-free piezoelectric ceramic provided by the invention has the advantages of mature process and simple flow, and is beneficial to industrial scale production.
Drawings
FIG. 1 is an X-ray diffraction pattern of a potassium sodium niobate-potassium sodium antimonate-based lead-free piezoelectric ceramic prepared in examples 1 to 4.
FIG. 2 shows the X-ray diffraction refinement pattern (a) and the phase content (b) of the sodium potassium niobate-sodium potassium antimonate lead-free piezoelectric ceramic prepared in example 4.
FIG. 3 is a scanning electron micrograph of the potassium sodium niobate-potassium sodium antimonate-based lead-free piezoelectric ceramic prepared in example 4.
FIG. 4 shows the electrical properties of the potassium sodium niobate-potassium sodium antimonate-based lead-free piezoelectric ceramics prepared in examples 1 to 4.
FIG. 5 shows the dielectric temperature diagram (a) and the phase diagram (b) of the potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic prepared in examples 1 to 4.
FIG. 6 is a graph showing the change in piezoelectric properties with annealing temperature of the potassium sodium niobate-potassium sodium antimonate-based lead-free piezoelectric ceramic prepared in example 4.
FIG. 7 is a graph showing the uniaxial strain with temperature of the potassium sodium niobate-potassium sodium antimonate-based lead-free piezoelectric ceramic prepared in example 4.
The general formula of the lead-free piezoelectric ceramic is a general structure of potassium sodium niobate-potassium sodium antimonate series lead-free piezoelectric ceramic designed according to the raw material proportion.
Detailed Description
The technical solutions of the present invention will be described in detail and fully with reference to the accompanying drawings, which are used for describing the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example preparation is represented by the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]-0.01Bi2O3-0.0025Fe2O3-0.03ZrO2The lead-free piezoelectric ceramic represented by the formula (sample 1), wherein x is 0.01, specifically comprises the following steps:
(1) the raw materials are mixed and stirred,with K2CO3、Na2CO3、Nb2O5、Sb2O is used as a raw material and is represented by a general formula K0.54Na0.476NbO3And K0.54Na0.476SbO3Weighing and proportioning the chemical formula (1);
(2) pre-sintering, namely mixing and ball-milling the raw materials prepared in the step (1) for 24 hours by using absolute ethyl alcohol as a ball-milling medium through a rolling ball milling method, drying to obtain a dry powder, and then pre-sintering at about 850 ℃ for about 6 hours for K0.54Na0.476NbO3And K0.54Na0.476SbO3Synthesizing;
(3) compounding with K0.54Na0.476NbO3、K0.54Na0.476SbO3、Bi2O3、Fe2O3、ZrO2As raw material, according to the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]-0.01Bi2O3-0.0025Fe2O3-0.03ZrO2Weighing and proportioning the materials according to a chemical formula determined by the set value of the medium x;
(4) presintering, namely, taking absolute ethyl alcohol as a ball milling medium for the raw materials prepared in the step (3), mixing and ball milling the raw materials for about 24 hours by using a rolling ball milling method, drying the mixture to obtain dry powder, and presintering the dry powder at about 750 ℃ for about 8 hours to synthesize niobate compounds to obtain presintering powder;
(5) molding, namely adding a polyvinyl alcohol aqueous solution with the mass concentration of 5% into the pre-sintered powder for granulation, pressing the obtained granules into ceramic green sheets with the thickness of 1mm by using a mold with the diameter of 10mm under the pressure of 10Mpa, and discharging glue;
(6) calcining, namely sintering the ceramic blank sheet subjected to compression molding at about 1060 ℃ for about 6 hours to obtain sintered ceramic;
(7) and (3) polarization, namely plating a silver electrode on the sintered ceramic, putting the sintered ceramic into silicon oil, applying a direct current electric field of 3kV/mm for polarization, and polarizing for about 30min to obtain the high-voltage high-Curie point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic.
Example 2
This example preparation is represented by the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]-0.01Bi2O3-0.0025Fe2O3-0.03ZrO2The lead-free piezoelectric ceramic represented by the formula, wherein x is 0.02 (sample 2), specifically comprises the following steps:
(1) compounding with K2CO3、Na2CO3、Nb2O5、Sb2O is used as a raw material and is represented by a general formula K0.54Na0.476NbO3And K0.54Na0.476SbO3Weighing and proportioning the chemical formula (1);
(2) presintering, namely mixing and ball-milling the raw materials prepared in the step (1) for 24 hours by using absolute ethyl alcohol as a ball-milling medium through a rolling ball milling method, drying to obtain a dry powder, presintering the obtained dry powder at about 850 ℃ for about 6 hours, and performing K0.54Na0.476NbO3And K0.54Na0.476SbO3Synthesizing;
(3) compounding with K0.54Na0.476NbO3、K0.54Na0.476SbO3、Bi2O3、Fe2O3、ZrO2As raw material, according to the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]-0.01Bi2O3-0.0025Fe2O3-0.03ZrO2Weighing and proportioning the materials according to a chemical formula determined by the set value of the x;
(4) presintering, namely, taking absolute ethyl alcohol as a ball milling medium for the raw materials prepared in the step (3), mixing and ball milling the raw materials for about 24 hours by using a rolling ball milling method, drying the mixture to obtain a dry powder, and presintering the obtained dry powder at about 800 ℃ for about 6 hours to synthesize a niobate compound to obtain presintered powder;
(5) molding, namely adding a polyvinyl alcohol aqueous solution with the mass concentration of 6% into the pre-sintered powder for granulation, pressing the obtained granules under 10MPa into ceramic blank sheets with the thickness of 1mm by using a mold with the diameter of 10mm, and discharging glue;
(6) calcining, namely sintering the ceramic blank sheet subjected to compression molding at about 1070 ℃ for about 4h to obtain sintered ceramic;
(7) and (3) polarization, namely plating a silver electrode on the sintered ceramic, putting the sintered ceramic into silicon oil, applying a direct current electric field of 2.5kV/mm for polarization, and polarizing for about 25min to obtain the high-voltage high-Curie point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic.
Example 3
This example preparation is represented by the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]–0.01Bi2O3-0.0025Fe2O3-0.03ZrO2The lead-free piezoelectric ceramic represented by the formula, wherein x is 0.025 (sample 3), specifically comprises the following steps:
(1) compounding with K2CO3、Na2CO3、Nb2O5、Sb2O3As a raw material, according to the general formula K0.54Na0.476NbO3And K0.54Na0.476SbO3Weighing and proportioning the chemical formula (1);
(2) presintering, namely mixing and ball-milling the raw materials prepared in the step (1) for 24 hours by using absolute ethyl alcohol as a ball-milling medium through a rolling ball milling method, drying to obtain a dry powder, presintering the obtained dry powder at about 850 ℃ for about 6 hours, and performing K0.54Na0.476NbO3And K0.54Na0.476SbO3Synthesizing;
(3) compounding with K0.54Na0.476NbO3、K0.54Na0.476SbO3、Bi2O3、Fe2O3、ZrO2As raw material, according to the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]-0.01Bi2O3-0.0025Fe2O3-0.03ZrO2Weighing and proportioning the materials according to a chemical formula determined by the set value of the x;
(4) presintering, namely, taking absolute ethyl alcohol as a ball milling medium for the raw materials prepared in the step (3), mixing and ball milling the raw materials for about 24 hours by using a rolling ball milling method, drying the mixture to obtain dry powder, and presintering the obtained dry powder at about 850 ℃ for about 4 hours to synthesize niobate compounds to obtain presintered powder;
(5) molding, namely adding a 7% polyvinyl alcohol aqueous solution into the pre-sintered powder for granulation, pressing the obtained granules under 10MPa into ceramic green sheets with the thickness of 1mm by using a mold with the diameter of 10mm, and discharging glue;
(6) calcining, namely sintering the ceramic green sheets subjected to compression molding at about 1080 ℃ for about 3 hours to obtain sintered ceramic;
(7) and (3) polarization, namely plating a silver electrode on the sintered ceramic, putting the sintered ceramic into silicon oil, applying a direct current electric field of 2kV/mm for polarization, and polarizing for about 20min to obtain the high-voltage high-Curie point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic.
Example 4
This example preparation is represented by the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]–0.01Bi2O3-0.0025Fe2O3-0.03ZrO2The lead-free piezoelectric ceramic represented by the formula, wherein x is 0.03 (sample 4), specifically comprises the following steps:
(1) compounding with K2CO3、Na2CO3、Nb2O5、Sb2O3As a raw material, according to the general formula K0.54Na0.476NbO3And K0.54Na0.476SbO3Weighing and proportioning the chemical formula (1);
(2) presintering, namely, taking absolute ethyl alcohol as a ball milling medium for the raw materials prepared in the step (1), mixing and ball milling for about 24 hours by using a rolling ball milling method, then drying to obtain dry powder, presintering the obtained dry powder for about 6 hours at about 850 ℃ to obtain K0.54Na0.476NbO3And K0.54Na0.476SbO3Synthesizing;
(3) compounding with K0.54Na0.476NbO3、K0.54Na0.476SbO3、Bi2O3、Fe2O3、ZrO2As raw material, according to the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]-0.01Bi2O3-0.0025Fe2O3-0.03ZrO2Weighing and proportioning the materials according to a chemical formula determined by the set value of the x;
(4) presintering, namely, taking absolute ethyl alcohol as a ball milling medium for the raw materials prepared in the step (3), mixing and ball milling the raw materials for about 24 hours by using a rolling ball milling method, drying the mixture to obtain a dry powder, and presintering the obtained dry powder at about 900 ℃ for about 4 hours to synthesize a niobate compound to obtain presintered powder;
(5) molding, namely adding a 7% polyvinyl alcohol aqueous solution into the pre-sintered powder for granulation, pressing the obtained granules under 10MPa into ceramic green sheets with the thickness of 1mm by using a mold with the diameter of 10mm, and discharging glue;
(6) calcining, namely sintering the ceramic blank sheet subjected to compression molding at about 1080 ℃ for about 2 hours to obtain sintered ceramic;
(7) and (3) polarization, namely plating a silver electrode on the sintered ceramic, putting the sintered ceramic into silicon oil, applying a direct current electric field of 2kV/mm for polarization, and polarizing for about 15min to obtain the high-voltage high-Curie point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic.
Example 5
This example is prepared from the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]–0.01Bi2O3-0.0025Fe2O3-0.03ZrO2The lead-free piezoelectric ceramic represented by the formula (sample 5), wherein x is 0.03, specifically includes the following steps:
(1) compounding with K2CO3、Na2CO3、Nb2O5、Sb2O3As a raw material, according to the general formula K0.54Na0.476NbO3And K0.54Na0.476SbO3Weighing and proportioning the chemical formula (1);
(2) pre-sintering, namely mixing and ball-milling the raw materials prepared in the step (1) for about 24 hours by using absolute ethyl alcohol as a ball-milling medium through a rolling ball milling method, drying to obtain dry powder, and then putting the obtained dry powder in a ball millPreburning at about 800 deg.C for about 6h to perform K0.54Na0.476NbO3And K0.54Na0.476SbO3Synthesizing;
(3) compounding with K0.54Na0.476NbO3、K0.54Na0.476SbO3、Bi2O3、Fe2O3、ZrO2As raw material, according to the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]-0.01Bi2O3-0.0025Fe2O3-0.03ZrO2Weighing and proportioning the materials according to a chemical formula determined by the set value of the x;
(4) presintering, namely, taking absolute ethyl alcohol as a ball milling medium for the raw materials prepared in the step (3), mixing and ball milling the raw materials for about 24 hours by using a rolling ball milling method, drying the mixture to obtain a dry powder, and presintering the obtained dry powder at about 900 ℃ for about 4 hours to synthesize a niobate compound to obtain presintered powder;
(5) molding, namely adding a polyvinyl alcohol aqueous solution with the mass concentration of 7% into the pre-sintered powder for granulation, pressing the obtained granules under 10Mpa into ceramic blank sheets with the thickness of 1mm by using a mold with the diameter of 10mm, and discharging glue;
(6) calcining, namely sintering the ceramic green sheets subjected to compression molding at about 1080 ℃ for about 2 hours to obtain sintered ceramic;
(7) and (3) polarization, namely plating a silver electrode on the sintered ceramic, putting the sintered ceramic into silicon oil, applying a direct current electric field of 2kV/mm for polarization, and polarizing for about 15min to obtain the high-voltage high-Curie point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic.
Example 6
This example preparation is represented by the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]–0.01Bi2O3-0.0025Fe2O3-0.03ZrO2The lead-free piezoelectric ceramic represented by the formula, wherein x is 0.03 (sample 6), specifically comprises the steps of:
(1) compounding with K2CO3、Na2CO3、Nb2O5、Sb2O3As a raw material, according to the general formula K0.54Na0.476NbO3And K0.54Na0.476SbO3Weighing and proportioning the chemical formula (1);
(2) presintering, namely mixing and ball-milling the raw materials prepared in the step (1) for about 24 hours by using absolute ethyl alcohol as a ball-milling medium through a rolling ball milling method, drying to obtain dry powder, presintering the obtained dry powder for about 4 hours at about 900 ℃, and performing K0.54Na0.476NbO3And K0.54Na0.476SbO3Synthesizing;
(3) compounding with K0.54Na0.476NbO3、K0.54Na0.476SbO3、Bi2O3、Fe2O3、ZrO2As raw material, according to the general formula 0.965[ (1-x) K0.54Na0.476NbO3-xK0.54Na0.476SbO3]-0.01Bi2O3-0.0025Fe2O3-0.03ZrO2Weighing and proportioning the materials according to a chemical formula determined by the set value of the x;
(4) presintering, namely, mixing and ball-milling the raw materials prepared in the step (3) for about 24 hours by using absolute ethyl alcohol as a ball-milling medium through a rolling ball-milling method, drying to obtain dry powder, and then presintering the obtained dry powder at about 900 ℃ for about 4 hours to synthesize niobate compounds to obtain presintering powder;
(5) molding, namely adding a 7% polyvinyl alcohol aqueous solution into the pre-sintered powder for granulation, pressing the obtained granules under 10MPa into ceramic green sheets with the thickness of 1mm by using a mold with the diameter of 10mm, and discharging glue;
(6) calcining, namely sintering the ceramic green sheets subjected to compression molding at about 1080 ℃ for about 2 hours to obtain sintered ceramic;
(7) and (3) polarization, namely plating a silver electrode on the sintered ceramic, putting the sintered ceramic into silicon oil, applying a direct current electric field of 2kV/mm for polarization, and polarizing for about 15min to obtain the high-voltage high-Curie point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic.
The potassium sodium niobate-potassium sodium antimonate-based lead-free piezoelectric ceramics prepared in examples 1 to 4 were analyzed for structure and properties as follows.
(I) structural analysis
The potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramics (samples 1 to 4) prepared in examples 1 to 4 were subjected to X-ray diffraction analysis, and the analysis results are shown in fig. 1; the X-ray diffraction refinement pattern and phase content of sample 4 are shown in figure 2. As can be seen from fig. 1, all samples are mixed phases of a trigonal phase and a tetragonal phase; from fig. 2, it can be known that the tetragonal phase content is as high as 70% or more, and the electrical properties of the tetragonal phase have good temperature stability due to the high tetragonal phase content. Scanning Electron microscopy of sample 4, as shown in FIG. 3, benefits from Bi2O3、Fe2O3、ZrO2The addition of (3) has the defects of large and small crystal grain inclusion and compact microstructure. Based on the above, the potassium-sodium niobate-potassium-sodium antimonate lead-free piezoelectric ceramic provided by the invention has good piezoelectric coefficient, high Curie temperature and temperature stability, and can be used in the field of high-temperature sensing.
(II) analysis of piezoelectric Properties
1. Analysis of Electrical Properties
The potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramics (samples 1 to 4) prepared in examples 1 to 4 were left to stand in the air for 24 hours and then subjected to electrical property analysis using the IEEE standard, and the analysis results are shown in FIG. 4.
As can be seen from FIG. 4, the dielectric constant εrPiezoelectric constant d33And strain SuniAre all accompanied by K0.54Na0.476SbO3Increase in the amount of addition, indicating that K0.54Na0.476SbO3The addition of (a) contributes to improvement of the electrical properties of the lead-free piezoelectric ceramic, and particularly when x is 0.03, the piezoelectric constant of sample 4 reached 505pC/N and the dielectric constant ∈r2770 is achieved, and strain reaches 0.178%, indicating that the sample has excellent electrical properties.
2. Curie temperature analysis
The potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramics (samples 1 to 4) prepared in examples 1 to 4 were subjected to dielectric temperature spectrum analysis at a temperature ranging from 0 to 500 ℃, and the analysis results are shown in fig. 5. As can be seen from FIG. 5, although the Curie temperature T is presentcWith K0.54Na0.476SbO3The addition is decreased, but it is still maintained at a higher curie temperature. When x is 0.03, the curie temperature of sample 5 is Tc285 ℃, indicating that the sample still has a higher curie temperature. This is because of the introduced Bi2O3、Fe2O3、ZrO2K can be reduced when a three-square phase boundary is constructed0.54Na0.476SbO3So that the sample still maintains a high curie temperature.
(III) thermal stability of piezoelectric constant
The sodium potassium niobate-sodium potassium antimonate-based lead-free piezoelectric ceramic (sample 4) prepared in example 4 was annealed at 20 to 300 ℃ for 30min at each annealing temperature. Testing the piezoelectric performance of the ceramics at each annealing temperature, and measuring the d of the annealed ceramics at each annealing temperature at the corresponding annealing temperature33And normalized, the results are shown in fig. 6. As can be seen from FIG. 6, when the annealing temperature is less than 260 deg.C, d thereof is33The normalized value can still be kept above 90.2%; when the annealing temperature is less than 280 ℃, d thereof33The normalized value can still be kept above 89.1%. The potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic prepared by the invention has good piezoelectric constant thermal stability.
(IV) temperature stability of Strain
The potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic (sample 4) prepared in example 4 was uniaxially strained at 25 to 200 ℃ (S)uni) And (3) testing, namely measuring the corresponding Suni of the ceramic wafer at each test temperature, and normalizing, wherein the obtained result is shown in figure 7. As can be seen in fig. 7, when the annealing temperature is less than 160 ℃, the Suni normalized value can still be maintained above 90.5%; when the annealing temperature is less than 200 ℃, the Suni normalized value can still be kept above 85.3%. The potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic prepared by the invention has good strain thermal stability.
In conclusion, the potassium-sodium niobate-potassium-sodium antimonate lead-free piezoelectric ceramic provided by the inventionSimultaneously has good piezoelectric coefficient, Curie temperature and temperature stability, and the piezoelectric constant d33Can reach about 505pC/N and Curie temperature TCThe temperature is maintained to be more than 285 ℃, so that the system which is excellent in both the temperature and the temperature is obtained for the first time in the field, and the key technical problem which is always concerned in the field is solved: namely, how to solve the contradiction relationship between the high piezoelectric constant and the high curie temperature, and make the two exist together. The temperature application range of the ceramic is further widened, the piezoelectric ceramic has wide applicability in the field of piezoelectric sensors, and can be used in the field of high-temperature sensing.
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.

Claims (5)

1. A preparation method of high-voltage high-Curie point potassium sodium niobate-potassium sodium antimonate leadless piezoelectric ceramics is characterized in that the general formula of the leadless piezoelectric ceramics is as follows:
0.965[(1-x)K0.54Na0.476NbO3-xK0.54Na0.476SbO3]-0.01Bi2O3-0.0025Fe2O3-0.03ZrO2
in the general formula, x is: x is more than or equal to 0.01 and less than or equal to 0.03;
the preparation method of the lead-free piezoelectric ceramic comprises the following steps:
(1) compounding with K2CO3、Na2CO3、Nb2O5、Sb2O3As a raw material, according to the general formula K0.54Na0.476NbO3And K0.54Na0.476SbO3The molar ratios determined by the chemical formulas are respectively weighed and proportioned;
(2) pre-burning, grinding and drying the raw materials prepared in the step (1) respectivelyThen pre-burning for 4-6 h at 800-900 ℃ for K0.54Na0.476NbO3And K0.54Na0.476SbO3Synthesizing;
(3) compounding with K0.54Na0.476NbO3、K0.54Na0.476SbO3、Bi2O3、Fe2O3、ZrO2Weighing and proportioning raw materials according to a chemical formula determined by a set value of x in the general formula of the leadless piezoelectric ceramic;
(4) pre-sintering, namely grinding and drying the raw materials prepared in the step (3), and then pre-sintering at 750-900 ℃ for 4-8 h to synthesize a niobate compound to obtain pre-sintered powder;
(5) molding, namely adding a polyvinyl alcohol aqueous solution with the mass concentration of 5-7% into the obtained pre-sintered powder for granulation, and pressing and molding the obtained granules by using a mold;
(6) calcining, namely sintering the ceramic blank subjected to compression molding at 1060-1080 ℃ for 2-6 h to obtain sintered ceramic;
(7) and (3) polarizing, namely plating an electrode on the obtained sintered ceramic, putting the sintered ceramic into silicon oil, applying a direct current electric field of 2-3 kV/mm for polarization, and polarizing for 15-30 min to obtain the high-voltage high-Curie point potassium sodium niobate-potassium sodium antimonate lead-free piezoelectric ceramic.
2. The method for preparing a high-voltage high-curie-point potassium-sodium niobate-potassium-sodium antimonate lead-free piezoelectric ceramic according to claim 1, wherein x in the formula is 0.03.
3. The method for preparing high-voltage high-curie-point potassium-sodium niobate-sodium potassium antimonate leadless piezoelectric ceramics according to claim 1, wherein the prepared raw materials in the steps (2) and (4) are ground by using absolute ethyl alcohol as a ball milling medium.
4. The method for preparing high-voltage high-curie-point potassium-sodium niobate-sodium potassium antimonate leadless piezoelectric ceramics according to claim 3, characterized in that the prepared raw materials in steps (2) and (4) are ground by a rolling ball milling method with absolute ethyl alcohol as a ball milling medium.
5. The high-voltage high-Curie-point potassium-sodium niobate-sodium potassium antimonate lead-free piezoelectric ceramic prepared by the preparation method of any one of claims 1 to 4.
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