CN111592352A - High-performance potassium sodium niobate series lead-free electrostrictive ceramic and preparation and application thereof - Google Patents
High-performance potassium sodium niobate series lead-free electrostrictive ceramic and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a high-performance potassium sodium niobate series leadless electrostrictive ceramic and a preparation method and application thereof, wherein the leadless piezoelectric ceramic is prepared by a general formula [ (K)0.5Na0.5)1‑x‑Bix](Nb1‑(2/3)x‑Ni(2/3)x)O3Expressed in the formula, x is more than or equal to 0.03 and less than or equal to 0.07. The lead-free electrostrictive ceramic prepared by the invention has good electrostrictive coefficient and temperature stability, and the electrostrictive coefficient can reach 0.0456m4/C2The electrostriction coefficient is kept stable in a wide temperature range from room temperature to 180 ℃, can be applied to electronic devices such as drivers and micro-displacement controllers, and has great significance for replacing lead-based electrostriction materials.
Description
Technical Field
The invention belongs to the field of lead-free electrostrictive ceramics, relates to preparation of perovskite type potassium-sodium niobate-based lead-free electrostrictive ceramics, and particularly relates to high-performance potassium-sodium niobate-based lead-free electrostrictive ceramics as well as a preparation method and application thereof.
Background
The electrostrictive ceramic can convert electric energy and mechanical energy into each other, has the advantages of no hysteresis, high temperature stability, no need of polarization treatment and the like, has wide application in the aspects of micro-displacement control of drivers, high-precision displacement sensors and the like, and has been deeply applied to various fields of national safety and national economy. At present, the market is wideThe electrostrictive ceramic above is mostly a lead-based electrostrictive ceramic including, for example, Pb (Mg)1/3Nb2/3)O3(PMN)、Pb(Zn1/3Nb2/3)O3(PZN) ceramics, etc., the electrostrictive coefficient of the lead-based electrostrictive ceramics is 0.015 to 0.025m4/C2And the temperature stability is better. However, lead is a toxic heavy metal element, lead oxide in the raw materials for producing electrostrictive ceramics is toxic and has a content of more than 60%, and serious harm is brought to the environment and human health in large-scale production, use and waste processes. With the increasing awareness of the protection of the ecological environment, many countries have established relevant laws to limit the use of lead elements in electronic and electrical products. Therefore, the development of lead-free electrostrictive materials which are environmentally friendly has become an urgent and significant research task.
Disclosure of Invention
Aiming at the problems of heavy metal pollution and the like in the production process of the current lead-based electrostrictive ceramic, the invention aims to provide the high-performance potassium-sodium niobate system lead-free electrostrictive ceramic which has high electrostrictive coefficient and excellent temperature stability.
The second purpose of the invention is to provide a method for preparing the high-performance potassium-sodium niobate system lead-free electrostrictive ceramic, so as to avoid the problem of heavy metal pollution in the production process of the lead-based electrostrictive ceramic.
The third purpose of the invention is to provide the application of the potassium-sodium niobate system lead-free electrostrictive ceramic in the manufacture of drivers and high-precision micro displacement sensing devices.
Aiming at the first invention purpose, the high-performance potassium-sodium niobate system lead-free electrostrictive ceramic provided by the invention has a molecular general formula as follows: [ (K)0.5Na0.5)1-x-Bix](Nb1-(2/3)x-Ni(2/3)x)O3In the general formula, x is: x is more than or equal to 0.03 and less than or equal to 0.07.
In the above technical solution, x in the general formula of the high-performance potassium-sodium niobate system lead-free electrostrictive ceramic is preferably set to a value: x is more than or equal to 0.04 and less than or equal to 0.06; further preferred are: x is 0.05.
In order to solve the second object of the present invention, the method for preparing the high-performance potassium sodium niobate-based lead-free electrostrictive ceramic includes the steps of:
(1) compounding with Na2CO3,K2CO3,Nb2O5,Bi2O3And NiO2Is prepared from the general formula [ (K)0.5Na0.5)1-x-Bix](Nb1-(2/3)x-Ni(2/3)x)O3Weighing and proportioning the materials according to a chemical formula determined by the set value of the x;
(2) ball milling, namely ball milling the prepared raw materials, and drying after ball milling to obtain a dry powder;
(3) pre-sintering, namely pre-sintering the dry powder at 800-900 ℃ for 3-6 h to synthesize a niobate compound to obtain pre-sintered powder;
(4) molding, namely adding a polyvinyl alcohol aqueous solution with the mass concentration of 5-9% into the obtained pre-sintered powder, granulating to obtain granules, and pressing and molding the obtained granules by using a mold;
(5) and (3) calcining, namely sintering the ceramic blank subjected to compression molding at 1120-1180 ℃ for 1-5 hours to obtain sintered ceramic, and sintering and infiltrating the electrode with the obtained sintered ceramic to obtain the high-performance potassium-sodium niobate leadless electrostrictive ceramic.
In the step (2) of the preparation method of the high-performance potassium-sodium niobate system lead-free electrostrictive ceramic, ball milling is carried out by adopting a ball milling process commonly used in the field, for example, absolute ethyl alcohol is used as a ball milling medium, and a rolling ball milling method is adopted for grinding.
The high-performance potassium sodium niobate leadless electrostrictive ceramic provided by the invention has higher electrostrictive coefficient and excellent temperature stability, and can be used for manufacturing drivers and high-precision micro-displacement sensing devices.
The present invention is proposed based on the following knowledge: potassium sodium niobate (K)0.5Na0.5NbO3: KNN) series ceramic is perovskite type ferroelectric, belongs to one of oxygen-containing octahedral ferroelectrics, and has a general formula of ABO3The top corner is occupied by the larger a ions,the body center is occupied by the smaller B ions and the six face centers are occupied by O ions. These oxygen ions form oxygen octahedrons, with ion B in the center of the oxygen octahedron. The crystal structure of potassium-sodium niobate ceramic can be obtained by doping Bi at the A site3+And B site doped with Ni2+Obtaining high electrostrictive coefficient, namely passing through A-bit Bi3+Doping and B-site Ni2+Doping to break the long-range ferroelectric order of original system, inducing relaxation phase near room temperature, and doping Bi due to A position3+Has an ionic radius smaller than K at the A position in the KNN group+And Na+The radius of the ions can cause the moving range of B-site ions to be limited, a large electrostrictive effect is generated, and therefore a high electrostrictive coefficient is obtained, and meanwhile, the electrostrictive coefficient presents excellent temperature stability due to the high stability of the relaxation phase. In addition, Bi3+And Ni2+The relatively high doping amount enables the relaxation characteristics to be more obvious, and is beneficial to obtaining pure electrostrictive performance.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention provides a high-performance potassium-sodium niobate leadless electrostrictive ceramic, which passes through A-position Bi in a potassium-sodium niobate ceramic system3+Doping and B-site Ni2+Random fields in the local area structure are enhanced by doping, the original long-range ferroelectric order is broken, and the lead-free electrostriction ceramic has good electrostriction coefficient and temperature stability. As shown in the specific embodiment, when x in the general formula is 0.05, the magnetostriction coefficient can reach 0.0456m4/C2And the electrostriction coefficient is kept stable in a wide temperature range from room temperature to 180 ℃.
2. The potassium sodium niobate leadless electrostrictive ceramic provided by the invention can be obtained by adopting industrial raw materials through the traditional ceramic preparation technology, has mature process and simple flow, is easy to realize, and is beneficial to industrial scale production.
3. The potassium-sodium niobate leadless electrostrictive ceramic provided by the invention is based on good electrostrictive coefficient and temperature stability, is environment-friendly, can be applied to electronic devices such as drivers and micro displacement controllers, and has great significance for replacing lead-based electrostrictive materials.
Drawings
FIG. 1 is an X-ray diffraction pattern of a potassium sodium niobate-based lead-free electrostrictive ceramic prepared in example 3;
FIG. 2 is a dielectric temperature spectrum and relaxation factor of the potassium sodium niobate-based lead-free electrostrictive ceramic prepared in example 3;
FIG. 3 is a hysteresis loop and a strain loop of a potassium sodium niobate-based lead-free electrostrictive ceramic prepared in example 3;
FIG. 4 is an electrostrictive test result of the potassium sodium niobate-based lead-free electrostrictive ceramics prepared in examples 1 to 5; wherein (a) is a schematic view of electrostriction at room temperature of the potassium sodium niobate-based lead-free electrostrictive ceramic prepared in example 3, and (b) is an electrostriction coefficient at room temperature of the potassium sodium niobate-based lead-free electrostrictive ceramic prepared in examples 1 to 5;
fig. 5 is a graph showing changes in the electrostrictive coefficient with temperature of the potassium sodium niobate-based lead-free electrostrictive ceramic prepared in example 3.
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 [ (K)0.5Na0.5)1-x-Bix](Nb1-(2/3)x-Ni(2/3)x)O3The lead-free electrostrictive ceramic represented by the formula, wherein x is 0.03 (sample 1), specifically comprises the following steps:
(1) compounding with Na2CO3,K2CO3,Nb2O5,Bi2O3And NiO2Is prepared from the raw material according to the chemical formula [ (K)0.5Na0.5)0.97-Bi0.03](Nb0.98-Ni0.02)O3Weighing and proportioning;
(2) ball milling, namely ball milling the prepared raw materials, and drying after ball milling to obtain a dry powder;
(3) presintering, namely presintering the dry powder for about 3 hours at about 900 ℃ to synthesize a niobate compound, and cooling to room temperature to obtain presintered powder;
(4) molding, namely grinding the pre-sintered powder uniformly, adding a polyvinyl alcohol aqueous solution with the mass concentration of about 5% for granulation to obtain granules, pressing the granules into ceramic blank sheets with the thickness of 0.5mm by using a mold with the diameter of 10mm under the pressure of 10Mpa, and discharging glue;
(5) calcining, namely, sintering the ceramic blank sheet subjected to glue discharge at 1180 ℃ for about 1h in a heat preservation way, cooling to room temperature, taking out the ceramic blank sheet to obtain sintered ceramic, and sintering the sintered ceramic to infiltrate silver into the electrode to obtain the high-performance potassium sodium niobate leadless electrostrictive ceramic.
Example 2
This example preparation is represented by the general formula [ (K)0.5Na0.5)1-x-Bix](Nb1-(2/3)x-Ni(2/3)x)O3The lead-free electrostrictive ceramic expressed by the formula, wherein x is 0.04 (sample 2), specifically comprises the following steps:
(1) compounding with Na2CO3,K2CO3,Nb2O5,Bi2O3And NiO2Is prepared from the raw material according to the chemical formula [ (K)0.5Na0.5)0.96-Bi0.04](Nb0.973-Ni0.027)O3Weighing and proportioning;
(2) ball milling, namely ball milling the prepared raw materials, and drying after ball milling to obtain a dry powder;
(3) presintering, namely presintering the dry powder for about 5 hours at the temperature of about 850 ℃ to synthesize a niobate compound, and cooling to room temperature to obtain presintered powder;
(4) molding, namely grinding the pre-sintered powder uniformly, adding a polyvinyl alcohol aqueous solution with the mass concentration of about 6% for granulation to obtain granules, pressing the granules into ceramic blank sheets with the thickness of 0.5mm by using a mold with the diameter of 10mm under the pressure of 10Mpa, and discharging glue;
(5) and calcining, namely, carrying out heat preservation sintering on the ceramic blank sheet subjected to the binder removal at the temperature of about 1160 ℃ for about 3h, cooling to room temperature, taking out the ceramic blank sheet to obtain sintered ceramic, and sintering the sintered ceramic to infiltrate the silver electrode to obtain the high-performance potassium sodium niobate leadless electrostrictive ceramic.
Example 3
This example preparation is represented by the general formula [ (K)0.5Na0.5)1-x-Bix](Nb1-(2/3)x-Ni(2/3)x)O3The lead-free electrostrictive ceramic expressed by the formula, wherein x is 0.05 (sample 3), specifically comprises the following steps:
(1) compounding with Na2CO3,K2CO3,Nb2O5,Bi2O3And NiO2Is prepared from the raw material according to the chemical formula [ (K)0.5Na0.5)0.95-Bi0.05](Nb0.967-Ni0.033)O3Weighing and proportioning;
(2) ball milling, namely ball milling the prepared raw materials, and drying after ball milling to obtain a dry powder;
(3) presintering, presintering the dry powder for about 4 hours at about 850 ℃ to synthesize niobate compounds, and cooling to room temperature to obtain presintered powder;
(4) molding, namely grinding the pre-sintered powder uniformly, adding a polyvinyl alcohol aqueous solution with the mass concentration of about 7% for granulation to obtain granules, pressing the granules into ceramic blank sheets with the thickness of 0.5mm by using a mold with the diameter of 10mm under the pressure of 10Mpa, and discharging glue;
(5) and (3) calcining, namely, carrying out heat preservation sintering on the ceramic blank sheet subjected to glue discharge at about 1150 ℃ for about 3h, cooling to room temperature, taking out to obtain sintered ceramic, and sintering the sintered ceramic to infiltrate silver into the electrode to obtain the high-performance potassium sodium niobate leadless electrostrictive ceramic.
Example 4
This example preparation is represented by the general formula [ (K)0.5Na0.5)1-x-Bix](Nb1-(2/3)x-Ni(2/3)x)O3A lead-free electrostrictive ceramic represented by the formula, wherein x is 0.06 (sample 4), comprising in particular the following steps:
(1) compounding with Na2CO3,K2CO3,Nb2O5,Bi2O3And NiO2Is prepared from the raw material according to the chemical formula [ (K)0.5Na0.5)0.94-Bi0.06](Nb0.96-Ni0.04)O3Weighing and proportioning;
(2) ball milling, namely ball milling the prepared raw materials, and drying after ball milling to obtain a dry powder;
(3) presintering, presintering the dry powder for about 4 hours at about 850 ℃ to synthesize niobate compounds, and cooling to room temperature to obtain presintered powder;
(4) molding, namely grinding the pre-sintered powder uniformly, adding a polyvinyl alcohol aqueous solution with the mass concentration of about 8% for granulation to obtain granules, pressing the granules into ceramic blank sheets with the thickness of 0.5mm by using a mold with the diameter of 10mm under the pressure of 10Mpa, and discharging glue;
(5) calcining, namely, carrying out heat preservation sintering on the ceramic blank sheet subjected to glue discharge at about 1140 ℃ for about 4h, cooling to room temperature, taking out the ceramic blank sheet to obtain sintered ceramic, and sintering the sintered ceramic to infiltrate silver into the electrode to obtain the high-performance potassium sodium niobate leadless electrostrictive ceramic.
Example 5
This example preparation is represented by the general formula [ (K)0.5Na0.5)1-x-Bix](Nb1-(2/3)x-Ni(2/3)x)O3The lead-free electrostrictive ceramic represented by the formula (sample 5), wherein x is 0.07, specifically comprises the following steps:
(1) compounding with Na2CO3,K2CO3,Nb2O5,Bi2O3And NiO2Is prepared from the raw material according to the chemical formula [ (K)0.5Na0.5)0.93-Bi0.07](Nb0.953-Ni0.047)O3Weighing and proportioning;
(2) ball milling, namely ball milling the prepared raw materials, and drying after ball milling to obtain a dry powder;
(3) presintering, namely presintering the dry powder for about 6 hours at about 800 ℃ to synthesize a niobate compound, and cooling to room temperature to obtain presintered powder;
(4) molding, namely grinding the pre-sintered powder uniformly, adding a polyvinyl alcohol aqueous solution with the mass concentration of about 9% for granulation to obtain granules, pressing the granules into ceramic blank sheets with the thickness of 0.5mm by using a mold with the diameter of 10mm under the pressure of 10Mpa, and discharging glue;
(5) calcining, namely, carrying out heat preservation sintering on the ceramic blank sheet subjected to glue discharge at about 1120 ℃ for about 5h, cooling to room temperature, taking out to obtain sintered ceramic, and sintering the obtained sintered ceramic to infiltrate silver into the electrode to obtain the high-performance potassium sodium niobate leadless electrostrictive ceramic.
The structures and properties of the potassium sodium niobate-based lead-free electrostrictive ceramics prepared in examples 1 to 5 were analyzed as follows.
(I) structural analysis
The X-ray diffraction analysis of the potassium sodium niobate-based lead-free electrostrictive ceramic (sample 3) prepared in example 3 was performed, and the analysis result is shown in fig. 1. As can be seen from fig. 1, the lead-free electrostrictive ceramic exhibits a single cubic structure, no second phase is generated, and all diffraction peaks are unimodal, indicating that the potassium-sodium niobate-based lead-free electrostrictive ceramic has a pseudo cubic phase structure.
(II) analysis of Properties
1. Dielectric properties
Dielectric properties of the potassium sodium niobate-based lead-free electrostrictive ceramic (sample 3) prepared in example 3 were analyzed. The dielectric temperature relationship and the relaxation factor change under different frequencies are shown in fig. 2, and it can be seen from fig. 2 that the dielectric property of the lead-free electrostrictive ceramic shows obvious relaxation characteristics, i.e. the curie temperature is not a definite point any more, but a temperature range, and has good spectral dispersion, and the relaxation factor gamma (dispersion index) is 1.88. This indicates that the lead-free electrostrictive ceramic is a ferroelectric having a dispersion phase transition. The electrical hysteresis loop is shown in FIG. 3, and it can be seen from FIG. 3 that the electrical hysteresis loop of the sample is relatively thin and long, and the remanent polarization and coercive electric field are relatively small, which indicates that Bi passes through the A site3+Doping and B-site Ni2+Doping breaks the original long-range ferroelectric order, and the ferroelectricity of the ferroelectric is weakened.
2. Electrostrictive properties
The potassium sodium niobate-based lead-free electrostrictive ceramic (sample 3) prepared in example 3 was subjected to electrostrictive performance analysis. As shown in FIG. 3, it can be seen from FIG. 3 that the maximum strain amount is 0.07% at a maximum electric field strength of 60 kV/cm. The electrostrictive diagram at room temperature is shown in FIG. 4, and from FIG. 4(a), it can be seen that the S-P curve fits very well to a parabola, and in combination with FIG. 4(b), it can be seen that all samples prepared by the method of the present invention have good electrostrictive effect, and that the electrostrictive coefficient of sample 3 at room temperature is as high as 0.0456m4/C2. This is due to the A-site doped Bi3+Has an ionic radius smaller than K at the A position in the KNN group+And Na+The radius of the ions causes the moving range of B-site ions to be limited, and a large electrostrictive effect is generated, so that a high electrostrictive coefficient is obtained, which is almost twice of the phase performance of the traditional lead-based electrostrictive material.
(III) temperature stability
The temperature stability of the electrostrictive coefficient of the potassium sodium niobate-based lead-free electrostrictive ceramic (sample 3) prepared in example 3 was analyzed, and the analysis result is shown in fig. 5. As can be seen from FIG. 5, the electrostriction coefficient remains stable in a wide temperature range from room temperature to 180 ℃, indicating that the electrostriction coefficient of the potassium-sodium niobate leadless electrostriction ceramic prepared by the present invention exhibits excellent temperature stability. This is because the relaxation phase has high stability, so that the electrostrictive coefficient is stable in a wide temperature range from room temperature to 180 ℃.
In conclusion, the high-performance potassium sodium niobate-based lead-free electrostrictive ceramic provided by the invention utilizes non-equivalent ions to replace ions, which is beneficial to destroying long-range ordered structures and increasing relaxation type, so that the ceramic has good electrostrictive coefficient and temperature stability at the same time, can be applied to electronic devices such as drivers and micro displacement controllers, and has great significance for replacing lead-based electrostrictive materials.
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 present invention, and these changes and combinations are within the scope of the present invention.
Claims (5)
1. A high-performance potassium sodium niobate series lead-free electrostrictive ceramic is characterized in that the molecular general formula of the lead-free electrostrictive ceramic is as follows: [ (K)0.5Na0.5)1-x-Bix](Nb1-(2/3)x-Ni(2/3)x)O3In the general formula, x is as follows: x is more than or equal to 0.03 and less than or equal to 0.07.
2. The high-performance potassium sodium niobate-based lead-free electrostrictive ceramic according to claim 1, wherein x in the general formula of the lead-free electrostrictive ceramic is represented by: x is more than or equal to 0.04 and less than or equal to 0.06.
3. The high-performance potassium sodium niobate-based lead-free electrostrictive ceramic according to claim 2, wherein x in the general formula of the lead-free electrostrictive ceramic is represented by: x is 0.05.
4. A method for producing the high-performance potassium sodium niobate-based lead-free electrostrictive ceramic claimed in claim 1, 2, or 3, characterized by comprising the steps of:
(1) compounding with Na2CO3,K2CO3,Nb2O5,Bi2O3And NiO2Is prepared from the general formula [ (K)0.5Na0.5)1-x-Bix](Nb1-(2/3)x-Ni(2/3)x)O3Weighing and proportioning the materials according to a chemical formula determined by the set value of the x;
(2) ball milling, namely ball milling the prepared raw materials, and drying after ball milling to obtain a dry powder;
(3) pre-sintering, namely pre-sintering the dry powder at 800-900 ℃ for 3-6 h to synthesize a niobate compound to obtain pre-sintered powder;
(4) molding, namely adding a polyvinyl alcohol aqueous solution with the mass concentration of 5-9% into the obtained pre-sintered powder, granulating to obtain granules, and pressing and molding the obtained granules by using a mold;
(5) and (3) calcining, namely sintering the ceramic blank subjected to compression molding at 1120-1180 ℃ for 1-5 hours to obtain sintered ceramic, and sintering and infiltrating the electrode with the obtained sintered ceramic to obtain the high-performance potassium-sodium niobate leadless electrostrictive ceramic.
5. Use of the high performance potassium sodium niobate-based lead-free electrostrictive ceramic of claim 1, 2, or 3 in the manufacture of actuators and high precision micro displacement sensing devices.
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