CN117800723A - Piezoelectric ceramic and preparation method and application thereof - Google Patents
Piezoelectric ceramic and preparation method and application thereof Download PDFInfo
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- CN117800723A CN117800723A CN202310115095.0A CN202310115095A CN117800723A CN 117800723 A CN117800723 A CN 117800723A CN 202310115095 A CN202310115095 A CN 202310115095A CN 117800723 A CN117800723 A CN 117800723A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
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- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
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Abstract
A piezoelectric ceramic and a preparation method and application thereof mainly relate to the field of piezoelectric ceramics. The piezoelectric ceramic preparation method provided by the embodiment of the invention comprises the steps of mixing K 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 、Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 Cu and Cu 2 Ta 4 O 12 Reasonable configuration is carried out, so that the KNNLS-BKNZH-x% mol CTO piezoelectric ceramic provided by the application can simultaneously realize the reduction of sintering temperature, the widening of sintering temperature area, the improvement of the density, the process stability and the mechanical quality factor of the piezoelectric ceramic and the reduction of dielectric quality factor in the preparation processThe technical effect of loss is further good in process mass production stability and product application effect, so that the piezoelectric ceramic and the preparation method thereof provided by the embodiment of the invention have important industrial mass production application value.
Description
The application is as follows: 202211208144.7, the invention name is: patent application of piezoelectric ceramics and its preparation method and application.
Technical Field
The invention relates to the field of piezoelectric ceramics, in particular to a piezoelectric ceramic, a preparation method and application thereof.
Background
Piezoelectric ceramics are important functional materials capable of realizing the mutual conversion of mechanical energy and electric energy, and occupy a considerable proportion in the field of electronic materials. In recent years, the annual sales of piezoelectric ceramics worldwide has increased by about 20%.
Currently, lead zirconate titanate (PZT) -based ceramic materials are dominant in piezoelectric materials, however, lead is a toxic substance and volatilizes severely. The lead-based ceramics cause great harm to the ecological environment and human body in the production, use and waste treatment processes. Therefore, research and development of lead-free piezoelectric ceramics have been paid attention to, and at present, research of lead-free piezoelectric ceramics has been mainly focused on bismuth layered structure ceramics, tungsten bronze structure ceramics, titanate series ceramics, and potassium sodium niobate series ceramics. Among them, potassium sodium niobate (KNN) based leadless piezoelectric ceramics has the characteristics of good piezoelectric performance, good ferroelectric performance, high Curie temperature, etc., is an excellent leadless piezoelectric material, and has been widely paid attention to by researchers.
However, the potassium sodium niobate (KNN) -based leadless piezoelectric ceramic in the prior art has the defects of poor compactness, narrow sintering temperature range and unstable material performance, and it needs to be described that in the prior art, the characteristic parameters such as piezoelectric performance, mechanical quality factor, dielectric loss and the like of the KNN-based piezoelectric ceramic are not balanced, so that the mass production application of the KNN-based leadless piezoelectric ceramic in various fields is seriously affected.
Disclosure of Invention
The invention aims to provide a preparation method of piezoelectric ceramics, which can overcome the defects of poor density, narrow sintering temperature area and unstable performance of the piezoelectric ceramics, and can balance the characteristic parameters of piezoelectric performance, mechanical quality factor, dielectric loss and the like of the piezoelectric ceramics, thereby being beneficial to the application of industrial mass production.
Another object of the present invention is to provide a piezoelectric ceramic, which is prepared by the above method, and the piezoelectric ceramic has better compactness, wider sintering temperature zone, lower dielectric loss, higher piezoelectric performance and mechanical quality factor, and good performance stability.
Another object of the present invention is to provide an application of the piezoelectric ceramic provided above in the laser display field.
The invention solves the technical problems by adopting the following technical scheme.
The invention provides a preparation method of piezoelectric ceramics, which comprises the following steps:
selecting raw materials according to chemical formula 0.96[ K ] 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]-0.04[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]-x％molCu 2 Ta 4 O 12 Calculating and batching to obtain a first raw material, wherein the value range of x is [0.25,1 ]]；
Ball milling is carried out on the first raw material, and presintering is carried out to obtain a first product;
and after the first product is molded and adhesive is discharged, sintering, silver electrode polarization and high-voltage polarization are sequentially carried out.
Further, in the preferred embodiment of the present invention, the chemical formula is 0.96[ K ] 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]-0.04[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]-x％molCu 2 Ta 4 O 12 In (2) said Cu 2 Ta 4 O 12 The corresponding raw materials are prepared by the following method:
according to Cu 2 Ta 4 O 12 After calculation and batching of the chemical formula of (C) to obtain Cu 2 Ta 4 O 12 Raw materials;
the Cu is treated with 2 Ta 4 O 12 The raw materials are subjected to ball milling treatment and presintering in sequence.
Advancing oneFurther, in the preferred embodiment of the present invention, the Cu is treated by 2 Ta 4 O 12 The ball milling treatment and presintering of the raw materials in sequence comprise:
at the Cu 2 Ta 4 O 12 Adding absolute ethyl alcohol into the raw materials for ball milling to obtain ball milling raw materials, wherein the ball milling time is 8-24 h, and the rotating speed is 150-500 r/min;
presintering the ball-milling raw materials, wherein the presintering temperature is 800-950 ℃, and the heat preservation time is 3-6 h.
Further, in the preferred embodiment of the present invention, the value of x is in the range of [0.5,1].
Further, in the preferred embodiment of the present invention, the value of x is 0.75.
Further, in the preferred embodiment of the present invention, when the first raw material is subjected to the ball milling treatment, the ball milling time is 8-24 hours, and the rotational speed is 150-500 rpm; and the presintering comprises the following steps: preserving heat for 6-10 h at 800-950 ℃;
the molding process of the first product includes: grinding the first product, adding a binder polyvinyl alcohol solution with the mass fraction of 5-12% for granulating, and tabletting with the pressure value of 10-20 MPa in a die.
Further, in a preferred embodiment of the present invention, the sintering includes: firstly preserving heat for 1-15 min at the sintering temperature of 1100-1200 ℃, and then reducing the temperature to 900-1030 ℃ for 3-25 h, wherein the temperature reduction speed is 5-20 ℃/min.
The invention also provides piezoelectric ceramics, which are prepared according to the preparation method of the piezoelectric ceramics.
Further, in the preferred embodiment of the present invention, the content of Na, K, cu, zr, nb, sb, hf, ta and Bi elements in the piezoelectric ceramic is 6.94-7.95%, 12.16-13.17%, 0.09-0.66%, 6.01-8.78%, 55.93-59.04%, 4.08-4.69%, 4.33-5.72%, 0.72-5.36% and 1.58-2.14% by mass, respectively.
The invention also provides application of the piezoelectric ceramic, and particularly relates to application of the piezoelectric ceramic to the technical field of laser display.
The piezoelectric ceramic provided by the embodiment of the invention and the preparation method and application thereof have the beneficial effects that:
by combining K 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 、Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 Cu and Cu 2 Ta 4 O 12 The preparation method has the advantages that reasonable configuration is carried out, so that the KNNLS-BKNZH-x% mol CTO piezoelectric ceramic provided by the application can simultaneously realize the technical effects of reducing sintering temperature, widening sintering temperature area, improving the compactness, process stability and mechanical quality factor of the piezoelectric ceramic and reducing dielectric loss, and further, the process mass production stability and the product effect are good, and therefore, the piezoelectric ceramic and the preparation method thereof provided by the application embodiment have important industrial mass production application value.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a KNNLS-BKNZH-x% mol CTO leadless piezoelectric ceramic wafer provided in an embodiment of the invention when x is different in value;
FIG. 2 is an XRD diagram of KNNLS-BKNZH-x% mol CTO leadless piezoelectric ceramic wafer provided by the embodiment of the invention when x takes different values;
3a, 3b, 3c and 3d are EDS test spectrograms of KNLS-BKNZH-x% mol CTO piezoelectric ceramic provided by the embodiment of the invention when x is equal to 0.25, 0.5, 0.75 and 1 respectively;
FIG. 4 shows a KNLS-BKNZH-D of x% molCTO leadless piezoelectric ceramic chip when x takes different values 33 And a kp plot;
FIG. 5 is a graph of Qm and dielectric loss of a KNNLS-BKNZH-x% mol CTO leadless piezoelectric ceramic wafer provided by an embodiment of the invention when x is different in value;
FIG. 6 is a Tc and dielectric constant chart of a KNNLS-BKNZH-x% mol CTO lead-free piezoelectric ceramic wafer provided by an embodiment of the invention when x takes different values;
7a, 7b, 7c and 7d are respectively the dielectric temperature curves of KNLS-BKNZH-x% mol CTO piezoelectric ceramics provided by the embodiment of the invention when x is equal to 0.25, 0.5, 0.75 and 1;
FIG. 8 is an SEM image of the KNNLS-BKNZH-0.75% mol CTO piezoelectric ceramic sintered at 980-1090 ℃ provided by the embodiment of the invention;
FIG. 9 shows d corresponding to sintering of KNLS-BKNZH-0.75% mol CTO piezoelectric ceramic provided by the embodiment of the invention at 980-1090deg.C 33 And Qm performance profile.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Before describing the embodiments of the present invention, applicant first needs to further detail the shortcomings of the prior art or the more specific background of the prior art before applicant's study. Specifically, potassium sodium niobate (KNN) lead-free piezoelectric ceramics mainly consist of KNbO 3 、NaNbO 3 And KNbO 3 -NaNbO 3 Is composed of a solid solution of (a). The sintering temperature of the traditional solid phase reaction method is generally 1090-1120 ℃, the temperature is higher, excessive volatilization of alkali metal elements such as K, na and the like easily occurs in the sintering process, the stoichiometric ratio of the formula is finally deviated, and a ceramic finished product with good compactness is difficult to obtain; at the same time, the K,Volatilization of alkali metal ions such as Na and the like at high temperature often causes narrowing of a sintering temperature zone of the material (often causes great changes of sintering density and crystal grains due to 5-10 ℃), so that the KNN ceramic is not easy to compact into porcelain and the performance is not easy to stabilize; in addition, in the aspect of improving the sintering process, the new sintering means developed in recent years are mostly dependent on special sintering equipment and test processes, such as hot pressing or plasma sintering, and the ceramic with the relative density of 99% can be obtained, but the stability of the material is poor, the cost of the process equipment is high, and the industrial production is difficult to realize; in particular, in recent years, the piezoelectric performance of KNN ceramics is the most often focused, however, the application of the device needs to focus on parameters such as mechanical performance and loss of the piezoelectric ceramics, such as kp (planar electromechanical coupling coefficient), qm (mechanical quality factor), tan delta (dielectric loss), etc., because kp, qm, tan delta affects the effect and service life of certain device applications (such as transducers, etc.) even more than d 33 Larger.
Further specifically, the performance research of KNN ceramics in the prior art is mainly focused on the piezoelectric performance d 33 Less research is done on mechanical properties and dielectric loss, see table 1. As is clear from the data in Table 1, researchers have improved the piezoelectric properties d of KNN ceramics 33 Along with the decrease of the mechanical quality factor Qm and the increase of the dielectric loss tan delta: such as KNNS-BNZ-BZ ceramic d of Shandong university 33 610pC/N, mechanical quality factor qm=34, dielectric loss tan δ=5.5%; d of KNNS-BNKZ-F-AS ceramic of university of Sichuan 33 650pC/N, but the mechanical quality factor Qm is only 30, and the dielectric loss tan delta is 7.8%; at the same time, as can be seen from Table 1, KNN ceramics with higher Qm tend to have piezoelectric properties d 33 And is very low: qm=137, d of e.g. KNNCL-KTN-M-C ceramic 33 =264 pC/N. While the common lead-based PZT piezoelectric ceramics such as P51 series have the piezoelectric property d 33 At 550-700pC/N, the mechanical quality factor qm=80, the dielectric loss is only 2.5%, i.e. d 33 Higher, also higher mechanical quality factor and lower dielectric loss. In contrast, the piezoelectric properties d of KNN ceramics 33 Parameters such as mechanical quality factor Qm and dielectric loss tan deltaThe numbers tend to be difficult to balance. It should be noted that the larger the dielectric loss is, the lower the conversion rate between the electrical energy and the mechanical energy of the piezoelectric ceramic is, and at the same time, the higher the dielectric loss is a main factor causing ceramic heating, while the higher the internal temperature of the ceramic is, the larger the dielectric loss is, so that a vicious circle is formed in the working process of the ceramic, so that the working efficiency and the service life of the KNN piezoelectric ceramic are affected, and even the piezoelectric element is damaged. Therefore, the problem that the KNN-based lead-free piezoelectric ceramic is difficult to balance the piezoelectric performance and the mechanical performance is one of difficulties that prevent the lead-based piezoelectric ceramic from being replaced. In the work of KNN piezoelectric ceramics, in addition to piezoelectric property d 33 In addition, the mechanical quality factor and dielectric loss are also very important performance parameters.
Based on the above state of the art, the applicant has studied and the piezoelectric ceramics according to the embodiments of the present invention, and the preparation method and application thereof will be specifically described.
Embodiments of the invention
The embodiment of the invention provides a preparation method of piezoelectric ceramics, which comprises the following steps:
s1, proportioning: according to chemical formula 0.96[ K 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]-0.04[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]-x％molCu 2 Ta 4 O 12 (KNLS-BKNZH-x% mol CTO) and preparing to obtain a first material, wherein x has a value of [0.25,1 ]]. The embodiment of the invention is 0.96[ K ] 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]-0.04[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]Is systematically doped with Cu 2 Ta 4 O 12 To form a novel piezoelectric ceramicThe system KNNLS-BKNZH-x% mol CTO has better compactness, wider sintering temperature area, lower dielectric loss, higher piezoelectric performance and mechanical quality factor and good performance stability. Note that, [ K ] 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]Front 0.96 and [ Bi ] 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]The units corresponding to the former 0.04 are all mol, that is to say in the KNLS-BKNZH-x% molCTO system provided in the examples of the invention, three main components [ K 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]、[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]And Cu 2 Ta 4 O 12 The molar ratio is 0.96:0.04: x%.
It is further noted that in the examples of the present invention, the chemical formula was 0.96[ K ] 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]-0.04[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]-x％molCu 2 Ta 4 O 12 Calculated to correspond to greater than 99% purity of the selected starting material for each element, and alternatively, the starting material providing the Na element may be Na 2 CO 3 The raw material for providing K element can be K 2 CO 3 The raw material for providing Nb element can be Nb 2 O 5 The raw material for providing Sb element can be Sb 2 O 3 The raw material for providing Bi element may be Bi 2 O 3 The raw material for providing Li element can be Li 2 CO 3 The raw material for providing Zr element can be ZrO 2 The raw material for providing Hf element may be HfO 2 The raw material for providing Cu element can be CuO, and the raw material for providing Ta element can be Ta 2 O 5 . It should be emphasized that, among other embodiments of the present invention, not only are each provided in an embodiment of the present inventionThe raw material to which the element corresponds may be other raw materials to which each element corresponds as long as it can provide the first raw material with the corresponding element.
Further alternatively, the above formula is 0.96[ K ] 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]-0.04[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]-x％molCu 2 Ta 4 O 12 Cu in (B) 2 Ta 4 O 12 The corresponding raw materials are prepared by the following method: according to Cu 2 Ta 4 O 12 After calculation and batching of the chemical formula of (C) to obtain Cu 2 Ta 4 O 12 Raw materials; cu is added with 2 Ta 4 O 12 The raw materials are subjected to ball milling treatment and presintering in sequence. Specifically, in the case of Cu 2 Ta 4 O 12 The ball milling treatment and presintering of the raw materials in sequence comprise: in Cu 2 Ta 4 O 12 Absolute ethyl alcohol is added into the raw materials for ball milling to obtain ball milling raw materials, wherein the ball milling time is 8-24 h, and the rotating speed is 150-500 r/min, so as to ensure that the particle size of the ball milling raw materials is kept within a reasonable size range and is uniform enough; presintering the ball-milling raw materials, wherein the presintering temperature is 800-950 ℃, and the heat preservation time is 3-6 h. By doping Cu as a component 2 Ta 4 O 12 The ball milling and presintering and other technological treatments of the raw materials are carried out, so that the raw materials provide good material component basis and sufficient reaction conditions for the subsequent KNLS-BKNZH-x% mol CTO.
Preferably, in the method for preparing KNNLS-BKNZH-x% mol cto piezoelectric ceramic according to the preferred embodiment of the present invention, the value range of x is [0.5,1], and more preferably, the value of x may be 0.75 and values near thereto.
S2, ball milling is carried out on the first raw material, and presintering is carried out, so that a first product is obtained. Further specifically, in the preferred embodiment of the invention, when the first raw material is subjected to ball milling treatment, the ball milling time is 8-24 hours, and the rotating speed is 150-500 rpm, so as to ensure that the particle size of the first raw material after ball milling is kept within a reasonable size range and is uniform enough; the presintering process comprises the following steps: preserving heat for 6-10 h at 800-950 ℃. It should be noted that, by ball milling the first raw material, the powder of the first raw material can be better dispersed and the specific surface is larger, so as to facilitate the presintering of the next step; the presintering is a heat treatment process for the first raw material after ball milling, and aims to improve the components and microstructure of the first raw material, so that the subsequent processing efficiency can be increased and the processing cost can be reduced.
And S3, after the first product is molded and subjected to glue discharging, sintering, silver electrode polarization and high-voltage polarization are sequentially carried out.
Further specifically, the molding process of the first product includes: grinding the first product, adding a binder polyvinyl alcohol solution with the mass fraction of 5-12% for granulating, and tabletting with the pressure value of 10-20 MPa in a die. It should be noted that, in the embodiment of the present invention, the first product forming processing mode is a granulating and tabletting, that is, the target forming mode is a sheet shape, and the formed and processed product is a piezoelectric ceramic sheet, but in other embodiments of the present invention, the forming processing mode is not limited to the one forming processing mode of the embodiment of the present invention, and piezoelectric ceramics in other forms formed by other forming processing modes, such as a piezoelectric ceramic tube formed by extrusion molding or other forms of piezoelectric ceramic products formed by casting molding, may be provided.
Further, the purpose of the glue discharging is to remove the binder added during molding after molding, so as to provide a good material basis and a sintering environment basis for subsequent sintering.
Further, in a preferred embodiment of the present invention, the sintering process includes: firstly, preserving heat for 1-15 min at the sintering temperature of 1100-1200 ℃, and then cooling to 900-1030 ℃ for 3-25 h, wherein the cooling speed is 5-20 ℃/min. The sintering process is an important link for sintering the products after the glue is discharged into porcelain, and the heat preservation parameter and the cooling parameter are important indexes in the sintering process, so that the essential properties of the final piezoelectric ceramic are determined. In order to optimize and control the good performance of the final piezoelectric ceramic, the embodiment of the invention is required to be limited in the process of cooling to 900-1030 ℃ during sintering, wherein the cooling speed is 5-20 ℃/min (the cooling speed can inhibit the grain boundary migration after a communicated framework is formed among grains in a ceramic microstructure, and the ceramic sample is fully dense by utilizing the grain boundary diffusion effect).
Further, the silver electrode process includes: brushing silver paste on the surface of the ceramic sample sintered in the step S3, and preserving the temperature for 10-40 min at 500-900 ℃. It should be noted that, in other embodiments of the present invention, the electrode may be silver coated by sintering, chemical deposition and vacuum coating of the silver layer.
Further, the high voltage polarization process includes: and (3) placing the ceramic sheet subjected to silver electrode in a constant temperature environment of 20-90 ℃, and applying high pressure of 2-4 kv for polarization, wherein the pressure maintaining time is 15-30 min. The piezoelectric performance of the ceramic is maximized by orienting the internal electrical domains of the ceramic by high-voltage polarization. In addition, it should be noted that, the preparation method of the piezoelectric ceramic provided by the embodiment of the invention further includes an aging test, namely: the piezoelectric ceramic obtained after high-voltage polarization is aged for 24 hours at normal temperature, and then performance test is carried out (various indexes are detected after aging stabilization to see whether the expected performance requirement is met).
The embodiment of the invention also provides piezoelectric ceramics, which are prepared according to the preparation method of the piezoelectric ceramics. Optionally, in the preferred embodiment of the present invention, the content of Na, K, cu, zr, nb, sb, hf, ta and Bi elements in the piezoelectric ceramic is 6.94-7.95%, 12.16-13.17%, 0.09-0.66%, 6.01-8.78%, 55.93-59.04%, 4.08-4.69%, 4.33-5.72%, 0.72-5.36% and 1.58-2.14% by mass. It should be emphasized that, because there is a certain error in the actual testing process of the elements of the piezoelectric ceramic, the mass percentage content of the above elements provided in the embodiment of the present invention is only a preferred reference value, and in other embodiments of the present invention, the element content of the finally obtained piezoelectric ceramic is not limited by the quantization standard, so long as it is prepared according to the formulation proportion in the preparation process of the piezoelectric ceramic, and belongs to the content corresponding to each element finally obtained by reasonable inference, which is within the scope of the present invention.
It should be further emphasized that, in the method for preparing a piezoelectric ceramic and the piezoelectric ceramic provided in the embodiments of the present invention, any parameter value related to a parameter range may be any point value corresponding to the parameter range, and the method is not limited to the point value or the preferred value given in the embodiment, for example, in the ball milling process, the ball milling time is limited to 8-24 h, the rotational speed of the corresponding ball mill is limited to 150-500 rpm, the corresponding ball milling time may be any time (for example, 8.5 hours, 9 hours or 10 hours, etc.) in the 8-24 h interval, the rotational speed of the ball mill is any rotational speed (for example, 160 rpm, 182 rpm, 265 rpm, etc.) in the parameter interval cannot be listed in the embodiment, so the corresponding parameter range substantially represents each point value of the parameter interval range, and the parameter adjustment is not fully exemplified in the embodiment of the present specification.
The invention also provides application of the piezoelectric ceramic, and particularly relates to application of the piezoelectric ceramic to the technical field of laser display. Optionally, the laser display technology includes a laser display device, where the laser display device includes an optical fiber scanner, and the optical fiber scanner includes an actuating portion, where the piezoelectric ceramic is configured to the actuating portion, and the actuating portion uses an inverse piezoelectric effect of the piezoelectric ceramic to control the optical fiber on the actuating portion to perform vibration scanning, so as to implement laser scanning imaging. It should be emphasized that, in other embodiments of the present invention, the application provided by the embodiments of the present invention is not limited to this application, and may be other applications, such as configuring the piezoelectric ceramic application provided by the embodiments of the present invention as an atomization sheet.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a preparation method of piezoelectric ceramics, which comprises the following specific steps:
and (2) material preparation 1: according to chemical formula Cu 2 Ta 4 O 12 Calculating and batching;
ball milling 1: to be prepared with Cu 2 Ta 4 O 12 Putting the raw materials into a ball milling tank filled with ball milling beads, adding absolute ethyl alcohol, transferring to a ball mill for ball milling for 8-24 hours at a rotating speed of 150-500 r/min;
presintering 1: ball-milling Cu 2 Ta 4 O 12 The raw materials of (2) are transferred to a muffle furnace for presintering, the presintering temperature is 800-950 ℃, and the heat preservation time is 3-6 h, thus synthesizing Cu 2 Ta 4 O 12 A compound;
and (2) material mixing: formula 0.96[ K ] according to the present example 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]-0.04[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]-x％molCu 2 Ta 4 O 12 Performing batch calculation and batch weighing, wherein x=0.25;
ball milling 2: putting the prepared raw materials into a ball milling tank filled with ball milling beads, adding absolute ethyl alcohol, transferring to a ball mill for ball milling for 8-24 hours at a rotating speed of 150-500 rpm;
presintering 2: transferring the sample obtained in the ball milling step 2 into a muffle furnace, and preserving heat for 6-10 h at 800-950 ℃;
granulating and tabletting; placing the sample obtained in the presintering step 2 into a mortar, finely grinding, adding a binder PVA solution (5-12 wt%) for granulating, pouring into a die with the diameter of 10-15 mm, and tabletting under the pressure of 10-20 MPa by using a powder tabletting machine;
and (3) glue discharging: transferring the sample obtained by granulating and tabletting into a glue discharging furnace, and preserving heat at 500-950 ℃ to discharge glue;
sintering: sintering the sample obtained after the glue discharging by adopting a two-step sintering method, wherein the sintering temperature of the first step is 1100-1200 ℃, the temperature is kept for 1-15 min, the temperature is quickly reduced to 900-1030 ℃, and the temperature is kept for 3-25 h;
silver electrode: brushing silver paste on the upper and lower surfaces of the sintered KNNLS-BKNZH-0.25% mol CTO leadless piezoelectric ceramics, and preserving heat for 10-40 min at 500-900 ℃; placing the treated silver-plated ceramic sheet into a silicon oil bath with constant temperature of 20-90 ℃, and applying high voltage of 2-4 KV for polarization, wherein the pressure maintaining time is 15-30 min; and aging for at least 24 hours at normal temperature after polarization.
The embodiment of the invention also provides the piezoelectric ceramic, which is prepared by the preparation method of the piezoelectric ceramic provided by the embodiment.
The embodiment of the invention also provides an application of the piezoelectric ceramic, which comprises the following steps: the piezoelectric ceramic provided in the present embodiment is configured as an actuating portion on an optical fiber scanner in the technical field of laser display.
Example 2
The present embodiment provides a method for producing a piezoelectric ceramic, which is substantially the same as that of the piezoelectric ceramic of embodiment 1, except that in the method for producing a piezoelectric ceramic of embodiment, x is 0.5, that is, the formula chemical formula is 0.96[ K ] 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]-0.04[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]-0.5％molCu 2 Ta 4 O 12 。
The embodiment of the invention also provides the piezoelectric ceramic, which is prepared by the preparation method of the piezoelectric ceramic provided by the embodiment.
The embodiment of the invention also provides an application of the piezoelectric ceramic, which comprises the following steps: the piezoelectric ceramic provided in the present embodiment is configured as an actuating portion on an optical fiber scanner in the technical field of laser display.
Example 3
The present embodiment provides a method for producing a piezoelectric ceramic, which is substantially the same as that of the piezoelectric ceramic of embodiment 1, except that in the method for producing a piezoelectric ceramic of embodiment, x is 0.75, that is, the formula chemical formula is 0.96[ K ] 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]-0.04[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]-0.75％molCu 2 Ta 4 O 12 。
The embodiment of the invention also provides the piezoelectric ceramic, which is prepared by the preparation method of the piezoelectric ceramic provided by the embodiment.
The embodiment of the invention also provides an application of the piezoelectric ceramic, which comprises the following steps: the piezoelectric ceramic provided in the present embodiment is configured as an actuating portion on an optical fiber scanner in the technical field of laser display.
Example 4
The present embodiment provides a method for producing a piezoelectric ceramic, which is substantially the same as that of the piezoelectric ceramic of embodiment 1, except that in the method for producing a piezoelectric ceramic of embodiment, x is 1, that is, the formula chemical formula is 0.96[ K ] 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]-0.04[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]-1％molCu 2 Ta 4 O 12 。
The embodiment of the invention also provides the piezoelectric ceramic, which is prepared by the preparation method of the piezoelectric ceramic provided by the embodiment.
The embodiment of the invention also provides an application of the piezoelectric ceramic, which comprises the following steps: the piezoelectric ceramic provided in the present embodiment is configured as an actuating portion on an optical fiber scanner in the technical field of laser display.
Test examples
In order to verify and prove the beneficial effects of the piezoelectric ceramic and the preparation method thereof provided by the embodiment of the invention, the samples provided by the embodiments 1-4 are used as test examples for analysis, test and characterization, and the results are as follows:
firstly, SEM characterization test is performed, as shown in fig. 1, it can be known from fig. 1 that as CTO content increases, the density of KNNLS-BKNZH-x% mol CTO piezoelectric ceramic is increased and then decreased, and the density of ceramic is the best when x=0.75, but as a whole, the density of KNNLS-BKNZH-x% mol CTO piezoelectric ceramic provided by the embodiment of the invention is better.
Further, as shown in fig. 2, the results of XRD characterization test are that, as shown in fig. 2, KNNLS-BKNZH-x% mol CTO piezoelectric ceramic has R-T multiphase coexisting crystal structure at x=0.25, 0.5, 0.75 and 1.00, the sample has typical perovskite structure, the doping of CTO does not significantly change the position of each characteristic peak of ceramic in XRD, which indicates that the addition of CTO does not change lattice parameter of KNNLS-BKNZH piezoelectric ceramic and has no significant hetero-phase structure.
It should be further noted that, because there may be loss of some elements and volatilization of oxides such as carbon dioxide during sintering, the stoichiometric ratio after sintering is different from the design formula, so in the test example of the present invention, tests of element content and spectrogram of the ceramic after sintering of the KNNLS-BKNZH-x% molCTO lead-free piezoelectric ceramic are also performed, and the element proportions and spectrogram are shown in the following table 2 and fig. 3 a-3 d, respectively. It can be confirmed from table 2 and fig. 3a to 3d that "the mass percentages of Na, K, cu, zr, nb, sb, hf, ta and Bi elements in the piezoelectric ceramic in the embodiment of the present invention are 6.94 to 7.95%, 12.16 to 13.17%, 0.09 to 0.66%, 6.01 to 8.78%, 55.93 to 59.04%, 4.08 to 4.69%, 4.33 to 5.72%, 0.72 to 5.36% and 1.58 to 2.14%, respectively. "
Further, the embodiment of the invention provides the d of the KNLS-BKNZH-x% mol CTO lead-free piezoelectric ceramic sheet 33 And kp curves and data are shown in fig. 4. As can be seen from the data of FIG. 4, the piezoelectric properties of KNNLS-BKNZH-x% mol CTO ceramics gradually decrease with increasing CTO, but the electromechanical coupling systemThe number tends to increase gradually with the addition of CTO, kp is at most 0.43 when x=0.75, and d 33 And kp reaches an ideal equilibrium state.
Further, the curves and data of Qm and tan delta of the KNNLS-BKNZH-x% mol CTO lead-free piezoelectric ceramic wafer provided by the embodiment of the invention are shown in figure 5. As can be seen from fig. 5, as CTO increases, qm of KNNLS-BKNZH-x% mol CTO piezoelectric ceramic gradually increases, and when x=0.75, qm is 96 at maximum; at the same time, the dielectric loss also decreased first and then increased with increasing CTO, with a minimum of 2.27% when x=0.75, which corresponds to the SEM test conclusion in fig. 1 and the conclusion of the maximum kp when x=0.75 in fig. 4.
Further, the curie temperature and the dielectric constant of the KNNLS-BKNZH-x% mol cto lead-free piezoelectric ceramic provided by the embodiment of the invention are shown in fig. 6, and as can be seen from fig. 6, the KNNLS-BKNZH-x% mol cto piezoelectric ceramic has a higher curie temperature and dielectric constant as a whole, and when x=0.75, the curie temperature is 199 ℃, the dielectric constant is 2756, and the best performance balance state is achieved.
Further, the dielectric temperature curves measured by the KNNLS-BKNZH-x% mol CTO lead-free piezoelectric ceramic at 1000hz are shown in fig. 7a to 7d, and as can be seen from the combination of fig. 7a to 7d, the piezoelectric ceramic provided by the embodiment of the invention has lower dielectric loss and higher dielectric constant.
Furthermore, according to the conclusion of the above various tests, the present application also researches the temperature stability of the KNNLS-BKNZH-x% mol cto leadless piezoelectric ceramics and the preparation method thereof provided by the embodiments of the present invention:
in particular, it is known that, in summary, KNNLS-BKNZH-x% mol cto lead-free piezoelectric ceramic has optimal density and optimal piezoelectric and mechanical properties at x=0.75; meanwhile, in the research of the application, the addition of CTO greatly widens the sintering temperature zone of KNLS-BKNZH-x% mol CTO lead-free piezoelectric ceramics. It is known that the traditional KNN-based lead-free piezoelectric ceramic is very sensitive to sintering temperature, and the change of 5-10 ℃ often causes larger change of density and performance, which is also an important influence factor for preventing the KNN-based lead-free piezoelectric ceramic from replacing lead-based piezoelectric ceramic from vector production and industrialization. Thus, the present application investigated the densification and performance of KNNLS-BKNZH-x% mol cto lead-free piezoelectric ceramics after sintering at 980 ℃, 1000 ℃, 1030 ℃, 1060 ℃ and 1090 ℃ at x=0.75, respectively.
More specifically, FIG. 8 is an SEM image of KNLS-BKNZH-0.75% mol CTO ceramic sintered at 980-1090 ℃. Referring to fig. 8, it can be seen that the KNNLS-BKNZH-0.75% mol cto piezoelectric ceramic provided by the embodiment of the invention has better compactness after sintering at 980 ℃, 1000 ℃, 1030 ℃, 1060 ℃ and 1090 ℃, which indicates that the KNN system piezoelectric ceramic has the characteristics of good temperature stability, wide sintering temperature range and low-temperature sintering.
Further, FIG. 9 shows the piezoelectric properties d of the KNNLS-BKNZH-0.75% mol CTO piezoelectric ceramics sintered at 980 ℃, 1000 ℃, 1030 ℃, 1060 ℃ and 1090 ℃ according to the embodiment of the invention 33 And a graph of the mechanical quality factor Qm, table 3 is a corresponding parameter table.
TABLE 3 parameters of KNLS-BKNZH-0.75% mol CTO at different temperatures provided in the examples of the invention
As can be seen from fig. 8 and 9 and table 3, the KNNLS-BKNZH-x% mol cto piezoelectric ceramic has better compactness and piezoelectric performance after being sintered at 980-1090 ℃, the sintering temperature zone reaches 110 ℃ wide, which has not been reported in the previous study of KNN-based leadless piezoelectric ceramic system, the study result of the application effectively avoids the difficult problem of temperature sensitivity of KNN-based ceramic system, and simultaneously the sintering temperature is reduced from 1120-1090 ℃ to 980-1090 ℃ of the traditional KNN ceramic powder, so that the deviation of stoichiometric ratio and the reduction of crystal compactness caused by volatilization of alkali metal ions such as K and Na can be avoided in the sintering process. In addition, it is emphasized that the problem of volatilization and poor compactness of alkali metal caused by high temperature sensitivity and sintering temperature has been a serious problem for a long time, which plagues researchers and hinders the research of KNN ceramic powder from going to mass production and industrialization. By introducing CTO into KNN ceramic system, the sintering temperature is reduced (from 1120-1090deg.C to 980-1090deg.C), the sintering temperature zone is widened (from 5-10deg.C to 110deg.C), and the research result has profound significance for replacing lead-based piezoelectric ceramic with KNN-based lead-free piezoelectric ceramic and becoming industrialized piezoelectric ceramic powder.
In summary, the piezoelectric ceramic and the preparation method thereof provided by the embodiment of the invention are implemented by mixing K 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 、Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 Cu and Cu 2 Ta 4 O 12 The reasonable configuration is carried out, so that the piezoelectric ceramic provided by the application can simultaneously realize the reduction of sintering temperature, the widening of sintering temperature area, the improvement of the compactness, the process stability and the mechanical quality factor of the piezoelectric ceramic and the reduction of dielectric loss, and further the process mass production stability and the product application effect are excellent, and therefore, the piezoelectric ceramic and the preparation method thereof provided by the embodiment of the application have important industrial mass production application value.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (10)
1. The preparation method of the piezoelectric ceramic is characterized by comprising the following steps of:
selecting raw materials according to chemical formula 0.96[ K ] 0.48 Na 0.52 Nb 0.949 Li 0.001 Sb 0.05 O 3 ]-0.04[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]-x％molCu 2 Ta 4 O 12 Calculating and batching to obtain a first raw material, wherein the value range of x is [0.25,1 ]]；
Ball milling is carried out on the first raw material, and presintering is carried out to obtain a first product;
and after the first product is molded and adhesive is discharged, sintering, silver electrode polarization and high-voltage polarization are sequentially carried out.
2. The method of producing a piezoelectric ceramic according to claim 1, wherein the ratio of 0.96[ k ] 0.48 Na 0.52 Nb 0.94 9 Li 0.001 Sb 0.05 O 3 ]-0.04[Bi 0.5 (K 0.15 Na 0.85 ) 0.5 Zr 0.15 Hf 0.85 O 3 ]-x％molCu 2 Ta 4 O 12 In (2) said Cu 2 Ta 4 O 12 The corresponding raw materials are prepared by the following method:
according to Cu 2 Ta 4 O 12 After calculation and batching of the chemical formula of (C) to obtain Cu 2 Ta 4 O 12 Raw materials;
the Cu is treated with 2 Ta 4 O 12 The raw materials are subjected to ball milling treatment and presintering in sequence.
3. The method of producing a piezoelectric ceramic according to claim 2, wherein, in the case of the Cu 2 Ta 4 O 12 The ball milling treatment and presintering of the raw materials in sequence comprise:
at the Cu 2 Ta 4 O 12 Adding absolute ethyl alcohol into the raw materials for ball milling to obtain ball milling raw materials, wherein the ball milling time is 8-24 h, and the rotating speed is 150-500 r/min;
presintering the ball-milling raw materials, wherein the presintering temperature is 800-950 ℃, and the heat preservation time is 3-6 h.
4. A method of producing a piezoelectric ceramic according to any one of claims 1 to 3, wherein the value of x is in the range of [0.5,1].
5. The method of manufacturing a piezoelectric ceramic according to claim 4, wherein the value of x is 0.75.
6. The method for producing a piezoelectric ceramic according to claim 1, wherein when the first raw material is subjected to the ball milling treatment, the ball milling time is 8 to 24 hours, and the rotational speed is 150 to 500 rotations per minute; and the presintering comprises the following steps: preserving heat for 6-10 h at 800-950 ℃;
the molding process of the first product includes: grinding the first product, adding a binder polyvinyl alcohol solution with the mass fraction of 5-12% for granulating, and tabletting with the pressure value of 10-20 MPa in a die.
7. The method of manufacturing a piezoelectric ceramic according to claim 6, wherein the sintering is performed by: firstly preserving heat for 1-15 min at the sintering temperature of 1100-1200 ℃, and then reducing the temperature to 900-1030 ℃ for 3-25 h, wherein the temperature reduction speed is 5-20 ℃/min.
8. A piezoelectric ceramic, characterized in that it is produced according to the production method of a piezoelectric ceramic according to any one of claims 1 to 7.
9. The piezoelectric ceramic according to claim 8, wherein the content of Na, K, cu, zr, nb, sb, hf, ta and Bi elements in the piezoelectric ceramic is 6.94 to 7.95%, 12.16 to 13.17%, 0.09 to 0.66%, 6.01 to 8.78%, 55.93 to 59.04%, 4.08 to 4.69%, 4.33 to 5.72%, 0.72 to 5.36%, and 1.58 to 2.14%, respectively.
10. Use of a piezoelectric ceramic according to claim 8 or 9, in the field of laser display technology.
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