CN111925209A - Lead-free sound vibration piezoelectric transduction material and preparation method thereof - Google Patents
Lead-free sound vibration piezoelectric transduction material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a leadless sound vibration piezoelectric transduction material and a preparation method thereof, and the leadless sound vibration piezoelectric transduction material comprises the following chemical compositions: (1-x) (K)0.5Na0.5)(Nb0.95Sb0.05)O3‑xBi0.5(Na0.82K0.18)0.5HfO3Wherein x is 0.03-0.05. The preparation process provided by the invention is simple and environment-friendly, and the prepared lead-free acoustic vibration piezoelectric transduction material has a high piezoelectric constant, a good temperature stability within a certain temperature range and a wide application value.
Description
Technical Field
The application belongs to the technical field of lead-free piezoelectric ceramics, and particularly relates to a preparation method of a lead-free acoustic vibration piezoelectric transduction material.
Background
Piezoelectric ceramics have been widely used in a variety of electronic devices such as sensors, actuators, and the like. The conventional lead-based ceramics, although excellent in performance, are harmful to the environment and human health, and therefore, the development of high-performance lead-free materials has been diligent. In recent years, the number of studies on lead-free piezoelectric ceramics is large, and at present, studies on lead-free piezoelectric materials are mainly focused on systems such as bismuth sodium titanate (BNT), potassium sodium niobate (KNN), Barium Calcium Zirconate Titanate (BCZT), and the like. After long-time research, the lead-free piezoelectric ceramic materials have made certain progress in preparation and performance, but each material system has obvious defects on the whole, and no lead-free piezoelectric material can completely replace a lead-based material. Wherein the potassium sodium niobate-based ceramic [ (K, Na) NbO3,KNN]It shows great development potential due to its high piezoelectric coefficient and Curie transition temperature.
The current research on the potassium-sodium niobate-based piezoelectric ceramic material mainly focuses on designing a polymorphic phase boundary by using element doping so as to improve the piezoelectric performance of the material. Although the piezoelectric performance of the piezoelectric ceramic has been improved to some extent by means of element doping, the curie temperature of the piezoelectric ceramic is also generally drastically reduced with increasing content of the doping element, thereby affecting the temperature stability of the piezoelectric ceramic. In addition, the ceramic forming temperature of the ceramic is obviously different along with the change of the content of the doping element by using the element doping means, thereby bringing great difficulty to the sintering of the ceramic. Therefore, obtaining a good temperature stability characteristic within a certain temperature range while ensuring a high piezoelectric constant is a key problem to be solved for the practical application of the lead-free piezoelectric ceramic.
When the KNN-based ceramic is prepared, the problems of increased defects in the structure, low mechanical quality factor, weakened dielectric property and the like caused by the segregation of components volatilized by potassium and sodium elements in a system due to overhigh sintering temperature generally exist.
In order to improve the sinterability and electrical properties of the KNN-based ceramic, it is generally achieved by adding a sintering aid and a low-temperature solid solution having good sinterability. However, in order to prevent the formation of a foreign phase in the KNN-based ceramic structure and to improve the stability of the electrical properties, a high-quality powder of nano-micron level having a uniform composition, good crystallinity and a narrow particle size distribution is often required.
Aiming at the preparation of high-quality nano-micron powder, a solid phase method is rarely adopted generally, and the powder prepared by the solid phase method has large composition fluctuation, larger particle size, wide particle size distribution and the like; although the liquid phase method can prepare high quality powder with narrow particle size distribution and uniform components, the liquid phase method has the disadvantages of relatively complex process operation, relatively high equipment cost, difficulty in mass production and the like.
Therefore, optimizing the preparation process, realizing industrial mass production, and finally realizing mass continuous production of the lead-free piezoelectric ceramic material with excellent electrical properties is another important problem to be solved urgently in the field.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a leadless sound vibration piezoelectric transduction material with brand new components and a preparation method of the leadless sound vibration piezoelectric transduction material with optimized process.
Firstly, the invention provides a lead-free sound vibration piezoelectric transduction material, which comprises the following chemical components:
(1-x)(K0.5Na0.5)(Nb0.95Sb0.05)O3-xBi0.5(Na0.82K0.18)0.5HfO3wherein x is 0.03-0.05, preferably x is 0.035.
In another aspect of the invention, a preparation method of the lead-free acoustic vibration piezoelectric transduction material is also provided, wherein the preparation raw material comprises Na2CO3、K2CO3、Nb2O5、Sb2O3、Bi2O3、HfO2And polyethylene glycol.
Further, the preparation method comprises the following steps:
(1) using analytically pure Na2CO3、K2CO3、Nb2O5、Sb2O3、Bi2O3、HfO2Is prepared from raw materials according to the chemical formula (1-x) (K)0.5Na0.5)(Nb0.95Sb0.05)O3-xBi0.5(Na0.82K0.18)0.5HfO3Weighing the molar ratio of the medium metal atoms, and then performing ball milling for 20-30 h to obtain nano powder;
(2) calcining the obtained nano powder for 4-6h at the temperature of 850-900 ℃;
(3) mixing the calcined powder in the step (2) with an adhesive, and pressing and forming;
(4) and sintering and polarizing the press-formed sample to obtain the lead-free acoustic vibration piezoelectric transduction material.
Preferably, wherein step (1) is performed to Na2CO3、K2CO3、Nb2O5、Sb2O3、Bi2O3、HfO2Adding absolute ethyl alcohol into the mixture, and carrying out ball milling; the addition of the absolute ethyl alcohol can increase the viscosity of the raw materials, so that the mixing and grinding are more sufficient, the obtained powder is finer and more uniform, and the ball milling time is preferably 10 to 30 hours. Further, preferably, the ball milling time is 24 hours; during the mixing and grinding process, the powder becomes finer and more uniform.
Wherein, the calcining in the step (2) aims to ensure that the solid phase chemical reaction of each raw material is sufficient and uniform, so as to generate solid solution with fixed composition components and form a main crystal phase; and carbon dioxide and moisture in the raw materials are removed, and the sintering shrinkage and deformation of the rough blank are reduced, so that the appearance size of the ceramic product is controlled. Preferably, the calcination temperature is 850 ℃ and the calcination time is 6h, and under the pre-sintering condition, the solid-phase chemical reaction of each raw material is more sufficient and uniform.
Preferably, in the step (3), the calcined powder is mixed with polyethylene glycol (PVA), wherein the mass concentration of the PVA is 6-8%, more preferably, the mass concentration of the PVA is 8%, and more preferably, the addition amount of the PVA is 5-8% of the mass of the powder; the press forming refers to pressing a sample with the diameter of 10mm and the thickness of 1mm under the pressure of 10 Mpa.
Preferably, in the step (4), the sample is burnt in air at 1060-1090 ℃ for 1-4 hours.
More preferably, in the sintering in the step (4), the temperature is increased from room temperature to 150 ℃ at the speed of 10 ℃/min, the temperature is kept for 20min, then the temperature is increased to 500 ℃ at the speed of 10 ℃/min, finally the temperature is increased at the speed of 10 ℃/min, the sintering is carried out at the temperature of 1060 ℃ -1090 ℃, the sintering is carried out for 1-2 h, and then the sintering is naturally cooled to 20-30 ℃.
Further, the polarization in step (4) is preferably performed by plating electrodes on the ceramic element to facilitate polarization; and then, putting the ceramic element into 20 ℃ silicone oil, and applying 1-3kV/mm direct current to polarize for 5-15 min. Further preferably, the electrode is plated on the ceramic element by vacuum coating, and the ceramic element is plated with silver.
The invention has the beneficial effects that:
the inventor of the application researches the influence of different doping elements and multi-component doping on the electromechanical coupling performance of the material through a large number of experiments, and unexpectedly discovers that three elements of Sb, Bi and Hf are simultaneously doped in the lead-free piezoelectric ceramic, and the content of each chemical metal element is determined to have a chemical composition of (1-x) (K)0.5Na0.5)(Nb0.95Sb0.05)O3-xBi0.5(Na0.82K0.18)0.5HfO3And when x is 0.03-0.05, the inhomogeneous distribution of chemical components on the microscale of the lead-free piezoelectric ceramic material can be realized, so that a nano domain structure with ultrahigh ferroelectric activity is constructed, and the level of the lead-containing ceramic is reached.
In addition, the inventor finally creatively proposes through optimizing the piezoelectric material preparation process and flow, particularly the influence of the pre-sintering temperature, the post-treatment mode and the like on the electromechanical coupling performance of the material, and not only avoids the problems of increased defects in the structure, low mechanical quality factor, weakened dielectric property and the like caused by the segregation of components volatilized by potassium and sodium elements in a system due to overhigh temperature, but also can fully volatilize PVA and ensure the sintering effect.
In addition, the lead-free piezoelectric ceramic material containing the chemical components doped with the Sb, Bi and Hf elements is prepared by the process method, the obtained powder has the advantages of superfine property, high purity, good fluidity, narrow particle size distribution, light particle agglomeration degree and the like, and the prepared lead-free piezoelectric ceramic powder can be used for obtaining compact ceramic with the density of more than 98.5 percent of the theoretical density, and the electromechanical coupling factor is more than 36 percent.
The piezoelectric coefficient of the lead-free piezoelectric ceramic provided by the invention can reach 580pC/N, and the lead-free piezoelectric ceramic has higher Curie temperature Tc. The temperature is increased from 20 ℃ to 160 ℃, the piezoelectric coefficient is reduced by only 10 percent, and the ceramic has excellent stability performance, namely 10 DEG C6The normal work can still be carried out after one cycle.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
EXAMPLE 1 preparation of lead-free piezoceramic Material
Has a chemical formula of
0.965(K0.5Na0.5)(Nb0.95Sb0.05)O3-0.035Bi0.5(Na0.82K0.18)0.5HfO3The lead-free piezoelectric ceramic material is prepared by the following steps:
using analytically pure Na2CO3(99.8％)、K2CO3(99％)、Nb2O5(99.5％)、Sb2O3(99.99％)、Bi2O3(99.999％)、HfO2(99%) as raw materials, weighing according to the molar ratio of metal atoms in the chemical formula, ball-milling for 24 hours by taking ethanol as a medium, and then drying;
calcining the dried nano powder for 6 hours at the temperature of 850 ℃; mixing the calcined powder with a PVA aqueous solution with the mass concentration of 8% for granulation, and pressing the mixture into a sample with the diameter of 10mm and the thickness of 1mm under the pressure of 10 Mpa;
heating the sample from room temperature to 150 ℃ at the speed of 10 ℃/min, preserving the heat for 40min, removing the water adsorbed on the surface and the interior and removing PVA, and finally slowly volatilizing the PVA; then heating to 500 ℃ at the speed of 10 ℃/min, finally continuing heating at the speed of 10 ℃/min, sintering at 1060-1090 ℃ for 2h, and finally naturally cooling to 20-30 ℃;
and the polarization process comprises silver coated electrode and polarization, silver paste is uniformly coated on the upper surface and the lower surface of the sample by adopting a vacuum coating method to form the silver electrode with good conductivity, the silver coated sample is put into silicon oil with the temperature of 20 ℃ and direct current of 1 kV/mm, 2 kV/mm and 3kV/mm is applied to carry out polarization, and the polarization time is respectively 5min, 10 min and 15 min.
EXAMPLE 2 piezoelectric Performance test
The polarized lead-free piezoelectric ceramic sample prepared in example 1 was left to stand for 24 hours naturally, and the performance thereof was tested. The density is 98.5% of the theoretical density; piezoelectric coefficientd33At 580pC/N, its inverse piezoelectric coefficient d33﹡, the fluctuation of the temperature is not more than 10% in the temperature range of 20-100 ℃. Curie temperature Tc of 320 ℃ at 106The normal work can still be carried out after one cycle.
EXAMPLE 3 preparation of lead-free piezoceramic Material
Chemical formula is 0.97 (K)0.5Na0.5)(Nb0.95Sb0.05)O3-0.03Bi0.5(Na0.82K0.18)0.5HfO3The lead-free piezoelectric ceramic material is prepared by the following steps:
using analytically pure Na2CO3(99.8％)、K2CO3(99％)、Nb2O5(99.5％)、Sb2O3(99.99％)、Bi2O3(99.999％)、HfO2(99%) as raw materials, weighing according to the molar ratio of metal atoms in the chemical formula, ball-milling for 20h by taking ethanol as a medium, and then drying;
calcining the dried nano powder for 5 hours at the temperature of 900 ℃; mixing the calcined powder with a PVA aqueous solution with the mass concentration of 6% for granulation, and pressing the mixture into a sample with the diameter of 10mm and the thickness of 1mm under the pressure of 10 Mpa;
heating the sample from room temperature to 150 ℃ at the speed of 10 ℃/min, preserving the heat for 40min, removing the water adsorbed on the surface and the interior and removing PVA, and finally slowly volatilizing the PVA; then heating to 500 ℃ at the speed of 10 ℃/min, finally continuing heating at the speed of 10 ℃/min, sintering at 1060-1090 ℃ for 1.5h, and finally naturally cooling to 20-30 ℃;
and the polarization process comprises silver coated electrode and polarization, silver paste is uniformly coated on the upper surface and the lower surface of the sample by adopting a vacuum coating method to form the silver electrode with good conductivity, the silver coated sample is put into silicon oil with the temperature of 20 ℃ and direct current of 1 kV/mm, 2 kV/mm and 3kV/mm is applied to carry out polarization, and the polarization time is respectively 5min, 10 min and 15 min.
EXAMPLE 4 piezoelectric Performance test
The polarized leadless piezoelectric ceramic sample prepared in example 3 is naturally placed for 24h, and the performance of the sample is improvedAnd (6) testing. The density is 98.2% of the theoretical density; piezoelectric coefficient d33560pC/N, reverse piezoelectric coefficient d33﹡, the fluctuation of the temperature is not more than 10% in the temperature range of 20-100 ℃; curie temperature Tc of 310 ℃ at 106The normal work and the density can still be realized after one cycle.
EXAMPLE 5 preparation of lead-free piezoceramic Material
Chemical formula is 0.95 (K)0.5Na0.5)(Nb0.95Sb0.05)O3-0.05Bi0.5(Na0.82K0.18)0.5HfO3The lead-free piezoelectric ceramic material is prepared by the following steps:
using analytically pure Na2CO3(99.8％)、K2CO3(99％)、Nb2O5(99.5％)、Sb2O3(99.99％)、Bi2O3(99.999％)、HfO2(99%) as raw materials, weighing according to the molar ratio of metal atoms in the chemical formula, ball-milling for 30h by taking ethanol as a medium, and then drying;
calcining the dried nano powder for 4 hours at the temperature of 850 ℃; mixing the calcined powder with a PVA aqueous solution with the mass concentration of 7% for granulation, and pressing the mixture into a sample with the diameter of 10mm and the thickness of 1mm under the pressure of 10 Mpa;
heating the sample from room temperature to 150 ℃ at the speed of 10 ℃/min, preserving the heat for 40min, removing the water adsorbed on the surface and the interior and removing PVA, and finally slowly volatilizing the PVA; then heating to 500 ℃ at the speed of 10 ℃/min, finally continuing heating at the speed of 10 ℃/min, sintering at 1060-1090 ℃ for 2h, and finally naturally cooling to 20-30 ℃;
and the polarization process comprises silver coated electrode and polarization, silver paste is uniformly coated on the upper surface and the lower surface of the sample by adopting a vacuum coating method to form the silver electrode with good conductivity, the silver coated sample is put into silicon oil with the temperature of 20 ℃ and direct current of 1 kV/mm, 2 kV/mm and 3kV/mm is applied to carry out polarization, and the polarization time is respectively 5min, 10 min and 15 min.
EXAMPLE 6 piezoelectric Performance test
Example 5 preparationThe polarized lead-free piezoelectric ceramic sample is naturally placed for 24 hours, and the performance of the lead-free piezoelectric ceramic sample is tested. Its density is 98.3% of theoretical density; piezoelectric coefficient d33570pC/N, and a reverse piezoelectric coefficient d33﹡, the fluctuation of the temperature is not more than 10% in the temperature range of 20-100 ℃. Curie temperature Tc of 300 ℃ at 106The normal work can still be carried out after one cycle.
In light of the foregoing description of the preferred embodiments according to the present application, it is to be understood that various changes and modifications may be made without departing from the spirit and scope of the invention. The technical scope of the present application is not limited to the contents of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. The lead-free sound vibration piezoelectric transduction material is characterized by comprising the following chemical components:
(1-x)(K0.5Na0.5)(Nb0.95Sb0.05)O3-xBi0.5(Na0.82K0.18)0.5HfO3wherein x is 0.03-0.05.
2. The lead-free vibro-acoustic piezoelectric transduction material of claim 1, wherein x is 0.035.
3. A method for preparing the lead-free acoustic vibration piezoelectric transduction material according to claim 1, wherein the raw material for preparation comprises Na2CO3、K2CO3、Nb2O5、Sb2O3、Bi2O3、HfO2And polyethylene glycol.
4. The method of claim 3, comprising the steps of:
(1) using analytically pure Na2CO3、K2CO3、Nb2O5、Sb2O3、Bi2O3、HfO2Is prepared from raw materials according to the chemical formula (1-x) (K)0.5Na0.5)(Nb0.95Sb0.05)O3-xBi0.5(Na0.82K0.18)0.5HfO3Weighing the molar ratio of the medium metal atoms, and then performing ball milling for 20-30 h to obtain nano powder;
(2) calcining the obtained nano powder for 4-6h at the temperature of 850-900 ℃;
(3) mixing the calcined powder in the step (2) with an adhesive, and pressing and forming;
(4) and sintering and polarizing the press-formed sample to obtain the lead-free acoustic vibration piezoelectric transduction material.
5. The method of claim 4, wherein step (1) is performed to Na2CO3、K2CO3、Nb2O5、Sb2O3、Bi2O3、HfO2Adding absolute ethyl alcohol into the mixture, and carrying out ball milling for 24 hours.
6. The preparation method according to claim 4, wherein in the step (3), the calcined powder is mixed with polyethylene glycol, wherein the mass concentration of the polyethylene glycol is 6-8%.
7. The method according to claim 4, wherein the press forming in step (3) is pressing a sample having a diameter of 10mm and a thickness of 1mm under a pressure of 10 MPa.
8. The method according to claim 4, wherein the sample is fired in the air at 1060 to 1090 ℃ for 1 to 4 hours in the step (4).
9. The preparation method according to claim 4, wherein in the sintering in the step (4), the temperature is increased from room temperature to 150 ℃ at a speed of 10 ℃/min, the temperature is kept for 40min, then the temperature is increased to 500 ℃ at a speed of 10 ℃/min, finally the temperature is increased at a speed of 10 ℃/min, and the sintering is carried out at 1060 ℃ to 1090 ℃ for 1-2 h.
10. The preparation method according to claim 4, wherein the polarization process in step (4) comprises silver-coated electrode and high-voltage polarization, wherein the silver-coated electrode is vacuum-coated, and the high-voltage polarization is performed by putting a sample on the electrode, and then putting the sample in 20 ℃ silicone oil and applying 1-3kV/mm direct current to the sample for polarization, and the polarization time is 5-15 min.
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