CN108727024B - Leadless piezoelectric ceramic and preparation method thereof - Google Patents
Leadless piezoelectric ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 8
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- 230000010287 polarization Effects 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 12
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 12
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
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- 239000008187 granular material Substances 0.000 claims description 10
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- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
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- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
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- 150000002500 ions Chemical class 0.000 description 8
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- 229910021190 Li0.5TiO3 Inorganic materials 0.000 description 6
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000002269 spontaneous effect Effects 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
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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 4
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 4
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention discloses a lead-free piezoelectric ceramic and a preparation method thereof. The lead-free piezoelectric ceramic is represented by the following chemical formula I: (1-x-y) KaNabNbO3‑xBi0.5‑cMcLi0.5TiO3‑yBaHfO3+zMnO2(I) Wherein M is selected from any one of Ce, Sm, Nd and La, wherein x, y, z, a and b represent atomic percent, and z is MnO2Occupying compound (1-x-y) KaNabNbO3‑xBi1/2‑cMcLi1/ 2TiO3‑yBaHfO3Wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.10, z is more than 0 and less than or equal to 0.05, a is more than or equal to 0.2 and less than or equal to 0.8, b is more than or equal to 0.2 and less than or equal to 0.8, and c is more than or equal to 0 and less than or equal to 0.30.
Description
Technical Field
The invention relates to the technical field of piezoelectric ceramics, in particular to lead-free piezoelectric ceramics and a preparation method thereof.
Background
Piezoelectric ceramics can realize interconversion between electrical energy and mechanical energy, and have been widely used in sensors, drivers, transducers, frequency control devices, and electroacoustic devices. For example, acceleration sensors, camera focus motors, ultrasonic sensors, resonators, speakers, and the like.
The lead zirconate titanate based piezoelectric ceramic has the outstanding advantages of high piezoelectric performance, high temperature stability, high Curie temperature, adjustable performance and the like, and is most widely applied. However, in the lead zirconate titanate-based piezoelectric ceramic, the mass fraction of lead exceeds 60%. Lead and its compounds are highly toxic and seriously threaten the environment and human health.
At present, the comprehensive performance of potassium-sodium niobate ceramics is closest to that of lead zirconate titanate ceramics in lead-free piezoelectric ceramics. Although the piezoelectric coefficient of the pure potassium sodium niobate ceramic is only 80-120pC/N, the piezoelectric performance can be effectively improved by forming a solid solution with other perovskite phases and constructing a polycrystalline phase boundary or a morphotropic phase boundary. However, the phase transition temperature region of the potassium-sodium niobate ceramic is narrow, and the temperature stability of the corresponding piezoelectric performance is very poor, so that the use requirement of electronic equipment cannot be met.
Disclosure of Invention
The invention aims to provide a novel technical scheme of lead-free piezoelectric ceramics.
According to a first aspect of the present invention, there is provided a lead-free piezoelectric ceramic represented by the following chemical formula I:
(1-x-y)KaNabNbO3-xBi0.5-cMcLi0.5TiO3-yBaHfO3+zMnO2(I)
wherein M is any one of Ce, Sm, Nd and La,
wherein x, y, z, a and b represent atomic percent, and z is MnO2Occupying compound (1-x-y) KaNabNbO3-xBi1/2- cMcLi1/2TiO3-yBaHfO3The value of the mass percentage of (c),
wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.10, z is more than 0 and less than or equal to 0.05, a is more than or equal to 0.2 and less than or equal to 0.8, b is more than or equal to 0.2 and less than or equal to 0.8, and c is more than or equal to 0 and less than or equal to 0.30.
Optionally, x is more than or equal to 0.01 and less than or equal to 0.03, y is more than or equal to 0.05 and less than or equal to 0.08, z is more than or equal to 0.01 and less than or equal to 0.03, a is more than or equal to 0.4 and less than or equal to 0.6, b is more than or equal to 0.4 and less than or equal to 0.6, and c is more than or equal to 0.10.
Optionally, M is La.
Optionally, the lead-free piezoelectric ceramic is in a three-phase and four-phase coexistent state.
According to another aspect of the present invention, there is provided a method for preparing a lead-free piezoelectric ceramic, comprising the steps of:
s1, batching:
with K2CO3、Na2CO3、Li2CO3、BaCO3、Nb2O5、Bi2O3、TiO2、HfO2、MnO2And M oxide powder as raw materials, each according to the formula (1-x-y) KaNabNbO3-xBi0.5-cMcLi0.5TiO3-yBaHfO3+zMnO2Weighing and proportioning the set values;
wherein M is any one of Ce, Sm, Nd and La,
wherein x, y, z, a and b represent atomic percent, and z is MnO2Occupying compound (1-x-y) KaNabNbO3-xBi1/2- cMcLi1/2TiO3-yBaHfO3The value of the mass percentage of (c),
wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.10, z is more than 0 and less than or equal to 0.05, a is more than or equal to 0.2 and less than or equal to 0.8, b is more than or equal to 0.2 and less than or equal to 0.8, and c is more than or equal to 0 and less than or equal to 0.30;
s2 preparation
S21, synthesis: will K2CO3、Na2CO3、Li2CO3、BaCO3、Nb2O5、Bi2O3、TiO2、HfO2And the powder mixture of the oxide of M is subjected to a high-temperature reaction to form a synthetic product of a perovskite phase structure;
s22, granulating: preparing the synthesized product into powder and mixing with MnO2Mixing the powder, adding a binder and granulating to form granules;
s23, pressing: filling the granular materials into a mold, and pressing into a rough blank with a set shape;
s24, removing glue: carrying out glue discharging treatment on the rough blank;
s25, sintering: sintering the rough blank to obtain a compact ceramic element;
s3 polarization
And polarizing the ceramic element to obtain the lead-free piezoelectric ceramic device.
Optionally, in the step S21, the synthesis temperature is 800-1000 ℃, and the heat preservation time is 2-4 h.
Optionally, in the step S22, the binder is an aqueous solution of polyvinyl alcohol, and the mass concentration of the aqueous solution of polyvinyl alcohol is 3% to 10%.
Optionally, in the step S25, the sintering temperature is 1050-.
Optionally, before polarization, silver is coated on two sides of the ceramic element, and then silver firing is carried out, wherein the temperature of silver firing is 400-700 ℃, and the holding time is 1-3 h.
Optionally, in step S3, the temperature of polarization is 80-140 ℃ and the polarization voltage is 2-5 kV/mm.
According to one embodiment of the present disclosure, at KaNabNbO3Adding Bi into the mixture0.5-cMcLi0.5TiO3Thereby making KaNabNbO3The high temperature quadrature-tetragonal phase of (a) is shifted to low temperatures. BaHfO3Not only can make KaNabNbO3Is shifted to low temperature and also makes KaNabNbO3Low temperature quadrature-three-way phase change phase high temperature shift. By controlling Bi0.5-cMcLi0.5TiO3And BaHfO3Can be such that K isaNabNbO3The base piezoelectric ceramic has a trigonal-tetragonal phase transition at room temperature, thereby effectively enhancing the piezoelectric performance.
Furthermore, by adjusting Bi0.5-cMcLi0.5TiO3The proportion of M in (b) can play a role in activating the crystal lattice and optimizing the composition proportion of the cubic and tetragonal phases, thereby further enhancing the piezoelectric performance.
In addition, the adjustment of M enables the trigonal-tetragonal phase transition to become dispersed, thereby improving the temperature stability of the piezoelectric performance of the lead-free piezoelectric ceramic.
In addition, at the KaNabNbO3MnO is added into the base piezoelectric ceramic2. Mn during high temperature synthesis or sintering4+Ions will be partially formedMn3+And Mn2+Ions. The Mn ions with different valence states enter the crystal lattice partially and replace Nb5+、Ti4+And Hf4+Occupying the lattice site. Due to the electrovalence equilibrium, oxygen vacancies will form in the crystal lattice. And under the action of spontaneous polarization, low-valence Mn ions are combined with oxygen vacancies to form a defect dipole. The defect dipole can play a role in stabilizing a phase structure, so that a structure with three-phase and four-phase coexisting can exist in a wider temperature range, and the temperature stability of the piezoelectric performance of the lead-free piezoelectric ceramic is more effectively improved.
Other features of the present invention and advantages thereof will become apparent from the following detailed description of exemplary embodiments thereof, which proceeds with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
Fig. 1 is a flowchart of a method of manufacturing a lead-free piezoelectric ceramic according to an embodiment of the present invention.
Detailed Description
Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that: the relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate.
In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
According to one embodiment of the present invention, a lead-free piezoelectric ceramic is provided. The lead-free piezoelectric ceramic is represented by the following chemical formula I:
(1-x-y)KaNabNbO3-xBi0.5-cMcLi0.5TiO3-yBaHfO3+zMnO2(I)
wherein M is selected from any one of Ce, Sm, Nd and La elements,
wherein x, y, z, a and b represent atomic percent, and z is MnO2Occupying compound (1-x-y) KaNabNbO3-xBi1/2- cMcLi1/2TiO3-yBaHfO3The value of the mass percentage of (c),
wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.10, z is more than 0 and less than or equal to 0.05, a is more than or equal to 0.2 and less than or equal to 0.8, b is more than or equal to 0.2 and less than or equal to 0.8, and c is more than or equal to 0 and less than or equal to 0.30.
For example, 0. ltoreq. z.ltoreq.0.05, i.e. MnO2Occupying compound (1-x-y) KaNabNbO3-xBi1/2-cMcLi1/2TiO3-yBaHfO3The mass percentage of the component (A) is 0-0.05%.
In the present example, at KaNabNbO3Adding Bi into the mixture0.5-cMcLi0.5TiO3Thereby making KaNabNbO3The high temperature quadrature-tetragonal phase of (a) is shifted to low temperatures. BaHfO3Not only can make KaNabNbO3Is shifted to low temperature and also makes KaNabNbO3The low temperature orthogonal-trigonal phase change phase of (a) moves toward a high temperature. By controlling Bi0.5- cMcLi0.5TiO3And BaHfO3Can be such that K isaNabNbO3Base electrodeThe ceramic has a trigonal-tetragonal phase transition at room temperature, thereby effectively enhancing the piezoelectric performance.
Furthermore, by adjusting Bi0.5-cMcLi0.5TiO3The proportion of M in (b) can play a role in activating the crystal lattice and optimizing the composition proportion of the cubic and tetragonal phases, thereby further enhancing the piezoelectric performance.
In addition, the adjustment of M enables the trigonal-tetragonal phase transition to become dispersed, thereby improving the temperature stability of the piezoelectric performance of the lead-free piezoelectric ceramic.
In addition, at the KaNabNbO3MnO is added into the base piezoelectric ceramic2. Mn during high temperature synthesis or sintering4+Ions will partially form Mn3+And Mn2+Ions. The Mn ions with different valence states enter the crystal lattice partially and replace Nb5+、Ti4+And Hf4+Occupying the lattice site. Due to the electrovalence equilibrium, oxygen vacancies will form in the crystal lattice. And under the action of spontaneous polarization, low-valence Mn ions are combined with oxygen vacancies to form a defect dipole. The defect dipole can play a role in stabilizing a phase structure, so that a structure with three-phase and four-phase coexisting can exist in a wider temperature range, and the temperature stability of the piezoelectric performance of the lead-free piezoelectric ceramic is more effectively improved.
Preferably, x is more than 0.01 and less than or equal to 0.03, y is more than 0.05 and less than or equal to 0.08, z is more than 0.01 and less than or equal to 0.03, a is more than or equal to 0.4 and less than or equal to 0.6, b is more than or equal to 0.4 and less than or equal to 0.6, and c is more than or equal to 0.10 and less than or equal to 0.20. Within this ratio range, the temperature stability of the piezoelectric performance of the lead-free piezoelectric ceramic is more excellent.
Preferably, M is La. The element has wide sources and low cost, can ensure that the temperature stability of the piezoelectric property of the lead-free piezoelectric ceramic is higher, and has good three-square phase change controllability.
Preferably, the lead-free piezoelectric ceramic is of a perovskite phase structure. The structure has good piezoelectric performance.
Preferably, the lead-free piezoelectric ceramic is in a three-phase and four-phase coexistent state. The piezoelectric ceramic has three-square phase change at room temperature, so that the piezoelectric performance of the piezoelectric ceramic is effectively enhanced.
In one example, the lead-free piezoelectric ceramic has excellent piezoelectric properties and good temperature stability. Wherein, positive piezoelectric coefficient d33Can reach 290-400pC/N, is close to the performance of lead zirconate titanate-based ceramic, and has a positive piezoelectric coefficient d within the common temperature range of 25-70 DEG C33The variation is less than 20 percent; inverse piezoelectric coefficient d33 *Can reach 300-450pm/V and has inverse piezoelectric coefficient d within the temperature range of 25-150 DEG C33 *The variation is less than 15%.
According to another embodiment of the present invention, there is provided a method for preparing a lead-free piezoelectric ceramic, including the steps of:
s1, batching:
with K2CO3、Na2CO3、Li2CO3、BaCO3、Nb2O5、Bi2O3、TiO2、HfO2、MnO2And M oxide powder as raw materials, each according to the formula (1-x-y) KaNabNbO3-xBi0.5-cMcLi0.5TiO3-yBaHfO3+zMnO2Weighing and proportioning the set values;
wherein M is selected from any one of Ce, Sm, Nd and La, for example, when the preparation is carried out, each element of Ce, Sm, Nd and La is proportioned in the form of oxide;
wherein x, y, z, a and b represent atomic percent, and z is MnO2Occupying compound (1-x-y) KaNabNbO3-xBi1/2- cMcLi1/2TiO3-yBaHfO3The value of the mass percentage of (c),
wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.10, z is more than 0 and less than or equal to 0.05, a is more than or equal to 0.2 and less than or equal to 0.8, b is more than or equal to 0.2 and less than or equal to 0.8, and c is more than or equal to 0 and less than or equal to 0.30;
specifically, the raw materials are powder materials. And weighing and proportioning according to the proportional relation of each element in the chemical formula I. The amount of each raw material can be set by those skilled in the art according to actual needs. MnO2Can also be usedAnd the function of a sintering aid is realized. MnO2The sintering temperature of the potassium-sodium niobate ceramic can be reduced, so that the volatilization of alkali metal under high-temperature sintering is greatly reduced, and the compactness and the piezoelectric property of the potassium-sodium niobate ceramic are improved.
S2 preparation
S21, synthesis: will K2CO3、Na2CO3、Li2CO3、BaCO3、Nb2O5、Bi2O3、TiO2、HfO2And the powder mixture of the oxide of M is subjected to a high temperature reaction to form a synthetic product of a perovskite phase structure.
In this step, the powder of the above raw materials may be directly added and mixed in accordance with the particle size requirement, and then subjected to a high temperature reaction.
Or adding the block materials, the granular materials and the like of the raw materials into a ball mill for primary ball milling to obtain a powder mixture meeting the requirement of the granularity.
Preferably, in the first ball milling, the ball mill uses zirconia balls and/or agate balls for ball milling. The two balls are not easy to be damaged, and the powder mixture milled by the balls has less impurities.
Preferably, alcohol or deionized water is added into the ball milling tank during the first ball milling to increase the viscosity of the mixture, so that the ball milling is more complete and the obtained powder is finer and more uniform.
The addition of auxiliary agents, ball milling time and the like can be selected by those skilled in the art according to actual needs.
In the step, the synthesis temperature is 800-. At this temperature, the powder mixture is able to react sufficiently to form a synthetic product of perovskite phase structure.
In addition, under the condition, the reaction speed is moderate, and the conversion rate of the perovskite phase structure is high.
S22, granulating: preparing the synthesized product into powder and mixing with MnO2Mixing the powder, adding a binder and granulating to form granules;
the synthesized product is prepared into powder by, for example, second ball milling. MnO is added into the ball milling tank while the secondary ball milling is carried out2And (3) powder. MnO2The powder is mixed and milled with the synthesized product to a set particle size. Likewise, zirconia balls or agate balls are used. And adding assistants such as alcohol, deionized water and the like into the ball milling tank so as to ensure better quality of the mixed milling.
Drying the mixed and ground materials to remove alcohol, deionized water and the like. The binder is then added and milled. And sieving and granulating the ground material to form the granular material with the set particle size. The screening can remove larger and irregular materials, so that the size and the components of the granular materials are more uniform.
Preferably, the binder is an aqueous solution of polyvinyl alcohol. The binder has the characteristics of high viscosity and small using amount. The mass concentration of the aqueous solution of the polyvinyl alcohol is 3-10%. At this concentration, the granulation effect was good and the shape retention of the obtained green compact was good.
Those skilled in the art can select other granulating agents commonly used in the art according to actual needs.
S23, pressing: and (3) filling the granules into a mold, and pressing to obtain a rough blank with a set shape. In this step, a mold may be made in accordance with the shape of the piezoelectric ceramic article. The granules are filled and compacted in a mould to form a set shape.
S24, removing glue: and (4) carrying out glue discharging treatment on the rough blank to remove the binder.
The purpose of the binder removal is to remove high molecular compounds such as polyvinyl alcohol and the like from the rough blank so as to avoid adverse effects on sintering. The high molecular compound contains a large amount of carbon, and when oxygen is insufficient, carbon monoxide having a strong reducibility is produced by combustion. Carbon monoxide is capable of reducing the oxides in the feedstock to metals or suboxides. The metal or suboxide affects the color, ceramic forming, platability and polarization of the ceramic.
In one example, pre-dumping is first performed with an organic solvent. Namely, the blank is immersed into an organic solvent for pre-degumming. Optionally, the organic solvent for pre-dumping is one of trichloroethylene, carbon tetrachloride, chloroform and acetone.
Then, the rough blank after pre-degumming is subjected to degumming treatment at high temperature so as to completely remove organic matters such as polyvinyl alcohol and the like. The temperature of the glue discharging treatment is 400-600 ℃.
In another example, the green body is directly subjected to a debinding process at an elevated temperature. In this way, high molecular weight compounds such as polyvinyl alcohol can likewise be excluded. Preferably, the temperature of the gel discharging treatment is 400-600 ℃, and the gel discharging temperature is 2-3 hours.
S25, sintering: the green compact is sintered to obtain a dense ceramic element. For example, the sintering temperature is 1050-. Under this condition, the rough blank is sintered to form a ceramic element with a dense structure. The ceramic element is represented by compound I. Spontaneous polarization exists in all directions in the crystal of the ceramic element, and no polarity is presented to the outside from the macroscopic view. The regions where the spontaneous polarizations are in the same direction are called electric domains.
S3 polarization
And polarizing the ceramic element to obtain the lead-free piezoelectric ceramic device. The electric domain of the ceramic element is turned by polarization, namely the spontaneous polarization of the electric domain is forced by polarization to be directionally arranged, so that the ceramic element presents polarity.
For example, before polarization, the ceramic element is silver-coated on both sides and then silver firing is performed. Electrodes can be formed on both upper and lower surfaces of the ceramic element by silver coating or silver firing. And the flowing metal silver can enter the pores of the upper surface and the lower surface of the ceramic element, so that the silver electrode layers can be firmly bonded on the upper surface and the lower surface of the ceramic element.
Preferably, the silver firing temperature is 400-700 ℃, and the holding time is 1-3 h. Under the condition, the formed electrode has uniform thickness and good quality.
Preferably, the temperature of the polarization is 80-140 ℃ and the polarization voltage is 2-5 kV/mm. Under this condition, the ceramic element is sufficiently polarized to exhibit polarity.
By polarization, the ceramic element becomes a potassium-sodium niobate ceramic device having piezoelectric properties.
In other examples, the ceramic element is directly polarized in an atmospheric environment, which also enables the ceramic element to have piezoelectric properties.
The preparation method of the lead-free piezoelectric ceramic provided by the embodiment of the invention has the advantages of simple preparation process and low requirement on preparation conditions, and is suitable for large-scale production.
Although some specific embodiments of the present invention have been described in detail by way of examples, it should be understood by those skilled in the art that the above examples are for illustrative purposes only and are not intended to limit the scope of the present invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A lead-free piezoelectric ceramic represented by the following chemical formula I:
(1-x-y)KaNabNbO3-xBi0.5-cMcLi0.5TiO3-yBaHfO3+zMnO2(I)
wherein M is any one of Ce, Sm, Nd and La,
wherein x, y, z, a and b represent atomic percent, and z is MnO2Occupying compound (1-x-y) KaNabNbO3-xBi1/2- cMcLi1/2TiO3-yBaHfO3The value of the mass percentage of (c),
wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.10, z is more than 0 and less than or equal to 0.05, a is more than or equal to 0.2 and less than or equal to 0.8, b is more than or equal to 0.2 and less than or equal to 0.8, and c is more than or equal to 0 and less than or equal to 0.30.
2. The lead-free piezoelectric ceramic according to claim 1, wherein x is 0.01. ltoreq. x.ltoreq.0.03, y is 0.05. ltoreq. y.ltoreq.0.08, z is 0.01. ltoreq. z.ltoreq.0.03, a is 0.4. ltoreq. a.ltoreq.0.6, b is 0.4. ltoreq. b.ltoreq.0.6, and c is 0.10. ltoreq. c.ltoreq.0.20.
3. The lead-free piezoelectric ceramic according to claim 1, wherein M is La.
4. The lead-free piezoelectric ceramic according to claim 1, wherein the lead-free piezoelectric ceramic is in a three-phase and four-phase coexistent state.
5. A preparation method of lead-free piezoelectric ceramics comprises the following steps:
s1, batching:
with K2CO3、Na2CO3、Li2CO3、BaCO3、Nb2O5、Bi2O3、TiO2、HfO2、MnO2And M oxide powder as raw materials, each according to the formula (1-x-y) KaNabNbO3-xBi0.5-cMcLi0.5TiO3-yBaHfO3+zMnO2Weighing and proportioning the set values;
wherein M is any one of Ce, Sm, Nd and La,
wherein x, y, z, a and b represent atomic percent, and z is MnO2Occupying compound (1-x-y) KaNabNbO3-xBi1/2- cMcLi1/2TiO3-yBaHfO3The value of the mass percentage of (c),
wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.10, z is more than 0 and less than or equal to 0.05, a is more than or equal to 0.2 and less than or equal to 0.8, b is more than or equal to 0.2 and less than or equal to 0.8, and c is more than or equal to 0 and less than or equal to 0.30;
s2 preparation
S21, synthesis: will K2CO3、Na2CO3、Li2CO3、BaCO3、Nb2O5、Bi2O3、TiO2、HfO2And the powder mixture of the oxide of M is subjected to a high-temperature reaction to form a synthetic product of a perovskite phase structure;
s22, granulating: preparing the synthesized product into powder and mixing with MnO2Mixing the powder, adding a binder and granulating to form granules;
s23, pressing: filling the granular materials into a mold, and pressing into a rough blank with a set shape;
s24, removing glue: carrying out glue discharging treatment on the rough blank;
s25, sintering: sintering the rough blank to obtain a compact ceramic element;
s3 polarization
And polarizing the ceramic element to obtain the lead-free piezoelectric ceramic device.
6. The method as claimed in claim 5, wherein the synthesis temperature is 800-1000 ℃ and the holding time is 2-4h in the step S21.
7. The method according to claim 5, wherein in the step S22, the binder is an aqueous solution of polyvinyl alcohol, and the mass concentration of the aqueous solution of polyvinyl alcohol is 3-10%.
8. The method as claimed in claim 5, wherein the sintering temperature is 1050-1250 ℃ and the holding time is 2-6h in the step S25.
9. The method as claimed in claim 5, wherein before the polarization, the ceramic element is silver coated on both sides and then silver firing is performed at 400-700 ℃ for 1-3 h.
10. The method according to claim 5, wherein the temperature of the polarization is 80 to 140 ℃ and the polarization voltage is 2 to 5kV/mm in the step S3.
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Effective date of registration: 20201013 Address after: 261031 north of Yuqing street, east of Dongming Road, high tech Zone, Weifang City, Shandong Province (Room 502, Geer electronic office building) Patentee after: GoerTek Optical Technology Co.,Ltd. Address before: 261031 Dongfang Road, Weifang high tech Development Zone, Shandong, China, No. 268 Patentee before: GOERTEK Inc. |
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| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210707 Address after: F / F, phase II, Qingdao International Innovation Park, 1 Keyuan Weiyi Road, Laoshan District, Qingdao City, Shandong Province, 266104 Patentee after: Geer Microelectronics Co.,Ltd. Address before: 261031 north of Yuqing street, east of Dongming Road, high tech Zone, Weifang City, Shandong Province (Room 502, Geer electronics office building) Patentee before: GoerTek Optical Technology Co.,Ltd. |