CN113683409A - Tetragonal phase A and B position co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability and preparation method and application thereof - Google Patents

Tetragonal phase A and B position co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability and preparation method and application thereof Download PDF

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CN113683409A
CN113683409A CN202111004591.6A CN202111004591A CN113683409A CN 113683409 A CN113683409 A CN 113683409A CN 202111004591 A CN202111004591 A CN 202111004591A CN 113683409 A CN113683409 A CN 113683409A
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常云飞
寇蔷薇
刘琳婧
谢航
孙媛
杨彬
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Harbin Institute of Technology
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Abstract

Tetragonal phase A and B position co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability and a preparation method and application thereof, belonging to the field of piezoelectric materials. Solves the problem that the BT-based ceramic material has Curie temperature T in the prior artcDecrease in piezoelectric coefficient and deterioration in temperature stability of piezoelectric coefficient. The textured ceramic has a chemical formula of (Ba)1‑xCax)(Ti1‑yEy)O3At room temperatureIs a pure tetragonal phase perovskite structure, and is along [001 ]]cOr [111 ]]cThe preferred orientation degree is more than 90%. The method comprises the following steps: firstly, preparing a precursor base material; secondly, selecting and weighing template seed crystals; thirdly, preparing casting slurry; fourthly, preparing a ceramic green body; fifthly, preparing the tetragonal phase lead-free textured ceramic. The application comprises the following steps: the method is applied to electronic devices which can keep stable electromechanical output within the range of room temperature to 100 ℃.

Description

Tetragonal phase A and B position co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability and preparation method and application thereof
Technical Field
The invention belongs to the field of piezoelectric materials.
Background
Piezoelectric actuators, intelligent sensors, ultrasonic transducers, energy collectors and the like prepared on the basis of the unique electromechanical energy conversion capability of perovskite structure piezoelectric materials have important requirements in high and new technical fields such as information technology, advanced manufacturing, medical health, new energy sources and aerospace. Lead zirconate titanate (PZT) based piezoelectric ceramics have been the most widely used piezoelectric material and have occupied a major share of the market due to their outstanding electromechanical properties and temperature stability. However, such lead-based materials can pose a hazard to human health and the ecological environment during production, use and disposal. At present, the research and development of lead-free piezoelectric ceramics with high performance and good temperature stability to replace the traditional lead-based ceramics becomes a urgent subject worldwide and has great economic and social values. BaTiO 23(barium titanate, abbreviated BT) is the earliest lead-free piezoelectric system discovered and is considered one of the most promising lead-free systems for replacing lead-based ceramics.
In recent years, in order to solve the problem of insufficient piezoelectric performance of pure BT ceramics, researchers build multiphase critical points (such as cubic phase, orthorhombic phase, tetragonal phase and cubic phase coexisting four-phase critical points) near room temperature on the system by means of ion substitution, new component introduction, doping substitution and the like based on a solid solution concept, and synthesize the BT-based ceramics with randomly oriented crystal grains by combining a traditional ceramic preparation process, so that the room temperature piezoelectric coefficient of the BT-based ceramics is improved in a breakthrough manner. However, the increase in the piezoelectric coefficient thereof is generally accompanied by a Curie temperature TcThe temperature can be reduced from 120 ℃ of pure BT to 30-80 DEG CThe application temperature range of the ceramic material is severely limited. In addition, the two (multiple) phases of the ceramic coexist at room temperature, so that the temperature stability of the piezoelectric coefficient is poor, namely the ceramic has strong temperature sensitivity. For example, Ba (Ti) coexisting in multiple phases at room temperature0.89Sn0.11)O3The piezoelectric coefficient of the ceramic decreases by 86% when the temperature of the ceramic is raised from room temperature to 60 ℃ (Wang DW, Fan ZG, Rao GH, Wang G, Liu Y, Yuan CL, Ma T, Li DJ, Tan XL, Lu ZL, Feteira A, Liu SY, Zhou CR, Zhang SJ.ultra high piezoelectric activity in lead-free piezoelectric ceramics by synthetic design.Nano Energy 2020; 76: 104944); will (Ba)0.85Ca0.15)(Zr0.10Ti0.90)O3The piezoelectric coefficient of the ceramic decreases by 51% when the temperature of the ceramic is increased from room temperature to 105 ℃ (Acosta M, Novak N, Jo W, Rodel J0.2Ti0.8)O3–x(Ba0.7Ca0.3)TiO3lead-free semiconductors acta Mater 2014; 80:48-55). Curie temperature TcThe two defects of reduction and deterioration of the temperature stability of the piezoelectric coefficient are not favorable for device preparation and stable work, and the practical development of the BT-based ceramic is greatly limited. How to improve the temperature stability of the piezoelectric performance of the BT-based ceramic is an important direction for the research and development of lead-free piezoelectric ceramics in the future.
Disclosure of Invention
The invention aims to solve the problem that the BT-based ceramic material in the prior art has Curie temperature TcReduce the temperature stability of the piezoelectric coefficient and provide tetragonal phase A and B co-substituted leadless piezoelectric textured ceramics with excellent temperature stability and a preparation method and application thereof.
Tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability and chemical general formula of (Ba)1-xCax)(Ti1-yEy)O3Wherein E is Zr or Hf, x is more than 0.12 and less than 0.30, and y is more than 0 and less than 0.09;
the orthorhombic O-tetragonal T phase transition temperature T of the tetragonal phase A and B bit co-substituted leadless piezoelectric textured ceramic with excellent temperature stabilityo-tBelow room temperature, the ceramic is in a pure tetragonal phase (T) perovskite structure consisting of a [001 ] edge]cOr [111 ]]cThe preferred orientation degree is more than 90 percent; when the tetragonal phase grain is along [001 ]]cWhen the orientation is preferred, the ceramic section is in the shape of a cuboid brick wall; when the tetragonal phase grain is along [111 ]]cWhen preferred orientation is carried out, the ceramic section is in a rhomboid stacking shape;
the curie temperature of the tetragonal phase A and B position co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability is higher than 100 ℃, and the change rate of the piezoelectric coefficient in the range from room temperature to the curie temperature is lower than 15%.
The preparation method of tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability is completed according to the following steps:
firstly, preparing a precursor base material:
the chemical formula (Ba) of the target component of the textured ceramic1-xCax)(Ti1-yEy)O3According to the stoichiometric ratio of BaCO3Powder, CaCO3Powder, TiO2Powder and ZrO2The powder is taken as the raw material or called BaCO3Powder, CaCO3Powder, TiO2Powder and HfO2The powder is taken as a raw material; taking ethanol as a ball milling medium, and performing primary ball milling, drying, presintering, secondary ball milling, drying and sieving to obtain a precursor base material; wherein E is Zr or Hf, x is more than 0.12 and less than 0.30, and y is more than 0 and less than 0.09;
the TiO is2Powder, ZrO2Powder and HfO2The grain diameters of the powder are less than or equal to 60 nm; the precursor base material is a pure perovskite phase and has a particle size of below 300 nm;
secondly, selecting and weighing template seed crystals:
selecting BaTiO3Lamellar seed crystals or SrTiO3Using the flaky seed crystal as a template seed crystal, and respectively weighing a precursor base material and the template seed crystal; the molar ratio of the template seed crystal to the precursor base material is 3 (17-97);
the template seed crystal is of a pure perovskite structure and is arranged along the {001}cOr {111}cPreferred orientation is carried out, the diameter of the seed crystal of the template is less than 50 mu m, and the diameter-thickness ratio is more than or equal to 8;
thirdly, preparing casting slurry:
mixing a solvent, a dispersing agent, an adhesive, a plasticizer and the precursor base material weighed in the second step by ball milling to prepare base material slurry, adding the template seed crystal weighed in the second step into the base material slurry, and continuing ball milling to obtain casting slurry;
fourthly, preparing a ceramic green body:
casting and drying the casting slurry by using a casting machine to obtain a membrane with the thickness of 10-100 microns, sequentially cutting, laminating, hot water homogenizing, cutting and discharging the membrane, and finally performing cold isostatic pressing under the condition that the pressure is 150-300 MPa to obtain a ceramic green body;
fifthly, preparing tetragonal phase lead-free textured ceramic:
and (3) placing the ceramic green body in a high-temperature furnace, and sintering for 2-20 h under the conditions of air atmosphere and temperature of 1450-1600 ℃ to obtain the tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability.
The application of tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability is applied to electronic devices which can keep stable electromechanical output within the range of room temperature to 100 ℃; the electronic device is a piezoelectric actuator, an intelligent sensor, an ultrasonic transducer or an energy collector.
The principle is as follows: the invention adopts a new design strategy and a preparation technology which are different from the prior BT-based ceramic research, and selects a pure tetragonal phase perovskite structure at room temperature and Curie temperature TcAbove 100 deg.C (Ba)1-xCax)(Ti1-yEy)O3Wherein E is Zr or Hf, x is more than 0.12 and less than 0.30, and y is more than 0 and less than 0.09 as a texture system. For having ABO3Pure perovskite structure BaTiO3In the system, the A and B positions have ion substitution phenomena. The orthogonal O-tetragonal T phase boundary temperature T of the system to be protected of the inventiono-tBelow room temperature, no multi (two) phase coexisting dispersed phase boundary exists near room temperature, and the tetragonal T-cubic C phase transition temperature thereofDegree (i.e. Curie temperature T)c) Above 100 ℃, a wide temperature interval may be provided for the stable existence of pure tetragonal T phase. Based on the anisotropic characteristic of the piezoelectric effect of the perovskite structure, ceramic grains are subjected to preferred orientation growth (crystal orientation texture) according to the piezoelectric dominant direction, so that high polarization efficiency is obtained by utilizing the polarization expansion effect, and the piezoelectric coefficient of each directionally arranged grain in the ceramic body is remarkably improved by the vector accumulation of the piezoelectric performance of each directionally arranged grain. Meanwhile, the textured ceramic keeps a wide temperature range in which a tetragonal T phase of a designed system can stably exist, and compared with ordinary ceramic with randomly oriented crystal grains, the textured ceramic can enable an electric domain structure to be stable at room temperature to high temperature. The wide temperature range in which the tetragonal phase stably exists and the electric domain structure with good temperature stability are the main reasons for obtaining the piezoelectric coefficient with excellent temperature stability.
The invention has the beneficial effects that: aiming at breaking through the material modification technology of the traditional solid solution, the invention applies the pure tetragonal phase design and the crystal orientation texture concept of the material to design and prepare a novel edge [001 ]]cOr [111 ]]cPreferred orientation, having excellent temperature stability A&B-site disubstituted barium titanate-based lead-free piezoelectric textured ceramic. The invention can improve the electrical property and Curie temperature T of the material at room temperaturecWhen the temperature is higher than 100 ℃, the temperature stability of the piezoelectric coefficient is obviously improved, and a brand-new design and preparation idea is provided for obtaining the lead-free ceramic material with high electrical properties and excellent temperature stability. The lead-free piezoelectric textured ceramic material has a pure tetragonal perovskite structure at room temperature, and the grain edge [001 ]]cOr [111 ]]cPreferred orientation degree of preferred orientation is higher than 90%, Curie temperature is higher than 100 deg.C, and piezoelectric coefficient d is33 *(Smax/Emax)At room temperature to TcThe change rate in the interval is kept lower than 15 percent and is far lower than the BT-based ceramic material reported at present. The material prepared by the invention has excellent temperature stability, namely, the material still keeps higher piezoelectric coefficient at higher temperature, thereby obviously widening the temperature application range. In addition, the preparation process is simple and stable, and the cost is lowerAnd the chemical components are accurate and controllable, the method is suitable for large-scale industrial production, and the environmental pollution can be obviously reduced. These advantages make the material show great potential in the mass production and application of new generation of wide temperature zone piezoelectric devices such as piezoelectric actuators, intelligent sensors, ultrasonic transducers and energy collectors.
Drawings
FIG. 1 is an XRD pattern of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in example one;
FIG. 2 is an SEM picture of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in the first example;
FIG. 3 is a graph of the dielectric temperature spectrum of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in the first example;
FIG. 4 is the normalized piezoelectric coefficient d of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in the first example33 *A change with temperature;
FIG. 5 is an XRD pattern of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in example two;
FIG. 6 is an SEM picture of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in example two;
FIG. 7 is a graph of the dielectric temperature spectrum of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in example two;
FIG. 8 is the normalized piezoelectric coefficient d of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in example two33 *As a function of temperature.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, but includes any combination between the specific embodiments.
The first embodiment is as follows: this embodiment has a tetragonal phase with excellent temperature stabilityThe A and B position co-substituted leadless piezoelectric textured ceramic has the chemical general formula of (Ba)1-xCax)(Ti1-yEy)O3Wherein E is Zr or Hf, x is more than 0.12 and less than 0.30, and y is more than 0 and less than 0.09;
the orthorhombic O-tetragonal T phase transition temperature T of the tetragonal phase A and B bit co-substituted leadless piezoelectric textured ceramic with excellent temperature stabilityo-tBelow room temperature, the ceramic is in a pure tetragonal phase (T) perovskite structure consisting of a [001 ] edge]cOr [111 ]]cThe preferred orientation degree is more than 90 percent; when the tetragonal phase grain is along [001 ]]cWhen the orientation is preferred, the ceramic section is in the shape of a cuboid brick wall; when the tetragonal phase grain is along [111 ]]cWhen preferred orientation is carried out, the ceramic section is in a rhomboid stacking shape;
the curie temperature of the tetragonal phase A and B position co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability is higher than 100 ℃, and the change rate of the piezoelectric coefficient in the range from room temperature to the curie temperature is lower than 15%.
The beneficial effects of the specific implementation mode are as follows: aiming at breaking through the material modification technology of the traditional solid solution, the specific implementation mode applies the pure tetragonal phase design and the crystal orientation texture concept of the material to design and prepare a novel edge [001 ]]cOr [111 ]]cPreferred orientation, having excellent temperature stability A&B-site disubstituted barium titanate-based lead-free piezoelectric textured ceramic. The embodiment can improve the electrical property and Curie temperature T at the room temperature of the materialcWhen the temperature is higher than 100 ℃, the temperature stability of the piezoelectric coefficient is obviously improved, and a brand-new design and preparation idea is provided for obtaining the lead-free ceramic material with high electrical properties and excellent temperature stability. The lead-free piezoelectric textured ceramic material of the specific embodiment has a pure tetragonal perovskite structure at room temperature, and the grain edge is [001 ]]cOr [111 ]]cPreferred orientation degree of preferred orientation is higher than 90%, Curie temperature is higher than 100 deg.C, and piezoelectric coefficient d is33 *(Smax/Emax)At room temperature to TcThe change rate in the interval is kept lower than 15 percent and is far lower than the BT-based ceramic material reported at present. Book toolThe material prepared by the bulk embodiment has excellent temperature stability, namely, a higher piezoelectric coefficient is still kept at a higher temperature, so that the temperature application range is remarkably widened. In addition, the preparation method of the specific embodiment is simple and stable in preparation process, low in cost, accurate and controllable in chemical components, suitable for large-scale industrial production and capable of remarkably reducing environmental pollution. These advantages make the material show great potential in the mass production and application of new generation of wide temperature zone piezoelectric devices such as piezoelectric actuators, intelligent sensors, ultrasonic transducers and energy collectors.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the rate of change of the piezoelectric coefficient in the range from room temperature to Curie temperature is less than 10%. The rest is the same as the first embodiment.
The third concrete implementation mode: the preparation method of the tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability of the embodiment is completed by the following steps:
firstly, preparing a precursor base material:
the chemical formula (Ba) of the target component of the textured ceramic1-xCax)(Ti1-yEy)O3According to the stoichiometric ratio of BaCO3Powder, CaCO3Powder, TiO2Powder and ZrO2The powder is taken as the raw material or called BaCO3Powder, CaCO3Powder, TiO2Powder and HfO2The powder is taken as a raw material; taking ethanol as a ball milling medium, and performing primary ball milling, drying, presintering, secondary ball milling, drying and sieving to obtain a precursor base material; wherein E is Zr or Hf, x is more than 0.12 and less than 0.30, and y is more than 0 and less than 0.09;
the TiO is2Powder, ZrO2Powder and HfO2The grain diameters of the powder are less than or equal to 60 nm; the precursor base material is a pure perovskite phase and has a particle size of below 300 nm;
secondly, selecting and weighing template seed crystals:
selecting BaTiO3Lamellar seed crystals or SrTiO3Using the sheet seed crystal as a template seed crystal, and respectively weighing precursor base materialsAnd template seed crystals; the molar ratio of the template seed crystal to the precursor base material is 3 (17-97);
the template seed crystal is of a pure perovskite structure and is arranged along the {001}cOr {111}cPreferred orientation is carried out, the diameter of the seed crystal of the template is less than 50 mu m, and the diameter-thickness ratio is more than or equal to 8;
thirdly, preparing casting slurry:
mixing a solvent, a dispersing agent, an adhesive, a plasticizer and the precursor base material weighed in the second step by ball milling to prepare base material slurry, adding the template seed crystal weighed in the second step into the base material slurry, and continuing ball milling to obtain casting slurry;
fourthly, preparing a ceramic green body:
casting and drying the casting slurry by using a casting machine to obtain a membrane with the thickness of 10-100 microns, sequentially cutting, laminating, hot water homogenizing, cutting and discharging the membrane, and finally performing cold isostatic pressing under the condition that the pressure is 150-300 MPa to obtain a ceramic green body;
fifthly, preparing tetragonal phase lead-free textured ceramic:
and (3) placing the ceramic green body in a high-temperature furnace, and sintering for 2-20 h under the conditions of air atmosphere and temperature of 1450-1600 ℃ to obtain the tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability.
The fourth concrete implementation mode: the third difference between the present embodiment and the specific embodiment is that: BaCO described in step one3Powder, CaCO3Powder, TiO2Powder, ZrO2Powder and HfO2The purity of the powder is more than or equal to 99.9 percent; the primary ball milling time in the step one is 48-96 hours; the pre-sintering in the step one is to preserve heat for 1 to 10 hours under the condition that the temperature is 1000 to 1450 ℃; the secondary ball milling time in the step one is 24-72 h. The rest is the same as the third embodiment.
The fifth concrete implementation mode: this embodiment is different from the third or fourth embodiment in that: the ball milling and mixing time in the third step is 24-48 h; the continuous ball milling time in the third step is 15-60 min. The other is the same as the third or fourth embodiment.
The sixth specific implementation mode: the difference between this embodiment and one of the third to fifth embodiments is: in the third step, xylene-ethanol mixed solution is used as a solvent, herring oil is used as a dispersing agent, polyvinyl butyral is used as a bonding agent, and polyalkylene glycol and butyl benzyl phthalate are used as plasticizers. The rest is the same as the third to fifth embodiments.
The seventh embodiment: this embodiment differs from one of the third to sixth embodiments in that: the mass ratio of the xylene to the ethanol is 1: 1; the mass ratio of the polyalkylene glycol to the butyl benzyl phthalate is 1: 1. The others are the same as the third to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the third to seventh embodiments in that: the mass ratio of the precursor base material to the solvent in the third step is 1 (0.3-0.8); the mass ratio of the precursor base material to the dispersing agent in the third step is 1 (0.01-0.03); the mass ratio of the precursor base material to the adhesive in the third step is 1 (0.02-0.06); the mass ratio of the precursor base material to the plasticizer in the third step is 1 (0.02-0.08). The rest is the same as the third to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the second to eighth embodiments in that: the laminating in the fourth step is to keep the temperature and the pressure for 10min to 60min under the conditions that the temperature is 60 ℃ to 95 ℃ and the pressure is 10MPa to 50 MPa; the step four, the hot water pressure equalization, is to keep the temperature and the pressure for 15min to 60min under the conditions that the temperature is 60 ℃ to 95 ℃ and the pressure is 20MPa to 50 MPa; the rubber discharging in the fourth step is specifically that rubber is discharged for 1 to 6 hours at the temperature of 550 to 650 ℃; the cold isostatic pressing time in the fourth step is 2 min-20 min. The rest is the same as the second to eighth embodiments.
The detailed implementation mode is ten: the application of tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability is applied to electronic devices which can keep stable electromechanical output within the range of room temperature to 100 ℃; the electronic device is a piezoelectric actuator, an intelligent sensor, an ultrasonic transducer or an energy collector.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
the preparation method of tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability is completed according to the following steps:
firstly, preparing a precursor base material:
the chemical formula (Ba) of the target component of the textured ceramic0.85Ca0.15)(Ti0.95Zr0.05)O3According to the stoichiometric ratio of BaCO3Powder, CaCO3Powder, TiO2Powder and ZrO2The powder is taken as a raw material; taking ethanol as a ball milling medium, and performing primary ball milling, drying, presintering, secondary ball milling, drying and sieving to obtain a precursor base material;
the TiO is2The particle size of the powder is 20 nm; the ZrO2The particle size of the powder is 50 nm; the precursor base material is a pure perovskite phase and has an average particle size of 280 nm;
secondly, selecting and weighing template seed crystals:
choose the edge {001}cPreferentially oriented BaTiO3Using the flaky seed crystal as a template seed crystal, and respectively weighing a precursor base material and the template seed crystal; the molar ratio of the template seed crystal to the precursor base material is 5: 95;
the template seed crystal is of a pure perovskite structure, the diameter of the template seed crystal is 7-14 mu m, and the diameter-thickness ratio is more than or equal to 8;
thirdly, preparing casting slurry:
mixing a solvent, a dispersing agent, an adhesive, a plasticizer and the precursor base material weighed in the second step by ball milling to prepare base material slurry, adding the template seed crystal weighed in the second step into the base material slurry, and continuing ball milling to obtain casting slurry;
fourthly, preparing a ceramic green body:
casting and drying the casting slurry by using a casting machine to obtain a membrane with the thickness of 50 microns, sequentially cutting, laminating, hot water homogenizing, cutting and removing glue, and finally carrying out cold isostatic pressing under the pressure of 200MPa to obtain a ceramic green body;
fifthly, preparing tetragonal phase lead-free textured ceramic:
and (3) placing the ceramic green body in a high-temperature furnace, and sintering for 9 hours under the conditions of air atmosphere and temperature of 1575 ℃ to obtain the tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability.
BaCO described in step one3Powder, CaCO3Powder, TiO2Powder, ZrO2The purity of the powder is more than or equal to 99.9 percent; the primary ball milling time in the step one is 48 hours; the pre-sintering in the step one is specifically that heat is preserved for 1.5 hours at the temperature of 1250 ℃; the secondary ball milling time in the step one is 24 hours.
The ball milling mixing time in the third step is 48 hours; the continuous ball milling time in the third step is 30 min.
In the third step, xylene-ethanol mixed solution is used as a solvent, herring oil is used as a dispersing agent, polyvinyl butyral is used as a bonding agent, and polyalkylene glycol and butyl benzyl phthalate are used as plasticizers.
The mass ratio of the xylene to the ethanol is 1: 1; the mass ratio of the polyalkylene glycol to the butyl benzyl phthalate is 1: 1.
The mass ratio of the precursor base material to the solvent in the third step is 1:0.5, and the mass ratio of the precursor base material to the dispersing agent in the third step is 1: 0.018; the mass ratio of the precursor base material to the adhesive in the third step is 1: 0.045; the mass ratio of the precursor base material to the plasticizer in the third step is 1: 0.045.
The step four of laminating specifically comprises the steps of preserving heat and maintaining pressure for 30min under the conditions that the temperature is 75 ℃ and the pressure is 20 MPa; the step four of hot water pressure equalization is to keep the temperature and the pressure for 15min under the conditions that the temperature is 75 ℃ and the pressure is 20 MPa; the rubber discharging in the fourth step is specifically that rubber is discharged for 2 hours at the temperature of 600 ℃; and the cold isostatic pressing time in the fourth step is 3 min.
Template seed crystal reference described in step twoThe following documents were prepared: liu YC, Chang YF, Li F, Yang B, Sun Y, Wu J, Zhang ST, Wang RX, Cao WW, entrapment all high piezoelectric coefficient and low strain hystersis in grain-oriented (Ba, Ca) (Ti, Zr) O3through intergrating crystallographic texture and domain engineering.ACS Appl Mater Interfaces 2017；9:29863-71。
The tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability has a chemical general formula of (Ba)0.85Ca0.15)(Ti0.95Zr0.05)O3；
The orthorhombic O-tetragonal T phase transition temperature T of the tetragonal phase A and B bit co-substituted leadless piezoelectric textured ceramic with excellent temperature stabilityo-tBelow room temperature, the ceramic is in a pure tetragonal phase (T) perovskite structure consisting of a [001 ] edge]cThe preferred orientation degree is 94 percent; the ceramic section is in the shape of a cuboid brick wall;
the tetragonal phase A and B co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability has the Curie temperature of 109 ℃ and the change rate of the piezoelectric coefficient in the range from room temperature to the Curie temperature is lower than 6%.
Fig. 1 is an XRD pattern of tetragonal phase a and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in example one. As can be seen, the textured ceramic had a pure tetragonal perovskite phase structure, which is (001)cAnd (002)cThe intensity of the peak is very strong, while others are not {001}cThe peak intensity is very weak, showing that the material has a grain edge of [001 ]]cHighly preferred orientation. Using Lotgering factor (F)00l) Calculated by analytical method, the textured ceramic grain edge [001 ]]cPreferred degree of orientation F00lUp to 94%. For textured ceramics, F00lHas a value range of 0 < F001< 1, F thereof001Larger, ceramic [001 ]]cThe higher the degree of orientation.
Fig. 2 is an SEM picture of tetragonal phase a and B co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability prepared in example one. As can be seen, the microstructure of the ceramic is mainly composed of edges[001]cThe crystal grains with preferred orientation are formed, and the appearance of a cuboid brick wall is shown.
Fig. 3 is a dielectric temperature spectrum diagram of tetragonal phase a and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in the first example. As can be seen, the Curie temperature T of the texture samplec109 ℃ and the ferroelectric orthorhombic-tetragonal phase transition point is far away from the room temperature and is-13 ℃. These can guarantee that the tetragonal phase structure exists steadily in wide temperature interval, are favorable to the promotion of sample piezoelectric coefficient temperature stability.
FIG. 4 is the normalized piezoelectric coefficient d of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in the first example33 *As a function of temperature. It can be seen that the rate of change of the piezoelectric coefficient is very small when the operating temperature of the ceramic is raised from room temperature to 100 ℃. When the temperature is further increased to 109 ℃, the piezoelectric coefficient is only reduced by 5.3%, namely the piezoelectric coefficient of the texture sample has the change rate of less than 6% between the room temperature and the Curie temperature, and the excellent temperature stability is maintained, which is a great advantage of the invention.
Example two: the difference between the present embodiment and the first embodiment is: in the second step, the edge {111} is selectedcPreferentially oriented BaTiO3The flaky seed crystal is used as a template seed crystal, and the diameter of the template seed crystal is 20-40 mu m; putting the ceramic green body into a high-temperature furnace, and sintering for 9 hours under the condition of air atmosphere and 1595 ℃; the orthorhombic O-tetragonal T phase transition temperature T of the tetragonal phase A and B bit co-substituted leadless piezoelectric textured ceramic with excellent temperature stabilityo-tBelow room temperature, the ceramic is in a pure tetragonal phase (T) perovskite structure consisting of a ceramic body extending along [111 ]]cThe preferred orientation degree is 92%, and the ceramic section is in a rhombohedral stacking shape; the curie temperature of the tetragonal phase A and B co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability is 109 ℃, and the change rate of the piezoelectric coefficient in the range from room temperature to the curie temperature is lower than 14%. The rest is the same as the first embodiment.
The template seed crystal described in step two was prepared with reference to the following documents: li JL, Shen ZH, Chen XH, Yang S, Zhou WL, Wang MW, Wang LH, Kou QW, Liu YC, Li Q, Xu Z, Chang YF, Zhang SJ, Li F.gain-orientation-engineered multilayered ceramic capacitors for energy storage applications. Nat Mater 2020; 19:999-1005.
Fig. 5 is an XRD pattern of tetragonal phase a and B site co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability prepared in example two. As can be seen, the textured ceramic has a pure tetragonal perovskite phase structure, which is (111)cThe peak intensity is very strong, while others are not {111}cThe peak intensity is very weak, indicating that the material has a grain edge of [111 ]]cHighly preferred orientation. Using Lotgering factor (F)11l) Calculated by analytical method, the textured ceramic grain edge [111 ]]cPreferred degree of orientation F11lUp to 92%. For textured ceramics, F11lHas a value range of 0 < F111< 1, F thereof111Larger, ceramic [111 ]]cThe higher the degree of orientation.
Fig. 6 is an SEM picture of tetragonal phase a and B co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability prepared in example two. The ceramic microstructure is mainly composed of a rim [111 ]]cThe preferred orientation tetragonal phase crystal grain composition, the ceramic section presents a rhombus-like stacking appearance.
FIG. 7 is a graph of the dielectric temperature spectrum of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in example two. As can be seen, the Curie temperature T of the texture samplesc109 ℃ and a ferroelectric orthorhombic-tetragonal phase transition point far away from room temperature, which is-13 ℃. These can guarantee that the tetragonal phase structure exists steadily in wide temperature interval, are favorable to the promotion of sample piezoelectric coefficient temperature stability.
FIG. 8 is the normalized piezoelectric coefficient d of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in example two33 *As a function of temperature. As can be seen from the figure, the piezoelectric coefficient of the texture sample has the change rate of less than 14% between the room temperature and the Curie temperature, and good temperature stability is maintained, which is a great advantage of the invention.
ExamplesThirdly, the method comprises the following steps: the difference between the present embodiment and the first embodiment is: in the first step, the chemical general formula (Ba) of the texture ceramic target component is used0.85Ca0.15)(Ti0.94Hf0.06)O3According to the stoichiometric ratio of BaCO3Powder, CaCO3Powder, TiO2Powder and HfO2The powder is taken as a raw material; TiO described in step one2The particle size of the powder is 20 nm; HfO as described in step one2The particle size of the powder is 60 nm; the precursor base material in the step one is a pure perovskite phase and has an average particle size of 295 nm; the pre-sintering in the step one is specifically that the temperature is kept for 1.5 hours under the condition that the temperature is 1275 ℃; the mass ratio of the precursor base material to the solvent in the third step is 1: 0.45; the mass ratio of the precursor base material to the dispersing agent in the third step is 1: 0.015; the mass ratio of the precursor base material to the adhesive in the third step is 1: 0.04; the mass ratio of the precursor base material to the plasticizer in the third step is 1: 0.04; putting the ceramic green body into a high-temperature furnace, and sintering for 9 hours under the conditions of air atmosphere and 1525 ℃; the tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability has a chemical general formula of (Ba)0.85Ca0.15)(Ti0.94Hf0.06)O3(ii) a The orthorhombic O-tetragonal T phase transition temperature T of the tetragonal phase A and B bit co-substituted leadless piezoelectric textured ceramic with excellent temperature stabilityo-tBelow room temperature, the ceramic is in a pure tetragonal phase (T) perovskite structure consisting of a [001 ] edge]cThe preferred orientation degree is 92%, and the ceramic section is in the shape of a cuboid brick wall; the curie temperature of the tetragonal phase A and B co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability is 113 ℃, and the change rate of the piezoelectric coefficient in the range from room temperature to the curie temperature is lower than 8%. The rest is the same as the first embodiment.
The tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in the third embodiment has a pure tetragonal perovskite phase structure, and the grain edge of the textured ceramic is [001 ]]cPreferred degree of orientation F11lUp to 92%. The ceramic microstructure is mainly composed of edges [001 ]]cThe crystal grains with preferred orientation are formed, and the appearance of a cuboid brick wall is shown. Curie temperature T of the texture samplecThe temperature is 113 ℃, and the ferroelectric orthorhombic-tetragonal phase transformation point of the texture sample is far away from the room temperature and is-12 ℃. The tetragonal phase structure can be ensured to stably exist in a wide temperature range, and the improvement of the temperature stability of the piezoelectric coefficient of the sample is facilitated. The change rate of the piezoelectric coefficient of the texture sample between room temperature and Curie temperature is lower than 8%, and the excellent temperature stability is maintained, which is a great advantage of the invention.

Claims (10)

1. Tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability, and is characterized in that the chemical general formula of the tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic is (Ba)1-xCax)(Ti1-yEy)O3Wherein E is Zr or Hf, x is more than 0.12 and less than 0.30, and y is more than 0 and less than 0.09;
the orthorhombic O-tetragonal T phase transition temperature T of the tetragonal phase A and B bit co-substituted leadless piezoelectric textured ceramic with excellent temperature stabilityo-tBelow room temperature, the ceramic is in a pure tetragonal phase (T) perovskite structure consisting of a [001 ] edge]cOr [111 ]]cThe preferred orientation degree is more than 90 percent; when the tetragonal phase grain is along [001 ]]cWhen the orientation is preferred, the ceramic section is in the shape of a cuboid brick wall; when the tetragonal phase grain is along [111 ]]cWhen preferred orientation is carried out, the ceramic section is in a rhomboid stacking shape;
the curie temperature of the tetragonal phase A and B position co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability is higher than 100 ℃, and the change rate of the piezoelectric coefficient in the range from room temperature to the curie temperature is lower than 15%.
2. The tetragonal phase A and B site co-substituted lead-free piezoelectric textured ceramic with excellent temperature stability according to claim 1, characterized in that the variation rate of the piezoelectric coefficient in the interval from room temperature to Curie temperature is less than 10%.
3. The preparation method of tetragonal A and B site co-substituted leadless piezoelectric textured ceramic with excellent temperature stability as claimed in claim 1 is characterized by comprising the following steps:
firstly, preparing a precursor base material:
the chemical formula (Ba) of the target component of the textured ceramic1-xCax)(Ti1-yEy)O3According to the stoichiometric ratio of BaCO3Powder, CaCO3Powder, TiO2Powder and ZrO2The powder is taken as the raw material or called BaCO3Powder, CaCO3Powder, TiO2Powder and HfO2The powder is taken as a raw material; taking ethanol as a ball milling medium, and performing primary ball milling, drying, presintering, secondary ball milling, drying and sieving to obtain a precursor base material; wherein E is Zr or Hf, x is more than 0.12 and less than 0.30, and y is more than 0 and less than 0.09;
the TiO is2Powder, ZrO2Powder and HfO2The grain diameters of the powder are less than or equal to 60 nm; the precursor base material is a pure perovskite phase and has a particle size of below 300 nm;
secondly, selecting and weighing template seed crystals:
selecting BaTiO3Lamellar seed crystals or SrTiO3Using the flaky seed crystal as a template seed crystal, and respectively weighing a precursor base material and the template seed crystal; the molar ratio of the template seed crystal to the precursor base material is 3 (17-97);
the template seed crystal is of a pure perovskite structure and is arranged along the {001}cOr {111}cPreferred orientation is carried out, the diameter of the seed crystal of the template is less than 50 mu m, and the diameter-thickness ratio is more than or equal to 8;
thirdly, preparing casting slurry:
mixing a solvent, a dispersing agent, an adhesive, a plasticizer and the precursor base material weighed in the second step by ball milling to prepare base material slurry, adding the template seed crystal weighed in the second step into the base material slurry, and continuing ball milling to obtain casting slurry;
fourthly, preparing a ceramic green body:
casting and drying the casting slurry by using a casting machine to obtain a membrane with the thickness of 10-100 microns, sequentially cutting, laminating, hot water homogenizing, cutting and discharging the membrane, and finally performing cold isostatic pressing under the condition that the pressure is 150-300 MPa to obtain a ceramic green body;
fifthly, preparing tetragonal phase lead-free textured ceramic:
and (3) placing the ceramic green body in a high-temperature furnace, and sintering for 2-20 h under the conditions of air atmosphere and temperature of 1450-1600 ℃ to obtain the tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability.
4. The method for preparing tetragonal A and B site co-substituted leadless piezoelectric textured ceramic with excellent temperature stability as claimed in claim 3, wherein the BaCO in step one3Powder, CaCO3Powder, TiO2Powder, ZrO2Powder and HfO2The purity of the powder is more than or equal to 99.9 percent; the primary ball milling time in the step one is 48-96 hours; the pre-sintering in the step one is to preserve heat for 1 to 10 hours under the condition that the temperature is 1000 to 1450 ℃; the secondary ball milling time in the step one is 24-72 h.
5. The preparation method of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability according to claim 3, characterized in that the ball milling mixing time in the third step is 24-48 h; the continuous ball milling time in the third step is 15-60 min.
6. The method for preparing tetragonal A and B position co-substituted leadless piezoelectric textured ceramics with excellent temperature stability as claimed in claim 3, characterized in that in step three, xylene-ethanol mixed solution is used as solvent, molten herring oil is used as dispersant, polyvinyl butyral is used as binder, and polyalkylene glycol and butyl benzyl phthalate are used as plasticizer.
7. The method for preparing tetragonal phase A and B site co-substituted leadless piezoelectric textured ceramic with excellent temperature stability according to claim 6, characterized in that the mass ratio of xylene to ethanol is 1: 1; the mass ratio of the polyalkylene glycol to the butyl benzyl phthalate is 1: 1.
8. The preparation method of tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability according to claim 3, characterized in that the mass ratio of the precursor base material to the solvent in the third step is 1 (0.3-0.8); the mass ratio of the precursor base material to the dispersing agent in the third step is 1 (0.01-0.03); the mass ratio of the precursor base material to the adhesive in the third step is 1 (0.02-0.06); the mass ratio of the precursor base material to the plasticizer in the third step is 1 (0.02-0.08).
9. The method for preparing tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability according to claim 3, characterized in that the laminating in step four is carried out under the conditions of temperature of 60 ℃ to 95 ℃ and pressure of 10MPa to 50MPa, and the heat preservation and pressure maintaining are carried out for 10min to 60 min; the step four, the hot water pressure equalization, is to keep the temperature and the pressure for 15min to 60min under the conditions that the temperature is 60 ℃ to 95 ℃ and the pressure is 20MPa to 50 MPa; the rubber discharging in the fourth step is specifically that rubber is discharged for 1 to 6 hours at the temperature of 550 to 650 ℃; the cold isostatic pressing time in the fourth step is 2 min-20 min.
10. The use of the tetragonal phase a and B site co-substituted leadless piezoelectric textured ceramic with excellent temperature stability according to claim 1, characterized in that it is used in an electronic device which maintains stable electromechanical output in the range of room temperature to 100 ℃; the electronic device is a piezoelectric actuator, an intelligent sensor, an ultrasonic transducer or an energy collector.
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