CN113683409B - 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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CN113683409B
CN113683409B CN202111004591.6A CN202111004591A CN113683409B CN 113683409 B CN113683409 B CN 113683409B CN 202111004591 A CN202111004591 A CN 202111004591A CN 113683409 B CN113683409 B CN 113683409B
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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 art c Decrease in piezoelectric coefficient and deterioration in temperature stability of piezoelectric coefficient. The textured ceramic has a chemical formula of (Ba) 1‑x Ca x )(Ti 1‑y E y )O 3 A pure tetragonal phase perovskite structure at room temperature along [001 ]] c Or [111 ]] c The preferred orientation degree is more than 90%. The method comprises the following steps: 1. preparing a precursor base material; 2. selecting and weighing template seed crystals; 3. preparing casting slurry; 4. preparing a ceramic green body; 5. preparing tetragonal phase leadless 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 are in-situThe production, use and waste treatment process can cause harm to human health and ecological environment. 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 2 3 (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 T c The temperature can be reduced from 120 ℃ of pure BT to 30-80 ℃, and the 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 temperature 0.89 Sn 0.11 )O 3 The 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; will (Ba) 0.85 Ca 0.15 )(Zr 0.10 Ti 0.90 )O 3 The 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 J 0.2 Ti 0.8 )O 3 –x(Ba 0.7 Ca 0.3 )TiO 3 lead-free semiconductors acta Mater 2014; 80:48-55). Curie temperature T c Decrease and deterioration of temperature stability of piezoelectric coefficientThe existing method is not beneficial to device preparation and stable operation, and greatly limits the practical development of the BT-based ceramic. 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 T c Reduce 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-x Ca x )(Ti 1-y E y )O 3 Wherein E is Zr or Hf, and x is more than 0.12 and less than 0.30,0 and less than y 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 stability o-t Below room temperature, the ceramic is in a pure tetragonal phase (T) perovskite structure consisting of a [001 ] edge] c Or [111 ]] c The preferred orientation degree is more than 90 percent; when the tetragonal phase grain is along [001 ]] c When the orientation is preferred, the ceramic section is in the shape of a cuboid brick wall; when the tetragonal phase grain is along [111 ]] c When 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:
1. preparing a precursor base material:
the chemical formula (Ba) of the target component of the textured ceramic 1-x Ca x )(Ti 1-y E y )O 3 According to the stoichiometric ratio of BaCO 3 Powder, caCO 3 Powder, tiO 2 Powder and ZrO 2 The powder is taken as the raw material or called BaCO 3 Powder, caCO 3 Powder, tiO 2 Powder and HfO 2 The 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, and x is more than 0.12 and less than 0.30,0 and less than y and less than 0.09;
the TiO is 2 Powder, zrO 2 Powder and HfO 2 The grain diameters of the powder are less than or equal to 60nm; the precursor base material is a pure perovskite phase and has a particle size of below 300 nm;
2. selecting and weighing template seed crystals:
selecting BaTiO 3 Lamellar seed crystals or SrTiO 3 Using 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} c Or {111} c Preferred 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;
3. 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;
4. 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;
5. 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 previous BT-based ceramic research, selects a pure tetragonal phase perovskite structure at room temperature and has a Curie temperature T c Above 100 deg.C (Ba) 1-x Ca x )(Ti 1-y E y )O 3 Wherein E is Zr or Hf, and x is more than 0.12 and less than 0.30,0 and less than y and less than 0.09 is used as a texture system. For having ABO 3 Pure perovskite structure BaTiO 3 In 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 invention o-t Below room temperature, there is no dispersed phase boundary with coexisting multiple (two) phases near room temperature, and its tetragonal T-cubic C phase transition temperature (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 ]] c Or [111 ]] c Preferred 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 temperature c When 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 ]] c Or [111 ]] c Preferred orientation degree of preferred orientation is higher than 90%, curie temperature is higher than 100 deg.C, and piezoelectric coefficient d is 33 * (S max /E max) At room temperature to T c The 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 method 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.
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 site co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in example one;
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 example 33 * 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 site co-substituted leadless piezoelectric textured ceramics 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 two 33 * 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 of the specific embodiments.
The first embodiment is as follows: the embodiment has excellent temperature stability, and the tetragonal phase A and B sites of the tetragonal phase A co-replace leadless piezoelectric textured ceramic has a chemical general formula of (Ba) 1-x Ca x )(Ti 1-y E y )O 3 Wherein E is Zr or Hf, and x is more than 0.12 and less than 0.30,0 and less than y 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 stability o-t Below room temperature, the ceramic is in a pure tetragonal phase (T) perovskite structure consisting of a [001 ] edge] c Or [111 ]] c The preferred orientation degree is more than 90 percent; when the tetragonal phase grain is along [001 ]] c When the orientation is preferred, the ceramic section is in the shape of a cuboid brick wall; when the tetragonal phase grain is along [111 ]] c When 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: aim atBreaking 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 the novel edge [001 ]] c Or [111 ]] c Preferred 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 material c When 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 performance 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 ]] c Or [111 ]] c Preferred orientation degree of preferred orientation is higher than 90%, curie temperature is higher than 100 deg.C, and piezoelectric coefficient d is 33 * (S max /E max) At room temperature to T c The 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 specific embodiment has excellent temperature stability, namely, the material still keeps a higher piezoelectric coefficient at a higher temperature, so that the temperature application range of the material is remarkably widened. In addition, the preparation method of the embodiment has the advantages of simple and stable preparation process, lower cost, accurate and controllable chemical components, suitability for large-scale industrial production and remarkable reduction of 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:
1. preparing a precursor base material:
the chemical formula (Ba) of the target component of the textured ceramic 1-x Ca x )(Ti 1-y E y )O 3 According to the stoichiometric ratio of BaCO 3 Powder, caCO 3 Powder, tiO 2 Powder and ZrO 2 The powder is taken as a raw material or is called BaCO 3 Powder, caCO 3 Powder of TiO 2 Powder and HfO 2 The 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 0.30,0 and y is more than 0.09;
the TiO is 2 Powder, zrO 2 Powder and HfO 2 The grain diameters of the powder are less than or equal to 60nm; the precursor base material is a pure perovskite phase and has a particle size of below 300 nm;
2. selecting and weighing template seed crystals:
selecting BaTiO 3 Lamellar seed crystals or SrTiO 3 Using 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} c Or 111 c Preferred 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;
3. 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;
4. 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;
5. 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 one 3 Powder, caCO 3 Powder, tiO 2 Powder, zrO 2 Powder and HfO 2 The 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 is as follows: 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 concrete implementation mode: the difference between this embodiment mode and one of the third to sixth embodiment modes is: 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 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 carried out for 15-60 min under the conditions that the temperature is 60-95 ℃ and the pressure is 20-50 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 by the following steps:
1. preparing a precursor base material:
the chemical formula (Ba) of the target component of the textured ceramic 0.85 Ca 0.15 )(Ti 0.95 Zr 0.05 )O 3 According to the stoichiometric ratio of 3 Powder, caCO 3 Powder, tiO 2 Powder and ZrO 2 The 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 is 2 The particle size of the powder is 20nm; the ZrO 2 The particle size of the powder is 50nm; the precursor base material is pure perovskite phase and has the average grain diameter of280nm；
2. Selecting and weighing template seed crystals:
choose the edge {001} c Preferentially oriented BaTiO 3 Using the flaky seed crystals as template seed crystals, and respectively weighing precursor base materials and the template seed crystals; the molar ratio of the template seed crystal to the precursor base material is 5;
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;
3. 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;
4. 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;
5. 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 one 3 Powder, caCO 3 Powder of TiO 2 Powder, zrO 2 The purity of the powder is more than or equal to 99.9 percent; the time of primary ball milling 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 30min.
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; the mass ratio of the precursor base material to the adhesive in the third step is 1; the mass ratio of the precursor base material to the plasticizer in the third step is 1.
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 3min.
The template seed crystal described in step two was prepared with reference to the following documents: 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) O 3 through 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) 0.85 Ca 0.15 )(Ti 0.95 Zr 0.05 )O 3 ；
The orthorhombic O-tetragonal T phase transition temperature T of the tetragonal phase A and B position co-substituted leadless piezoelectric textured ceramic with excellent temperature stability o-t Below room temperature, the ceramic is in a pure tetragonal phase (T) perovskite structure consisting of a [001 ] edge] c The 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) c And (002) c The intensity of the peak is very strong, while others are not {001} c The peak intensity is very weak, showing that the material has a grain edge of [001 ]] c Highly preferred orientation. Using Lotgering factor (F) 00l ) Calculated by analytical method, the textured ceramic grain edge [001 ]] c Preferred degree of orientation F 00l Up to 94%. For textured ceramics, F 00l Has a value range of 0 < F 001 < 1, F thereof 001 Larger, ceramic [001 ]] c The higher the degree of orientation.
Fig. 2 is an SEM picture of tetragonal phase a and B site co-substituted leadless piezoelectric textured ceramic prepared in example one and having excellent temperature stability. As can be seen, the microstructure of the ceramic is mainly defined by the [001 ] edge] c The 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 sample c 109 ℃ and the ferroelectric orthorhombic-tetragonal phase transition point is far away from the room temperature and is-13 ℃. The structure can ensure that the tetragonal phase structure stably exists in a wide temperature range, and is beneficial to the improvement of the temperature stability of the piezoelectric coefficient of the sample.
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 example 33 * 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 continuously increased to 109 ℃ of the Curie temperature, the piezoelectric coefficient is only reduced by 5.3 percent, namely the piezoelectric coefficient of the texture sample between the room temperature and the Curie temperature is changed by less than 6 percent, and the excellent temperature stability is maintained, which is the inventionA great advantage.
The second embodiment: the difference between the present embodiment and the first embodiment is: in the second step, the edge {111} is selected c Preferentially oriented BaTiO 3 The 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 stability o-t Below room temperature, the ceramic is in a pure tetragonal phase (T) perovskite structure consisting of a ceramic body extending along [111 ]] c The 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 in 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 leadless piezoelectric textured ceramic prepared in example two having excellent temperature stability. As can be seen, the textured ceramic has a pure tetragonal perovskite phase structure, which is (111) c The peak intensity is very strong, while others are not {111} c The peak intensity is very weak, indicating that the material has a grain edge of [111 ]] c Highly preferred orientation. Using Lotgering factor (F) 11l ) Calculated by analytical method, the textured ceramic grain edge [111 ]] c Preferred degree of orientation F 11l Up to 92%. For textured ceramics, F 11l Has a value range of 0 < F 111 < 1, F thereof 111 Larger, ceramic [111 ]] c The higher the degree of orientation.
FIG. 6 shows tetragonal phase A and B co-substituted leadless piezoelectric textured ceramic with excellent temperature stability prepared in example twoSEM picture of (d). The ceramic microstructure is mainly composed of a rim [111 ]] c The 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 samples c 109 ℃ and a ferroelectric orthorhombic-tetragonal phase transition point far away from room temperature, which is-13 ℃. The structure can ensure that the tetragonal phase structure stably exists in a wide temperature range, and is beneficial to the improvement of the temperature stability of the piezoelectric coefficient of the sample.
FIG. 8 shows normalized piezoelectric coefficient d of tetragonal phase A and B site co-substituted leadless piezoelectric textured ceramics prepared in example two and having excellent temperature stability 33 * 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.
Example three: 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 used 0.85 Ca 0.15 )(Ti 0.94 Hf 0.06 )O 3 According to the stoichiometric ratio of BaCO 3 Powder, caCO 3 Powder, tiO 2 Powder and HfO 2 The powder is taken as a raw material; tiO described in step one 2 The particle size of the powder is 20nm; hfO as described in step one 2 The particle size of the powder is 60nm; the precursor base material in the step one is a pure perovskite phase and has an average particle size of 295nm; 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; the mass ratio of the precursor base material to the dispersing agent in the third step is 1; the mass ratio of the precursor base material to the adhesive in the third step is 1; the mass ratio of the precursor base material to the plasticizer in the third step is 1; putting the ceramic green body into a high-temperature furnace, and sintering for 9 hours under the conditions of air atmosphere and 1525 ℃; said IV having excellent temperature stabilityThe lead-free piezoelectric textured ceramic with both square phase A and B and its chemical general formula is (Ba) 0.85 Ca 0.15 )(Ti 0.94 Hf 0.06 )O 3 (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 stability o-t Below room temperature, the ceramic is a pure tetragonal phase (T) perovskite structure consisting of a rim [001 ]] c The 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 ]] c Preferred degree of orientation F 11l Up to 92%. The ceramic microstructure is mainly composed of edges [001 ]] c The crystal grains with preferred orientation are formed, and the appearance of a cuboid brick wall is shown. Curie temperature T of the texture sample c The 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-x Ca x )(Ti 1-y E y )O 3 Wherein E is Zr or Hf, and x is more than 0.12 and less than 0.30,0 and less than y 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 stability o-t Below room temperature, the ceramic is pure tetragonal phase (T) calcium at room temperatureTitanium ore structure, composed of edge [001 ]] c Or [111 ]] c The preferred orientation degree is more than 90 percent; when the tetragonal phase grain is along [001 ]] c When the orientation is preferred, the ceramic section is in the shape of a cuboid brick wall; when the tetragonal phase grain is along [111 ]] c When preferred orientation is adopted, the ceramic section is in a rhombus-like 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:
1. preparing a precursor base material:
the chemical formula (Ba) of the target component of the textured ceramic 1-x Ca x )(Ti 1-y E y )O 3 According to the stoichiometric ratio of BaCO 3 Powder, caCO 3 Powder, tiO 2 Powder and ZrO 2 The powder is taken as a raw material or is called BaCO 3 Powder, caCO 3 Powder, tiO 2 Powder and HfO 2 The 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 0.30,0 and y is more than 0.09;
the TiO is 2 Powder, zrO 2 Powder and HfO 2 The grain diameter of the powder is less than or equal to 60nm; the precursor base material is a pure perovskite phase and has a particle size of below 300 nm;
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 ℃;
2. selecting and weighing template seed crystals:
selecting BaTiO 3 Lamellar seed crystals or SrTiO 3 Using 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} c Or {111} c Preferred 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;
3. 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;
4. 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;
5. 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 one 3 Powder, caCO 3 Powder, tiO 2 Powder, zrO 2 Powder and HfO 2 The purity of the powder is more than or equal to 99.9 percent; the time of primary ball milling in the step one is 48-96 hours; 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 as claimed in 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 60min; 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 the 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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