CN112225550A - Piezoelectric ceramic material, preparation method thereof and piezoelectric ceramic sensor - Google Patents
Piezoelectric ceramic material, preparation method thereof and piezoelectric ceramic sensor Download PDFInfo
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Abstract
The invention relates to a piezoelectric ceramic material, a preparation method thereof and a piezoelectric ceramic sensor. The piezoceramic material is a samarium and scandium codoped bismuth ferrite-barium titanate-strontium titanate piezoceramic material which is made of a ferroelectric material BiFeO3、BaTiO3And SrTiO3Is prepared by doping Sm and Sc rare earth elements and sintering in a solid phase, and has the following chemical general formula: 0.4Bi0.85Sm0.15Fe0.95Sc0.05O3‑0.27BaTiO3‑0.33SrTiO3. Sm and Sc doped modified pure iron is utilized in the piezoelectric ceramic materialThe bismuth titanate-barium titanate-strontium titanate material has the technical problems that Sm replaces Bi in bismuth ferrite lattices, so that much Bi is volatilized due to overhigh temperature in the sintering process, the stoichiometric ratio is unbalanced, more impurity phases are generated, and the resistivity is sharply reduced; in addition, the doping of Sc can improve Fe3+Stability of (1), effective inhibition of Fe3+To Fe2+The conversion of (2) and further avoiding the charge flow between two valence state iron ions, and effectively improving the piezoelectric performance of the capacitor dielectric medium.
Description
Technical Field
The invention relates to the technical field of piezoelectric ceramic sensors, in particular to a piezoelectric ceramic material, a preparation method thereof and a piezoelectric ceramic sensor.
Background
The piezoelectric material is a functional material capable of realizing the interconversion between mechanical energy and electric signals, and is widely applied to the fields of national life, mechanical manufacturing, aerospace, exploration, military, national defense and the like. Piezoelectric materials include several major classes, including piezoelectric single crystals, piezoelectric ceramics, piezoelectric polymers, and piezoelectric composites. The piezoelectric ceramic occupies the market leading position of piezoelectric materials due to the characteristics of simple synthesis process, low synthesis cost, excellent piezoelectric performance, adjustable components and the like.
At present, Pb (Zr, Ti) O3The (PZT) ceramic material has excellent dielectric and piezoelectric properties, Curie temperature Tc360 ℃ is the hot material of high-temperature piezoelectric ceramics. However, PZT ceramic materials cannot work safely at temperatures above 200 ℃, and Pb is volatile, so that the pollution to the environment and human bodies is not negligible. Therefore, the research of Pb-free ceramic systems having high curie temperature and excellent piezoelectric properties is an urgent need in the fields of automobile manufacturing, aviation, petrochemical industry, and the like, which are increasing day by day. The existing Pb-free piezoelectric ceramic system mainly comprises barium titanate (BaTiO)3) Sodium magnesium titanate (Bi)0.5Na0.5TiO3) Potassium sodium based (KNaNbO)3) Miraculous layer base, tungsten bronze base, aluminic acid miraculous base (BiAlO)3) And ferrous acid secret group (BiFeO)3) And the like. In which BiFeO3Base ceramics due to their high Curie temperature (T)c830 deg.C) and denier temperature (T)N370 ℃) causes the compound to have wide application prospect in the fields of electronic devices and the like. However, since the piezoelectric ceramic of this system is sintered, Bi3+Volatile, and Fe3+Is reduced to Fe2+A large number of oxygen vacancy defects are generated, which results in low resistivity and large leakage current at room temperature, causes the defects of poor insulating property, high dielectric loss and the like, and is not beneficial to BiFeO3Ceramic materialThe preparation and high electric field polarization of (2) limit its practical application.
In order to improve BiFeO3The performance of the base piezoelectric ceramics is mainly optimized by the prior preparation process, such as water quenching, rapid liquid phase sintering and A, B bit element doping, such as A bit doping Sm3+、La3+,Nd3+Plasma, B site doping with Al3+,Sc3+,Ti4+Plasma, with other stable ABO3The structure forms a solid solution, e.g. BaTiO3，SrTiO3，NaNbO3Etc., wherein BiFeO3-BaTiO3Compared with pure BiFeO, the base material3The base material has more stable structure, better insulating property and piezoelectric property, but the application of the base material under high temperature and high electric field is limited.
Disclosure of Invention
Based on this, the present invention aims to overcome the disadvantages of the prior art and provide a piezoelectric ceramic material having the advantages of good piezoelectric performance, high curie temperature, excellent fatigue characteristics, etc.
The specific technical scheme of the invention is as follows:
a piezoelectric ceramic material is a samarium and scandium codoped bismuth ferrite-barium titanate-strontium titanate piezoelectric ceramic material, which is prepared from a ferroelectric material BiFeO3、BaTiO3And SrTiO3Is prepared by doping Sm and Sc rare earth elements and sintering in a solid phase, and has the following chemical general formula: 0.4Bi0.85Sm0.15Fe0.95Sc0.05O3-0.27BaTiO3-0.33SrTiO3。
Compared with the prior art, the Sm and Sc doped modified pure bismuth ferrite-barium titanate-strontium titanate material is adopted in the piezoelectric ceramic material, and Bi in bismuth ferrite crystal lattices is replaced by Sm, so that the technical problems that the stoichiometric ratio is unbalanced and more impurity phases are generated due to the fact that more Bi is volatilized caused by overhigh temperature in the sintering process, and meanwhile the resistivity is sharply reduced are solved; in addition, the doping of Sc can improve Fe3+Stability of (1), effective inhibition of Fe3+To Fe2+To thereby avoid two valence states of ironThe charge among the ions flows, and the piezoelectric property of the capacitor dielectric is effectively improved. The doping of rare earth elements Sm and Sc improves the pure BiFeO3Low resistivity and large leakage current, greatly improves the piezoelectric performance and fatigue property of the piezoelectric material, and has the piezoelectric constant d33120pC/N, aging time greater than 900h, fatigue cycle number greater than 105And has a higher Curie temperature Tc＝400℃。
In addition, the invention also provides a preparation method of the piezoelectric ceramic material, which comprises the following operation steps:
step S1, batching
Selecting analytically pure Bi2O3、BaCO3、TiO2、Sm2O3、Sc3O2、SrCO3And Fe2O3Is used as raw material and has the chemical formula of [0.4Bi0.85Sm0.15Fe0.95Sc0.05O3-0.27BaTiO3-0.33SrTiO3]Weighing the raw material powder according to the stoichiometric ratio required by the system;
step S2, ball milling
Performing ball milling treatment on the raw material powder obtained in the step S1 to obtain mixed powder; sealing and pre-burning the mixed powder for 2 hours, and performing secondary ball milling treatment on the pre-burned mixed powder;
step S3, grinding and granulating
Adding an adhesive into the mixed powder obtained in the step S2, fully grinding and granulating, and then pressing into a piezoelectric ceramic blank;
step S4, binder removal and sintering
And (5) carrying out glue discharging treatment on the piezoelectric ceramic blank obtained in the step (S3), then sealing and sintering the piezoelectric ceramic blank subjected to glue discharging treatment for 3 hours, and cooling to obtain the piezoelectric ceramic material.
In the preparation method of the piezoelectric ceramic material, weighed powder is primarily mixed by ball milling in the step S2, so that the preparation method is simple in process and easy to implement; volatile matters in the raw material powder can be removed by utilizing sealing and pre-burning so as to prevent cracks caused by excessive shrinkage in the sintering process and form a required crystal orientation; the target powder with more uniform components and finer particles can be obtained by performing secondary ball milling on the pre-sintered powder, so that the pressure resistance of the subsequent piezoelectric ceramic material is improved and the microstructure is optimized; the solid-phase sintering process of step S4 further promotes the formation of the desired crystal orientation and makes it more dense, so that the material structure is very dense, substantially no voids exist, and the crystal grains are clear and uniform in size, thereby obtaining the piezoelectric ceramic with excellent properties.
Compared with hot-pressing sintering and rapid liquid-phase sintering, the piezoelectric ceramic material is formed by sintering through a solid-phase sintering method, the piezoelectric ceramic material is basically free of impurity phase generation, compact in structure, uniform in components, excellent in piezoelectric performance, high in Curie temperature and excellent in fatigue property, and the preparation method is simple in process, high in production efficiency and easy to control generation of the ceramic structure.
Further, the ball milling treatment in the step S2 is to add zirconia balls and ethanol into the powder, and then ball mill the powder for 12-36 hours at a rotation speed of 300-500 rpm.
Further, in the step S2, the mass ratio of the powder to the zirconia grinding balls in the ball milling treatment is 1:1, and the diameter of the zirconia grinding balls is 3-6 mm.
Furthermore, in the step S2, the number ratio of the grinding balls with the diameter of 6mm, the grinding balls with the diameter of 4-5 mm and the grinding balls with the diameter of 3mm in the zirconia grinding balls is 1:2: 3.
The zirconia grinding ball has high density, fine texture, high surface smoothness after grinding, small friction coefficient, better grinding effect than grinding balls with single size and high grinding efficiency.
Further, in step S2, after the ball milling, the sealing and pre-sintering, and the secondary ball milling, drying the obtained mixed powder, and grinding the dried mixed powder without ethanol. Through ball milling for many times and grinding after drying at every time, the mixed powder can be further more uniform and finer in particle, and the ceramic structure obtained after calcination is more compact and the perovskite structure is more stable.
Further, the specific operation step of the sealing and pre-sintering in step S2 is to put the dried mixed powder into an alumina crucible, place the alumina crucible on an alumina sintering plate, and add a layer of raw powder with the same composition and ratio as the mixed powder around the alumina crucible along the circumferential direction; and then an alumina crucible is reversely placed above the alumina crucible containing the mixed powder, and a layer of alumina powder is covered on the opening of the reversely placed alumina crucible along the circumferential direction for sealing.
Further, the step S3 of removing the glue includes that the piezoelectric ceramic blank is first heat-insulated at 300 ℃ for 1 hour and then heated to 500 ℃ for 2 hours; the processing temperature of the sealing pre-sintering is 800 ℃, and the processing temperature of the sealing sintering is 1100 ℃.
Further, the specific operation step of the sealing sintering in step S4 is to place the ceramic green body on an alumina sintering plate, and add a layer of raw material powder with the same component and ratio as the mixed powder on the ceramic green body; and then an alumina crucible is placed above the ceramic blank in an inverted manner, and a layer of alumina powder is covered at the opening of the alumina crucible along the circumferential direction for sealing.
The aluminum oxide crucible is matched with the aluminum oxide sintering plate for sealing and high-temperature calcination, and can be matched with a muffle furnace or other heating equipment for laboratory heat treatment and other high-temperature experiments, so that the stability is high, the heat preservation durability is high, the automation degree is high, and the safety is high.
In addition, the invention also provides a piezoelectric ceramic sensor which comprises a piezoelectric ceramic capacitor, wherein the piezoelectric ceramic capacitor comprises a bottom electrode, a top electrode and a dielectric medium; the piezoelectric ceramic sensor is characterized in that the dielectric medium is positioned between the bottom electrode and the top electrode, the dielectric medium is the piezoelectric ceramic material, and the piezoelectric ceramic sensor is high in piezoelectric performance, high in piezoelectric output sensitivity, high in working temperature and long in service life.
Drawings
FIG. 1 is a comparative XRD diffraction pattern of a sample of BSFS-BT-ST ceramic according to the present invention;
FIG. 2 is an SEM cross-sectional representation of a BSFS-BT-ST ceramic sample according to the present invention;
FIG. 3 is a hysteresis loop plot of the BSFS-BT-ST ceramic of the present invention at different voltages;
FIG. 4 is a hysteresis loop plot of the BSFS-BT-ST ceramic of the present invention at different temperatures;
FIG. 5 is a graph of dielectric constant versus dielectric loss for BSFS-BT-ST ceramic of the present invention at different frequencies;
FIG. 6 shows the piezoelectric coefficient d of the BSFS-BT-ST ceramic of the present invention at different temperatures33And d31A graph of the change in value of (c);
FIG. 7 shows the piezoelectric coefficient d of the BSFS-BT-ST ceramic according to the present invention33Graph of time at room temperature;
FIG. 8 shows the piezoelectric coefficient d of the BSFS-BT-ST ceramic according to the present invention33Graph of fatigue cycle number at room temperature.
Detailed Description
Example 1
The embodiment of the invention provides a piezoceramic material, which is a samarium and scandium codoped bismuth ferrite-barium titanate-strontium titanate piezoceramic material and is prepared from a ferroelectric material BiFeO3、BaTiO3And SrTiO3Is prepared by doping Sm and Sc rare earth elements and sintering in a solid phase, and has the following chemical general formula: 0.4Bi0.85Sm0.15Fe0.95Sc0.05O3-0.27BaTiO3-0.33SrTiO3It is abbreviated as BSFS-BT-ST.
Compared with the prior art, the Sm and Sc doped modified pure bismuth ferrite-barium titanate-strontium titanate material is adopted in the piezoelectric ceramic material, and Bi in bismuth ferrite crystal lattices is replaced by Sm, so that the technical problems that the stoichiometric ratio is unbalanced and more impurity phases are generated due to the fact that more Bi is volatilized caused by overhigh temperature in the sintering process, and meanwhile the resistivity is sharply reduced are solved; in addition, the doping of Sc can improve Fe3+Stability of (1), effective inhibition of Fe3+To Fe2+And thus avoid bothThe charge flow between the valence state iron ions effectively improves the piezoelectric property of the capacitor dielectric medium. The doping of rare earth elements Sm and Sc improves the pure BiFeO3Low resistivity and large leakage current, greatly improves the piezoelectric performance and fatigue property of the piezoelectric material, and has the piezoelectric constant d33120pC/N, aging time greater than 900h, fatigue cycle number greater than 105And has a higher Curie temperature Tc＝400℃。
Example 2
Embodiment 2 of the present invention provides a method for preparing a piezoelectric ceramic material, which comprises the following steps:
step S1: ingredients
To analytically pure Bi2O3、BaCO3、TiO2、Sm2O3、Sc3O2、SrCO3And Fe2O3Is used as raw material and has a chemical formula of [0.4Bi0.85Sm0.15Fe0.95Sc0.05O3-0.27BaTiO3-0.33SrTiO3]Weighing the raw material powder according to the stoichiometric ratio required by the system.
It should be noted that, in the description of the embodiment of the present invention, the samarium-scandium co-doped bismuth ferrite-barium titanate-strontium titanate piezoelectric ceramic material is abbreviated as BSFS-BT-ST ceramic.
In this embodiment, the total amount of the BSFS-BT-ST ceramic powder to be prepared is 0.1mol, and the preparation raw materials of the BSFS-BT-ST ceramic powder are shown in table 1:
TABLE 1 preparation of BSFS-BT-ST powder
Please refer to table 1, which is a raw material for preparing BSFS-BT-ST ceramic powder, each raw material was weighed according to the weighed mass in table 1 using an electron level with an accuracy of 0.0001 to prepare a ceramic powder having a chemical formula of [0.4Bi [0.85Sm0.15Fe0.95Sc0.05O3-0.27BaTiO3-0.33SrTiO3]The powder of (1).
Step S2: synthesis of BSFS-BT-ST ceramic powder
The conventional methods for preparing piezoelectric ceramic powder mainly comprise a traditional solid phase method, a microwave hydrothermal method, a sol-gel method, a coprecipitation method, a molten salt method and the like, wherein powder samples prepared by the microwave hydrothermal method and the sol-gel method are high in purity and small in particle size, but the method is only suitable for basic research in a laboratory, is low in yield and is not suitable for large-scale industrial production. The samples prepared by the coprecipitation method and the molten salt method have high purity, good dispersibility and uniform size distribution, but the process flow is complex, so the method is not beneficial to industrial production, and the traditional solid phase method is suitable for industrial production and has the advantages of high yield, capability of meeting the requirement of industrial mass production and low cost.
In the embodiment of the invention, the synthesis of the BSFS-BT-ST ceramic powder adopts a traditional solid-phase sintering method, and specifically comprises the following steps:
s201: performing primary ball milling, namely putting the raw material powder weighed in the step S1 into a nylon ball milling tank, and then adding ethanol as a dispersing agent and zirconia grinding balls with different diameters as grinding media, wherein in the embodiment, the ratio of the total mass of the zirconia grinding balls to the total mass of the raw material powder is 1:1, the diameter of the zirconia grinding balls is 3-6 mm, and the number ratio of the grinding balls with the diameter of 6mm, the grinding balls with the diameter of 4-5 mm and the grinding balls with the diameter of 3mm is 1:2: 3; the total volume of the grinding balls, the raw material powder and the alcohol accounts for 60 percent of the total volume of the ball milling tank. And (3) putting the nylon ball milling tank into a ball mill for grinding, controlling the rotating speed of the ball mill to be 418 revolutions per minute, setting the primary ball milling time to be 24 hours, and drying the obtained mixed powder in an oven at 80 ℃ after the ball milling is finished.
S202: grinding, pouring the mixed powder dried in the step S201 into an agate mortar, and grinding for 20-30 minutes by using an agate rod;
s203: and (4) high-temperature presintering, pouring the mixed powder ground in the step S202 into an alumina crucible, sealing and calcining for 2 hours in a muffle furnace at 800 ℃, controlling the heating rate to be 8 ℃/min, and naturally cooling to room temperature along with the furnace after calcining is finished.
In this embodiment, the sealing and pre-sintering process includes the specific steps of placing the dried mixed powder into an alumina crucible, placing the alumina crucible on an alumina sintering plate, and adding a layer of raw powder with the same composition and ratio as the mixed powder around the alumina crucible along the circumferential direction; and then an alumina crucible is reversely placed above the alumina crucible containing the mixed powder, and a layer of alumina powder is covered on the opening of the reversely placed alumina crucible along the circumferential direction for sealing.
S202: grinding, pouring the mixed powder dried in the step S203 into an agate mortar, and grinding for 20-30 minutes by using an agate rod;
s205: performing secondary ball milling, namely putting the mixed powder obtained in the step S204 into a nylon ball milling tank, and then adding ethanol as a dispersing agent and zirconia grinding balls with different diameters as grinding media, wherein in the embodiment, the ratio of the total mass of the zirconia grinding balls to the total mass of the mixed powder is 1:1, the diameter of the zirconia grinding balls is 3-6 mm, and the number ratio of the grinding balls with the diameter of 6mm, the grinding balls with the diameter of 4-5 mm and the grinding balls with the diameter of 3mm is 1:2: 3; the total volume of the grinding balls, the raw material powder and the alcohol accounts for 60 percent of the total volume of the ball milling tank. Putting the nylon ball milling tank into a ball mill for grinding, controlling the rotating speed of the ball mill to be 418 revolutions per minute, setting the primary ball milling time to be 24 hours, and drying the obtained mixed powder in an oven at 80 ℃ after the ball milling is finished;
s202: and (4) grinding, namely pouring the dried mixed powder in the step S205 into an agate mortar, and grinding for 20-30 minutes by using an agate rod.
Step S3: molding tablet
The existing ceramic forming method mainly comprises cold isostatic pressing, ultrahigh pressure forming, dry pressing and the like. The cold static pressure forming is to use liquid as pressure transmission medium in a high-pressure container, so as to obtain the ceramic blank with high density and good uniformity. Ultrahigh pressure molding is a molding method which is developed quickly, and due to uneven stress caused by high pressure, the obtained sample is small. The dry pressing molding is simple in operation and low in cost, and is suitable for blanks with simple shapes and small sizes. The embodiment adopts dry pressing molding.
Specifically, the operation of this embodiment is to weigh 5g of the mixed powder prepared in step S2, add a certain amount of adhesive, and then fully grind and granulate, in this embodiment, the adhesive is polyvinyl alcohol (PVA) with a concentration of 2 wt%; then 0.5g of the granulated mixed powder is weighed and filled into a tabletting mold, and is pressed and formed by a powder tabletting machine in a single shaft way, the pressure is controlled to be 9MPa, and the pressure is maintained for 60 seconds, so that a BSFS-BT-ST ceramic blank with the diameter of 12mm and the thickness of 1mm is prepared.
Step S4: and (5) removing the glue and sintering.
And (5) carrying out glue discharging treatment on the piezoelectric ceramic blank obtained in the step (S3), then sealing and sintering the piezoelectric ceramic blank subjected to glue discharging treatment for 3 hours, and cooling to obtain the piezoelectric ceramic material.
As more organic binders, plasticizers and the like are added in the ceramic material forming process, such as paraffin wax and rolled films formed by hot-press casting, polyvinyl alcohol (PVA) and the like are added in the embodiment. During high-temperature sintering, a large amount of organic matters in the green body are melted, decomposed and volatilized, so that the green body is deformed and cracked, and meanwhile, the carbon content of the organic matters is high, and when oxygen is insufficient to form a reducing atmosphere, the sintering quality is influenced. Therefore, organic matters in the green body need to be removed before the green body is fired so as to meet the requirements of the shape, the size and the quality of a product, and the process is glue removal treatment.
In this embodiment, the operation of the binder removal sintering is to place the BSFS-BT-ST blank prepared in step S3 on an alumina sintering plate, lay a layer of raw material powder with the same composition and ratio as the mixed powder on the surface, place an alumina crucible upside down over the BSFS-BT-ST blank, place the alumina crucible in a muffle furnace in a sealed manner, control the temperature rise rate at 5 ℃/min, slowly raise the temperature to 300 ℃ for 1 hour, slowly raise the temperature to 550 ℃ for 2 hours, complete the binder removal process, control the temperature rise rate at 8 ℃/min, raise the temperature to 1100 ℃ for 3 hours, and naturally cool the furnace to room temperature, thereby obtaining the BSFS-BT-ST ceramic with a thickness of 1 mm.
In the preparation method of the piezoelectric ceramic material, weighed powder is primarily mixed by ball milling in the step S2, so that the preparation method is simple in process and easy to implement; volatile matters in the raw material powder can be removed by utilizing sealing and pre-burning so as to prevent cracks caused by excessive shrinkage in the sintering process and form a required crystal orientation; the target powder with more uniform components and finer particles can be obtained by performing secondary ball milling on the pre-sintered powder, so that the pressure resistance of the subsequent piezoelectric ceramic material is improved and the microstructure is optimized; in addition, the grinding ball is limited to be used for grinding, the weight ratio of the grinding balls of the zirconia with different diameters is limited, the compactness of the grinding ball of the zirconia is high, the texture is fine, after grinding, the surface smoothness is high, the friction coefficient is small, the grinding balls with different diameters are matched to be used, the grinding effect is better than that of the grinding balls with single size, and the grinding efficiency is high. In addition, through ball milling for many times and grinding after drying at every time, the mixed powder can be further more uniform and finer in particle, and the ceramic structure obtained after calcination is more compact and the perovskite structure is more stable.
The solid-phase sintering process of step S4 further promotes the formation of the desired crystal orientation and makes it more dense, so that the material structure is very dense, substantially no voids exist, and the crystal grains are clear and uniform in size, thereby obtaining the piezoelectric ceramic with excellent properties. And the alumina crucible is matched with the alumina sintering plate for sealing and high-temperature calcination, and can be matched with a muffle furnace or other heating equipment for laboratory heat treatment and other high-temperature experiments, so that the stability is high, the heat preservation durability is high, the automation degree is high, and the safety is high.
Compared with hot-pressing sintering and rapid liquid-phase sintering, the piezoelectric ceramic material is formed by sintering through a solid-phase sintering method, the piezoelectric ceramic material is basically free of impurity phase generation, compact in structure, uniform in components, excellent in piezoelectric performance, high in Curie temperature and excellent in fatigue property, and the preparation method is simple in process, high in production efficiency and easy to control generation of the ceramic structure.
Example 3
In this example, the piezoelectric ceramic material prepared in example 2 was subjected to a related performance test.
(I) pretreatment
In order to facilitate the performance test of the BSFS-BT-ST ceramic prepared by the preparation method described in example 2, the BSFS-BT-ST ceramic is also required to be pretreated.
The pretreatment is to add the following steps after the preparation process of the BSFS-BT-ST ceramic:
step S5: and (4) grinding and polishing, namely grinding the BSFS-BT-ST ceramic prepared in the step (S4) to a slice of 0.1-0.2mm by using sand paper, and grinding and polishing the slice to a BSFS-BT-ST ceramic slice of 0.17mm thick by using metallographic sand paper.
The polishing and burnishing operation in the embodiment is to polish and grind the BSFS-BT-ST ceramic on 200-mesh abrasive paper until the polished and ground surface of the BSFS-BT-ST ceramic is not obviously changed, and to change the polished and ground surface to 400 meshes, 800 meshes and 1000 meshes and perform the same operation; and polishing by using metallographic abrasive paper after finishing the operation on the 1000-mesh abrasive paper.
Step S6: and plating an electrode.
The electrode of ceramic is manufactured to make the sample conductive, and generally, a metal layer is uniformly coated on two surfaces of the ceramic wafer, wherein gold (Au), silver (Ag), copper (Cu), nickel (Ni), and the like can be used as the metal electrode, and in this embodiment, the Au electrode is preferred.
The upper and lower Au electrodes can be plated by ion sputtering, magnetron sputtering, electron beam evaporation, pulsed laser deposition, ion beam deposition, chemical vapor deposition, and the like. In this embodiment, an electrode is plated by an ion sputtering method, residual gas molecules are ionized under the action of high voltage 1500V in a vacuum container to form plasma, and cations bombard a metal target under the acceleration of an electric field to sputter metal atoms onto the surface of a sample to form a conductive film. The ion sputtering method has the advantages of strong adhesive force between the obtained coating film and the substrate, high deposition rate and high film density.
S601: bottom-plated electrode
Placing the BSFS-BT-ST ceramic wafer into a small ion sputtering instrument, and using Au as a target material at 2 x 10-3Growing an Au electrode film under Pa vacuum, controlling the sputtering current to be 8-10 mA, and carrying out argon sputteringThe target was sputtered in an atmosphere of gas (Ar) for 40 seconds, and the sputtering operation was repeated 4 times with an interval of 20 seconds. And taking out the sample after sputtering is finished, and baking the sample on a heating table at 90 ℃ for 6 minutes to ensure that the sputtered Au electrode is better adhered to the bottom surface of the ceramic chip.
S602: top-plated electrode
And placing a mask plate with a hole with the diameter of 1.5mm on the side, which is not plated with the electrode, of the BSFS-BT-ST ceramic sheet, and repeating the operation of plating the bottom electrode in the step S601 to obtain the top electrode. In this embodiment, the diameter of the holes on the mask is 1.5 mm.
(II) correlation Performance test
1) XRD diffraction measurement
Please refer to fig. 1, which is a XRD diffractogram of the BSFS-BT-ST ceramic sample of the present invention. The test result is obtained by a ray diffractometer (X' Pert PRO, PANALYTICAL X) test, and as can be seen from the figure, with the co-doping of Sm and Sc ions, the diffraction peak at the 2 theta of 31-32 degrees appears to be maximum, and the diffraction peak at the 2 theta of 38 degrees gradually weakens, and no other impurity phases are generated, and the phenomena show that the BSFS-BT-ST ceramic is a pure pseudo-cubic perovskite structure, and the BSFS and the BT-ST form a perfect solid solution.
2) SEM representation
Please refer to fig. 2, which is a SEM cross-sectional representation of a BSFS-BT-ST ceramic sample according to the present invention. The test results were obtained by testing BSFS-BT-ST ceramic obtained in step S4 of example 2 with a scanning electron microscope (ZEISS Gemini 500). As can be seen from the figure, the surface microstructure of the BSFS-BT-ST ceramic sample presents regular particles, and meanwhile, the BSFS-BT-ST ceramic sample has obvious grain boundaries and no holes, defects and impurities, and the ceramic sample grows compactly and has good crystallinity.
3) Hysteresis loop diagram
Referring to fig. 3 and 4, fig. 3 is a hysteresis loop diagram of the BSFS-BT-ST ceramic of the present invention at different voltages, and fig. 4 is a hysteresis loop diagram of the BSFS-BT-ST ceramic of the present invention at different temperatures. The test results were obtained by subjecting the BSFS-BT-ST ceramic obtained in step S6 of this example to a Ferroelectric Tester (radial Technology Ferroelectric Tester)And (4) electrically testing. As can be seen from FIG. 3, the BSFS-BT-ST ceramic has some typical ferroelectric hysteresis characteristics, and the saturation polarization value and the residual planned value gradually increase to reach 45.5 μ C/cm respectively with the increase of the applied voltage2And 19.5. mu.C/cm2The electric field strength can reach 162 kV/cm. It can be seen from FIG. 4 that the BSFS-BT-ST ceramic has excellent temperature stability in the range of 25-200 ℃.
4) Dielectric property test
Referring to fig. 5, fig. 5 is a graph of dielectric constant-dielectric loss at different frequencies of the BSFS-BT-ST ceramic, and the test results were obtained by testing the BSFS-BT-ST ceramic prepared in example 2 using a Ferroelectric Tester (radial Technology Ferroelectric Tester). The frequency range in fig. 5 shows that two peaks appear in the dielectric spectrum of the BSFS-BT-ST ceramic, and the peak at the high temperature position is a frequency-dependent peak, which moves towards the high temperature direction along with the increase of the frequency, so that the BSFS-BT-ST ceramic has a ferroelectric phase and a relaxation phase at the same time, and the dielectric constant corresponding to the peak decreases along with the increase of the frequency, and the corresponding temperature maximum can reach 400 ℃. Meanwhile, as can be seen from fig. 5, the dielectric loss is very small, and the values are all below 0.5, which indicates that the insulation of the sample is very good.
5) Piezoelectric performance test
Referring to FIG. 6, FIG. 7 and FIG. 8, FIG. 6 shows the piezoelectric constant d of BSFS-BT-ST ceramic at different temperatures33And d31FIG. 7 is a graph showing the piezoelectric constant d of the BSFS-BT-ST ceramic33FIG. 8 is the piezoelectric constant d of BSFS-BT-ST ceramic as a function of time at room temperature33Plot of unipolar cycle number as a function of room temperature. D in FIGS. 7 and 833The values of (A) are expressed as a percentage of the initial value of the BSFS-BT-ST ceramic. FIG. 6 shows the piezoelectric constant d of the BSFS-BT-ST ceramic33And d31The values are respectively 120pC/N and 80pC/N at room temperature under the condition of basically unchanged in the temperature of 20-200 ℃, and the BSFS-BT-ST ceramic has better thermal stability. From FIG. 7, it can be seen that the piezoelectric constant d is within 0 to 900 hours33Has a value of substantially constant, relatively changing<3 percent, which shows that the BSFS-BT-ST ceramic has excellent aging performance. The piezoelectricity of the BSFS-BT-ST ceramic can be seen from FIG. 8Constant d33The relative change is not obvious fluctuation along with the increase of the number of measurement cycles<3% and cycle number>105The BSFS-BT-ST ceramic has good fatigue property.
Example 4
Embodiment 4 of the present invention provides a piezoelectric ceramic sensor, which includes a piezoelectric ceramic capacitor, where the piezoelectric ceramic capacitor includes a bottom electrode, a top electrode, and a dielectric medium; the dielectric medium is located between the bottom electrode and the top electrode, the dielectric medium is the piezoelectric ceramic material in embodiment 1, and the piezoelectric ceramic sensor is high in piezoelectric performance, high in piezoelectric output sensitivity, high in working temperature and long in service life.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. A piezoceramic material, characterized by: is samarium and scandium codoped bismuth ferrite-barium titanate-strontium titanate piezoelectric ceramic material which is prepared from ferroelectric material BiFeO3、BaTiO3And SrTiO3Is prepared by doping Sm and Sc rare earth elements and sintering in a solid phase, and has the following chemical general formula: 0.4Bi0.85Sm0.15Fe0.95Sc0.05O3-0.27BaTiO3-0.33SrTiO3。
2. Method for the preparation of a piezoceramic material according to claim 1, characterized in that it comprises the following operative steps:
step S1, batching
Selecting analytically pure Bi2O3、BaCO3、TiO2、Sm2O3、Sc3O2、SrCO3And Fe2O3Is used as raw material and has the chemical formula of [0.4Bi0.85Sm0.15Fe0.95Sc0.05O3-0.27BaTiO3-0.33SrTiO3]Weighing the raw material powder according to the stoichiometric ratio required by the system;
step S2, ball milling
Performing ball milling treatment on the raw material powder obtained in the step S1 to obtain mixed powder; sealing and pre-burning the mixed powder for 2 hours, and performing secondary ball milling treatment on the pre-burned mixed powder;
step S3, grinding and granulating
Adding an adhesive into the mixed powder obtained in the step S2, fully grinding and granulating, and then pressing into a piezoelectric ceramic blank;
step S4, binder removal and sintering
And (5) carrying out glue discharging treatment on the piezoelectric ceramic blank obtained in the step (S3), then sealing and sintering the piezoelectric ceramic blank subjected to glue discharging treatment for 3 hours, and cooling to obtain the piezoelectric ceramic material.
3. The method for producing a piezoelectric ceramic material according to claim 2, characterized in that: the ball milling treatment in the step S2 is to add zirconium oxide grinding balls and ethanol into the powder and then ball mill the powder for 12-36 hours at a rotating speed of 300-500 r/min.
4. A method for producing a piezoelectric ceramic material according to claim 3, characterized in that: the mass ratio of the powder to the zirconia grinding balls in the ball milling treatment in the step S2 is 1:1, and the diameter of the zirconia grinding balls is 3-6 mm.
5. The method for producing a piezoelectric ceramic material according to claim 4, wherein: in the step S2, the number ratio of the grinding balls with the diameter of 6mm, the grinding balls with the diameter of 4-5 mm and the grinding balls with the diameter of 3mm in the zirconia grinding balls is 1:2: 3.
6. The method for producing a piezoelectric ceramic material according to claim 5, wherein: and step S2, drying the obtained mixed powder after the ball milling treatment, the sealing pre-sintering and the secondary ball milling treatment, and grinding the dried mixed powder without ethanol.
7. The method for producing a piezoelectric ceramic material according to claim 2, characterized in that: the specific operation steps of the sealing and pre-burning in the step S2 are to firstly place the dried mixed powder in an alumina crucible, place the alumina crucible on an alumina sintering plate, and add a layer of raw material powder with the same component and proportion as the mixed powder around the alumina crucible along the circumferential direction; and then an alumina crucible is reversely placed above the alumina crucible containing the mixed powder, and a layer of alumina powder is covered on the opening of the reversely placed alumina crucible along the circumferential direction for sealing.
8. The method for producing a piezoelectric ceramic material according to claim 2, characterized in that: step S3, the glue discharging treatment is that the piezoelectric ceramic blank is firstly insulated for 1 hour at 300 ℃ and then heated to 500 ℃ and insulated for 2 hours; the processing temperature of the sealing pre-sintering is 800 ℃, and the processing temperature of the sealing sintering is 1100 ℃.
9. The method for producing a piezoelectric ceramic material according to claim 8, wherein: the specific operation step of the sealed sintering in the step S4 is to place the ceramic blank on an alumina sintering plate, and add a layer of raw material powder with the same component and proportion as the mixed powder on the ceramic blank; and then an alumina crucible is placed above the ceramic blank in an inverted manner, and a layer of alumina powder is covered at the opening of the alumina crucible along the circumferential direction for sealing.
10. A piezoelectric ceramic sensor, characterized by: comprises a piezoelectric ceramic capacitor; the piezoelectric ceramic capacitor comprises a bottom electrode, a top electrode and a dielectric medium; the dielectric is located between the bottom electrode and the top electrode, and the dielectric is the piezoceramic material of claim 1.
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