CN109320244B - Low-temperature sintered piezoelectric ceramic material and preparation method thereof - Google Patents

Low-temperature sintered piezoelectric ceramic material and preparation method thereof Download PDF

Info

Publication number
CN109320244B
CN109320244B CN201811063463.7A CN201811063463A CN109320244B CN 109320244 B CN109320244 B CN 109320244B CN 201811063463 A CN201811063463 A CN 201811063463A CN 109320244 B CN109320244 B CN 109320244B
Authority
CN
China
Prior art keywords
powder
equal
temperature
lisbo
piezoelectric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811063463.7A
Other languages
Chinese (zh)
Other versions
CN109320244A (en
Inventor
范桂芬
曾子庆
王晓川
吕文中
郝孟猛
文玥
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN201811063463.7A priority Critical patent/CN109320244B/en
Publication of CN109320244A publication Critical patent/CN109320244A/en
Application granted granted Critical
Publication of CN109320244B publication Critical patent/CN109320244B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • C04B35/497—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates based on solid solutions with lead oxides
    • C04B35/499—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates based on solid solutions with lead oxides containing also titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/472—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on lead titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3258—Tungsten oxides, tungstates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3294—Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Abstract

The invention belongs to the field of novel inorganic non-metallic materials, and more particularly relates toAnd a low-temperature sintered piezoelectric ceramic material and a preparation method thereof. The chemical general formula is xPby(Yb1/2Nb1/2)O2+y‑(1‑x)PbyTiO2+y+u％LiSbO3+v％MaObWherein x is more than or equal to 0.48 and less than or equal to 0.52; y is more than or equal to 0.98 and less than or equal to 1.04; 0<u is less than or equal to 0.2, and v is less than or equal to 1 and more than or equal to 0. The sintering temperature of the ceramic is reduced from 1000 ℃ to 800-900 ℃ by adding the composite oxide dopant, and a large piezoelectric constant (d) can be obtained33Not less than 420pC/N), large electromechanical coupling coefficient (k)pNot less than 0.55) and high Curie Point (T)c>370 ℃ C and moderate dielectric constant: (r2000-3500) to meet the application requirements of the laminated piezoelectric driver on the ceramic material.

Description

Low-temperature sintered piezoelectric ceramic material and preparation method thereof
Technical Field
The invention belongs to the field of novel inorganic nonmetallic materials, and particularly relates to a low-temperature sintered piezoelectric ceramic material and a preparation method thereof.
Background
The piezoelectric ceramic micro-driver is a solid-state executive device manufactured by utilizing inverse piezoelectric effect, and is widely applied to high and new technical fields of precision optics, micromachines, microelectronic technology and the like. These applications require the development of piezoelectric ceramic devices toward small size, low driving voltage, large displacement, and integration. The piezoceramic material is used as a core material of the driver, and is required to have the characteristics of high sensitivity, large static output torque, good temperature stability and the like, and the specific requirements on the performance of the piezoceramic material are as follows: high piezoelectric constant to achieve low voltage drive and large output torque; high electromechanical coupling coefficient so as to have wider operating frequency and higher conversion efficiency; the high Curie point enables the device to have good temperature stability so as to adapt to severe application environment and avoid the performance deterioration of the device caused by heat generated in the working process of the device; moderate dielectric constant, avoiding heating under alternating electric field and higher input impedance.
Pb(Yb1/2Nb1/2)O3-PbTiO3PYN-PT is a typical composite perovskite piezoelectric ceramic material, has high piezoelectric constant, high electromechanical coupling coefficient and high Curie temperature, and is a key material of an electromechanical transducer and a piezoelectric driver. However, the piezoelectric ceramic sintering temperature of the system is not lower than 1000 ℃ and the structure is unstable, lead in the material is very easy to volatilize in the sintering process, the environment is polluted, and simultaneously, the stoichiometric ratio of the ceramic material is deviated, the perovskite structure is changed, the piezoelectric performance is deteriorated and the repeatability is deteriorated. In recent years, stacked piezoelectric devices have been widely used due to miniaturization and low power consumption of the devices. The laminated piezoelectric actuator is prepared by utilizing a tape casting process and a tape casting blank film and inner electrode one-time co-firing technology, in order to reduce the manufacturing cost, the tape casting film is commonly co-fired with an Ag-Pd electrode with low palladium content or even a pure silver electrode, and the piezoelectric ceramic is required to be modified to reduce the sintering temperature of the material.
The method for reducing the sintering temperature of the piezoelectric ceramic comprises the following steps: 1) the preparation process is improved, such as chemical method powder preparation, the powder activity is improved, and the ceramic sintering temperature is reduced, but the method has complex process and higher cost; 2) the glass powder or the low-melting-point oxide sintering aid is added, during the sintering process, the glass or the low-melting-point oxide forms a liquid phase, mass transfer is easy, the elimination of air holes and the densification of ceramics are facilitated, the cooling effect is very obvious, but a non-ferroelectric second phase is easily gathered at the crystal boundary of the ceramics, so that the material performance is rapidly deteriorated, and the application field with high performance level is not facilitated; 3) solid solution or doping oxide to form transition liquid phase sintering, forming a liquid phase in the early stage of sintering to promote mass transfer and reduce the sintering temperature, and enabling the liquid phase to enter crystal lattices in the later stage of sintering to reduce the generation of impurity phases and avoid the deterioration of the ceramic performance. The difficulty of low-temperature sintering research of piezoelectric ceramics is to combine low-temperature sintering of the piezoelectric ceramics and high-level piezoelectric performance.
Researchers at home and abroad explore PYN-PT piezoelectric ceramics, Dulan, American scholars, study the low-temperature sintering of the PYN-PT piezoelectric ceramics, and the sintering temperature of the material is reduced to 900-950 ℃ by adding PbO, but the piezoelectric property is reduced to a certain extent. By improving the pre-sintering ball milling process, the sintering temperature is reduced to 900-990 ℃ while the piezoelectric performance is considered, but the process is complex (CN 102623628A in China). The piezoelectric performance of the material can be effectively improved by solid solution of PZN in the PYN-PT piezoelectric ceramic material, but the Curie temperature of the material is reduced (<300 ℃), which is unfavorable for the application of a piezoelectric actuator. Therefore, the sintering temperature of the piezoelectric driving material is further reduced, the comprehensive piezoelectric performance of the piezoelectric driving material is further improved, the requirement of low-temperature co-firing of the pure silver inner electrode is met, the manufacturing cost is reduced, the yield of the device is improved, and the piezoelectric driving material is a problem to be solved in the field of low-temperature sintering research of piezoelectric ceramics.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low-temperature sintered piezoelectric ceramic material, and aims to solve the problems of unstable structure, extremely easy volatilization of lead, environmental pollution, deteriorated piezoelectric performance and poor repeatability of the material in the conventional piezoelectric ceramic sintering process.
In order to achieve the purpose, the invention provides a low-temperature sintering piezoelectric ceramic material which has a chemical general formula of xPby(Yb1/2Nb1/2)O2+y-(1-x)PbyTiO2+y+u％LiSbO3+v％MaObWherein M is a transition metal element, (Yb)1/ 2Nb1/2) The molar ratio of Ti to Pb is x: (1-x): y, wherein x is more than or equal to 0.48 and less than or equal to 0.52; y is more than or equal to 0.98 and less than or equal to 1.04;
xPby(Yb1/2Nb1/2)O2+y-(1-x)PbyTiO2+ydenotes a base ceramic powder, u% denotes LiSbO3The weight percentage of the base ceramic powder is that v% represents transition metal oxide MaOb0 weight percent of the base ceramic powder<u is less than or equal to 0.2, and v is less than or equal to 1 and more than or equal to 0; the values of a and b are obtained by valence equilibrium according to the valence state of the transition metal element M, and a and b are integers.
Preferably, M is one of the metal elements V, Mn, Fe or W.
According to another aspect of the present invention, there is provided a method for preparing the piezoelectric ceramic material, comprising the steps of:
s1: mixing PbO raw material powder and TiO2Raw material powder and YbNbO4Pre-burning the mixed precursors to obtain xPbby(Yb1/ 2Nb1/2)O2+y-(1-x)PbyTiO2+yMatrix ceramic powder;
s2: mixing LiSbO3Raw material powder, MaObAnd (2) doping raw material powder and the matrix ceramic powder to obtain mixed powder, performing ball milling, granulation and dry pressing on the mixed powder to form a blank sheet, and sintering the blank sheet to obtain the piezoelectric ceramic material.
Preferably, the YbNbO of step S14The precursor is prepared according to the following method: according to YbNb2O6Is a stoichiometric ratio of Yb2O3And Nb2O5Mixing the powder ingredients, ball-milling, drying and presintering to form YbNbO4A precursor.
Preferably, the LiSbO of step S23The raw material powder is prepared by the following method: according to LiSbO3Stoichiometric ratio of (A) to (B) of Li2CO3Powder and Sb2O5Mixing powder ingredients, ball-milling, drying and presintering to form the LiSbO3Raw material powder.
Preferably, in step S1, the pre-sintering temperature is 800 to 900 ℃, and the heat preservation time is 1 to 3 hours.
Preferably, in step S2, the sintering of the green sheet is performed in an air atmosphere, and the sintering temperature is 800 to 900 ℃.
Preferably, in step S2, the MaObM in the raw material powder is one of metal elements V, Mn, Fe or W.
Preferably, a silver burning polarization step is further included after step S2: and coating silver on the surface of the piezoelectric ceramic material, and carrying out polarization after calcining the silver-coated piezoelectric ceramic material.
Preferably, the calcining temperature is 550-650 ℃, and the heat preservation time is 10-20 minutes; the polarization conditions include: the polarization temperature is 100-140 ℃, the polarization voltage is 3.5-4.5 kV/mm, and the polarization time is 15-30 minutes.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
the invention reduces the sintering temperature of the ceramic material and improves the piezoelectric comprehensive performance of the ceramic material by adjusting the formula composition of the matrix and adding a sintering aid.
By adjusting the content of Pb, the densification and sintering of the ceramic are improved, and a proper amount of low-melting-point sintering aid LiSbO is combined3And MaObThe addition of the P-Ti-oxide-doped piezoelectric ceramic effectively reduces the sintering temperature of the PYN-PT ceramic, and enters crystal lattices at the later stage of sintering to regulate and control the electrical properties of the piezoelectric ceramic.
Sintering aid LiSbO3Sb in (1)5+The ions are used as a 'hard' dopant, and Curie temperature reduction caused by other doping can be compensated through regulation and compensation of valence states and vacancy. In addition, the doping can inhibit the volatilization of lead, protect the environment and reduce the manufacturing cost of the laminated piezoelectric device.
In addition, the invention has the advantages that the added sintering aid can improve the Curie temperature of the matrix formula and improve the temperature stability of the dielectric property. In the invention, LiSbO is adopted3The sintering aid is used for reducing the sintering temperature of the ceramic material and slightly increasing the Curie temperature of the material. The prepared low-temperature sintered piezoelectric ceramic material can obtain better working stability in severe environment change.
Drawings
FIG. 1 is a cross-sectional SEM photograph of a sintered ceramic sample at 900 ℃ as provided by an embodiment of the present invention;
FIG. 2 shows different LiSbO structures provided by embodiments of the present invention3A doping amount of ceramic sample XRD spectrum;
FIG. 3 shows different LiSbO structures provided by embodiments of the present invention3Doping amount of a ceramic sample dielectric temperature spectrum;
FIG. 4 is a drawing of the present inventionExamples provide different LiSbO3The doped amount of the ceramic sample is the hysteresis loop.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the embodiment of the invention, the general chemical formula xPb is usedy(Yb1/2Nb1/2)O2+y-(1-x)PbyTiO2+y+u％LiSbO3+v％MaObThe composition of the piezoceramic material is expressed, the piezoceramic material is a niobium ytterbium acid lead-lead titanate low-temperature sintering piezoceramic material, wherein a short transverse line is a connector, M is a transition metal element, (Yb)1/2Nb1/2) The molar ratio of Ti to Pb is x: (1-x): y, wherein x is more than or equal to 0.48 and less than or equal to 0.52; y is more than or equal to 0.98 and less than or equal to 1.04; xPby(Yb1/2Nb1/2)O2+y-(1-x)PbyTiO2+yDenotes a base ceramic powder, u% denotes LiSbO3The weight percentage of the ceramic powder in the matrix is that v% represents MaOb0 weight percent of the base ceramic powder<u is less than or equal to 0.2, and v is less than or equal to 1 and more than or equal to 0. Wherein, M can be any one of metal elements of vanadium V, manganese Mn, iron Fe or tungsten W.
The piezoelectric ceramic material provided by the embodiment of the invention is doped with LiSbO3And MaObSo that the material can be sintered at a lower temperature and has high piezoelectric constant, high electromechanical coupling coefficient, high Curie temperature and moderate dielectric constant.
The method for preparing the piezoelectric ceramic material provided by the embodiment of the invention comprises the process steps of mixing, presintering, granulating, tabletting, sintering, silver coating, polarizing and the like; by adding the composite oxide dopant, the sintering temperature of the ceramic can be reduced from 1000 ℃ to below 900 ℃, and a large piezoelectric constant (d) can be obtained33Not less than 450pC/N) and large electromechanical coupling coefficient (k)pNot less than 0.55) and high Curie Point (T)c>370 ℃) andmoderate dielectric constant: (r2000-3500) to meet the application requirements of the laminated piezoelectric driver on the ceramic material. The manufacturing cost of the laminated piezoelectric device is reduced while the volatilization of lead is inhibited to protect the environment.
The preferred preparation method of the low-temperature sintered piezoelectric ceramic material of the present invention comprises the steps of:
(1)YbNbO4preparation of precursor by analytically pure Yb2O3、Nb2O5The powder is used as raw material according to YbNbO4The YbNbO is synthesized by proportioning according to the stoichiometric ratio, ball-milling for 6 hours by using deionized water as a ball-milling medium, drying and sieving by using a 60-mesh sieve, and presintering for 4 hours at 1200 DEG C4A precursor.
(2) Pre-synthesis of powder, analytically pure PbO and TiO2And YbNbO4The powder is used as a raw material, the materials are mixed according to the stoichiometric ratio of the general formula, deionized water is used as a ball milling medium, ball milling is carried out for 6 hours, drying and 60-mesh sieving are carried out, and then presintering is carried out for 1-3 hours at 800-900 ℃ to obtain the presynthesized powder of the matrix ceramic material.
(3)LiSbO3Preparing raw material powder: according to LiSbO3Stoichiometric ratio of (A) to (B) of Li2CO3Powder and Sb2O5Mixing the powder ingredients, ball-milling, drying and presintering to form LiSbO3Raw material powder; the pre-sintering temperature is 600-650 ℃, and the heat preservation time is 1-2 h.
(4) The preparation of the piezoelectric ceramic comprises the steps of calculating the total weight of pre-synthesized matrix ceramic powder, and adding analytically pure LiSbO according to the weight percentage shown in the general formula3And MaObThe raw material powder is used as a doping agent, absolute ethyl alcohol is used as a ball milling medium, ball milling is carried out for 6 hours again, PVA is used for granulation after drying, the mixture is pressed into blank sheets with the diameter of 12mm and × 1mm under the pressure of 5-20 MPa, then heat preservation is carried out for 3-5 hours at the temperature of 800-900 ℃ in air atmosphere, and low-temperature sintering piezoelectric ceramics are obtained through sintering.
(5) And (3) silver burning, namely coating medium-temperature silver paste on two surfaces of the ceramic sample by using a screen mesh, putting the sample coated with the silver paste into an electric furnace for burning, wherein the burning temperature is 550-650 ℃, and the heat preservation time is 10-20 minutes.
(6) And (3) polarization, namely putting the ceramic sample with the electrode into silicone oil, and applying a strong electric field to the ceramic sample for polarization, wherein the polarization temperature is 100-140 ℃, the polarization voltage is 3.5-4.5 kV/mm, and the polarization time is 15-30 minutes. Preferably, the polarization temperature is 120 ℃, the polarization voltage is 4kV/mm, and the polarization time is 15 minutes.
In the embodiment of the invention, the piezoelectric ceramic material prepared by the method is subjected to the following performance tests:
(1) measurement of Density of piezoelectric ceramics
The density of the ceramic is measured by the Archimedes principle, and is calculated according to the formula 1-1 through the mass and the volume of a measured sample:
Figure BDA0001797709470000061
in the formula, M0，V0Respectively representing the mass and volume of the dried sample in air, M2Mass in air after the ceramic sample had absorbed sufficient water, M1Is the mass in water after the sample has absorbed water sufficiently.
(2) Analysis of phase composition of piezoelectric ceramics
The invention adopts XRD to analyze the phase structure of the ceramic. The apparatus used was Shimadzu XRD-7000, Japan.
(3) Analysis of piezoelectric ceramic microstructure
The invention adopts a Quanta 200 type scanning electron microscope to carry out microstructure analysis on the sintered natural surface. And observing the grain size, the grain boundary thickness and the ceramic compactness of the ceramic surface.
(4) Piezoelectric ceramic dielectric property test
And (3) placing the piezoelectric ceramic sample with the upper electrode on an Aglilent 4294A precision impedance analyzer to test the capacitance value and the dielectric loss under the test frequency of 1KHz in the room temperature environment. The relative dielectric constant of the material was then calculated according to equation 1-2r：
Figure BDA0001797709470000071
In this formula, C is the material capacitance and A is the sampleThe area of the upper and lower surfaces, t the thickness of the sample, d the diameter of the upper and lower surfaces of the sample,0is the dielectric constant in vacuum.
(5) Piezoelectric ceramic dielectric temperature spectrum test
The ferroelectric piezoelectric material has ferroelectricity in a certain temperature range, namely, the material has spontaneous polarization and the direction of the spontaneous polarization can be changed, and simultaneously, the ferroelectric piezoelectric material shows a ferroelectric hysteresis loop characteristic to the outside. When the temperature of the ferroelectric reaches a certain critical value, the ferroelectric will undergo phase transition, the ferroelectric phase will change into a cis-point phase, and spontaneous polarization is small, which is called the curie temperature Tc. Ferroelectric piezoelectric materials undergo abrupt changes in many physical properties (dielectric constant, heat capacity, etc.) at the curie temperature. We test the curie temperature of the material by testing the temperature of the discontinuity.
The present invention uses a sudden change in dielectric constant to test the curie temperature. The specific implementation is to test the dielectric constant of a sample with continuously increased temperature, and determine the Curie temperature of the material by depending on the maximum value of the dielectric constant.
(6) Piezoelectric performance test of piezoelectric ceramics
The ceramic sample tested by the experiment is a phi 15mm × 1mm thin wafer, the used testing instrument is a 4294A type precision impedance analyzer produced by Agilent company, and the resonant frequency f of the tested ceramic samplesAnd antiresonance frequency fpAnd the minimum impedance Z of the resonance frequencymin. And then calculating the piezoelectric parameters of the piezoelectric ceramics according to a piezoelectric material performance test method of the national standard GB 2414-81.
(a) Planar electromechanical coupling coefficient kp
kpSeries resonance frequency f of radial vibration of wafersAnd parallel resonant frequency fpThe relationship between f and f is complex and is not generally calculated directly but is instead determinedp、fsThrough (f)p-fs)/fs＝Δf/fsAnd σ is looked up to obtain kpThe value is obtained.
(b) Piezoelectric coefficient d33
Piezoelectric coefficient d of piezoelectric ceramic in this experiment33All adopt the sound of Chinese academy of sciencesZJ-3A quasi-static d produced by institute of science33The tester performs the measurement.
According to the invention, by adjusting the formula composition of the matrix and adding a sintering aid, the sintering temperature of the ceramic material is reduced and the piezoelectric comprehensive performance of the ceramic material is improved; by adjusting the content of Pb, the densification and sintering of the ceramic are improved, and a proper amount of low-melting-point sintering aid LiSbO is combined3And MaObThe addition of the PYN-PT ceramic effectively reduces the sintering temperature of the PYN-PT ceramic, and the PYN-PT ceramic enters crystal lattices at the later stage of sintering to regulate and control the electrical properties of the piezoelectric ceramic; and a sintering aid LiSbO3Sb in (1)5+The ions are used as a 'hard' dopant, and Curie temperature reduction caused by other doping can be compensated through regulation and compensation of valence states and vacancy. In addition, the doping can inhibit the volatilization of lead, protect the environment and reduce the manufacturing cost of the laminated piezoelectric device.
In addition, the invention has the advantages that the added sintering aid can improve the Curie temperature of the matrix formula and improve the temperature stability of the dielectric property. In the invention, LiSbO is adopted3The sintering aid is used for reducing the sintering temperature of the ceramic material and slightly increasing the Curie temperature of the material. The prepared low-temperature sintered piezoelectric ceramic material can obtain better working stability in severe environment change.
In the present example, piezoelectric ceramic materials of different compositions of examples 1 to 32 and their property lists as shown in tables 1 and 2 were prepared according to the above-described preparation methods.
TABLE 1 comparison of sintering behavior at 900 deg.C for samples of different ratios
Figure BDA0001797709470000081
In Table 1, M is Mn, the sintering temperature of the sample is 900 ℃, and the temperature is kept for 4 hours. As can be seen from the results shown in table 1, in example 8, when x is 0.505, y is 1.01, u is 0.05, and v is 0, and sintering is performed under the condition of maintaining at 900 ℃ for 4 hours, the best piezoelectric performance can be obtained: d33＝420pC/N，kp＝0.53，Tc＝378℃，r＝2188，tan＝0.0328。
TABLE 2 comparison of sintering behavior at 850 deg.C for samples of different ratios
Figure BDA0001797709470000091
The examples shown in Table 2 are lists of piezoceramic materials and properties of different compositions, with a sintering temperature of 850 ℃ and a holding time of 4 hours. In the compositions of examples 15 to 18, M is Mn element, in the compositions of examples 19 to 23, M is Fe element, in the compositions of examples 24 to 28, M is W element, and in the compositions of examples 29 to 32, M is V element.
FIG. 1 is an SEM photograph of the sintered ceramic material of example 4 of Table 1 at 900 ℃. As can be seen from figure 1, the sintered ceramic material has the grain size of 2-3 μm, uniform size, few pores and higher compactness.
FIG. 2 shows different LiSbO3XRD pattern of doped amount ceramic sample. FIG. 3 is a view showing LiSbO3The dielectric temperature spectrum curve of the doped ceramic sample, and FIG. 4 shows different LiSbO samples provided by the embodiments of the present invention3Doped ceramic sample hysteresis loop, LiSbO, as can be seen in FIGS. 2, 3 and 43The doping amount reaches 0.1 wt%, and a pure perovskite structure can be obtained by sintering at 900 ℃, and no second phase is generated; and its Curie temperature Tc follows that of LiSbO3The content increases, and the residual polarization intensity Pr of the LiSbO increases along with the LiSbO3The content gradually decreased and the appropriate amount of LiSbO was found from Table 13The doping can not only reduce the sintering temperature, but also improve the piezoelectric performance of the laminated piezoelectric device while improving the Curie temperature, which lays a good foundation for the wide application of the laminated piezoelectric device in medium-high temperature environment.
Compared with the PYN-PT piezoelectric ceramic without modification, the low-temperature sintered piezoelectric ceramic material can reduce the sintering temperature from 1000 ℃ to 900 ℃, and obtains excellent piezoelectric performance: large piezoelectric constant (d)33Not less than 420pC/N), large electromechanical coupling coefficient (k)pNot less than 0.5) and high Curie Point (T)c>375 deg.C and moderate dielectric constant: (r2000-2500), and the application requirements of the piezoelectric driver on the ceramic material are met. The sintering temperature of the piezoceramic material is greatly reduced, so that the manufacturing cost of the laminated piezoelectric driving device is facilitated, the finished product rate of the device manufacturing is improved, and the industrialized popularization and use of the piezoceramic material sintered at low temperature are facilitated; meanwhile, the content of Pd in the Ag-Pd internal electrode of the laminated device is reduced, so that the manufacturing cost of the device is reduced.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. The low-temperature sintered piezoelectric ceramic material is characterized in that the chemical general formula is xPby(Yb1/2Nb1/2)O2+y-(1-x)PbyTiO2+y+u％LiSbO3+v％MaObWherein M is a transition metal element, (Yb)1/2Nb1/2) The molar ratio of Ti to Pb is x: (1-x): y, wherein x is more than or equal to 0.48 and less than or equal to 0.52; y is more than or equal to 0.98 and less than or equal to 1.04;
xPby(Yb1/2Nb1/2)O2+y-(1-x)PbyTiO2+ydenotes a base ceramic powder, u% denotes LiSbO3The weight percentage of the base ceramic powder is that v% represents transition metal oxide MaOb0 weight percent of the base ceramic powder<u is less than or equal to 0.2, and v is less than or equal to 1 and more than or equal to 0; the values of a and b are obtained by valence equilibrium according to the valence state of the transition metal element M, and a and b are integers; m is one of metal elements V, Mn, Fe or W.
2. A method of preparing the piezoceramic material according to claim 1, comprising the steps of:
s1: mixing PbO raw material powder and TiO2Raw material powder and YbNbO4Pre-burning the mixed precursors to obtain xPbby(Yb1/2Nb1/2)O2+y-(1-x)PbyTiO2+yMatrix ceramic powder;
s2: mixing LiSbO3Raw material powder, MaObAnd (2) doping raw material powder and the matrix ceramic powder to obtain mixed powder, performing ball milling, granulation and dry pressing on the mixed powder to form a blank sheet, and sintering the blank sheet to obtain the piezoelectric ceramic material.
3. The method of claim 2, wherein the YbNbO of step S14The precursor is prepared according to the following method: according to YbNbO4Is a stoichiometric ratio of Yb2O3And Nb2O5Mixing the powder ingredients, ball-milling, drying and presintering to form YbNbO4A precursor.
4. The method of claim 2 wherein the LiSbO of step S23The raw material powder is prepared by the following method: according to LiSbO3Stoichiometric ratio of (A) to (B) of Li2CO3Powder and Sb2O5Mixing powder ingredients, ball-milling, drying and presintering to form the LiSbO3Raw material powder.
5. The method according to claim 2, wherein in step S1, the pre-firing temperature is 800 to 900 ℃ and the holding time is 1 to 3 hours.
6. The method according to claim 2, wherein in step S2, the green sheet sintering is performed in an air atmosphere, and the sintering temperature is 800 to 900 ℃.
7. The method of claim 2, further comprising a silver firing polarization step after the sintering of step S2: and coating silver on the surface of the piezoelectric ceramic material, and carrying out polarization after calcining the silver-coated piezoelectric ceramic material.
8. The method of claim 7, wherein the calcination temperature is 550 to 650 ℃ and the holding time is 10 to 20 minutes; the polarization conditions include: the polarization temperature is 100-140 ℃, the polarization voltage is 3.5-4.5 kV/mm, and the polarization time is 15-30 minutes.
CN201811063463.7A 2018-09-12 2018-09-12 Low-temperature sintered piezoelectric ceramic material and preparation method thereof Active CN109320244B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811063463.7A CN109320244B (en) 2018-09-12 2018-09-12 Low-temperature sintered piezoelectric ceramic material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811063463.7A CN109320244B (en) 2018-09-12 2018-09-12 Low-temperature sintered piezoelectric ceramic material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109320244A CN109320244A (en) 2019-02-12
CN109320244B true CN109320244B (en) 2020-10-16

Family

ID=65265882

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811063463.7A Active CN109320244B (en) 2018-09-12 2018-09-12 Low-temperature sintered piezoelectric ceramic material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109320244B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112142466B (en) * 2019-06-26 2021-05-25 中国科学院上海硅酸盐研究所 Lead niobate ytterbium acid based antiferroelectric ceramic material and preparation method thereof
CN113582689B (en) * 2021-08-27 2022-08-16 成都汇通西电电子有限公司 Low-temperature co-fired piezoelectric ceramic material for laminated actuator and preparation method thereof
CN115849905A (en) * 2022-12-24 2023-03-28 西安交通大学 High-temperature piezoelectric ceramic material, preparation method and application

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101337814B (en) * 2008-08-28 2011-05-04 陕西师范大学 Low temperature sintering lithium antimonite doped quinary system piezoelectric ceramics material and method for preparing same
CN102623628B (en) * 2012-03-31 2014-03-26 哈尔滨工业大学 Preparation method of lead niobate ytterbate-lead titanate piezoceramic
CN102850050B (en) * 2012-08-31 2014-03-12 华中科技大学 Low temperature sintering piezoelectric ceramic material and preparation method thereof

Also Published As

Publication number Publication date
CN109320244A (en) 2019-02-12

Similar Documents

Publication Publication Date Title
CN102850050B (en) Low temperature sintering piezoelectric ceramic material and preparation method thereof
CN107698252B (en) Application of ceramic material as high-temperature stable piezoelectric energy collecting material and preparation method thereof
CN109320244B (en) Low-temperature sintered piezoelectric ceramic material and preparation method thereof
CN109437895B (en) Preparation method of lead zirconate titanate-lead magnesium niobate piezoelectric ceramic
CN108546125B (en) Piezoceramic material applied to high-temperature environment and preparation method thereof
CN115340377B (en) Preparation method of high-performance piezoelectric ceramic
CN106518070B (en) A kind of polynary system high-voltage electricity active piezoelectric ceramic material and preparation method thereof
CN113213930A (en) Multi-element doped potassium-sodium niobate-based piezoelectric ceramic and preparation method thereof
CN112209711A (en) Zirconium-titanium-tin lead niobate thick film ceramic and preparation method and application thereof
CN113582667B (en) Low-temperature cofiring high-energy-storage antiferroelectric ceramic material and preparation method and application thereof
CN115093216A (en) Barium titanate doped lead-free ceramic with high electrostriction and low hysteresis and preparation method thereof
CN107226698A (en) A kind of piezoceramic material and preparation method applied to underwater acoustic transducer
CN111217604B (en) Preparation method of sodium bismuth titanate-based electronic ceramic with high energy storage density and efficiency
CN108863349A (en) A kind of barium titanate-based lead-free height Jie temperature-stable ceramic material and preparation method thereof
CN112759390A (en) Has high kpPSN-PZT piezoelectric ceramic and preparation method thereof
CN111253151A (en) Bismuth ferrite barium titanate-based ceramic with high energy storage density and high power density and preparation method thereof
CN113800904A (en) High-energy low-loss BNT-SBT-xSMN ceramic material and preparation method thereof
CN114478006A (en) KNNS-BNZ + CuO piezoceramic material and preparation method and application thereof
CN114956815A (en) Preparation method of novel high-strain high-Curie-temperature potassium-sodium niobate-based ferroelectric ceramic
CN107021753A (en) A kind of ion doping lead antimony manganese zirconia titanate piezoelectric ceramics material and preparation method thereof
CN112851336A (en) Preparation method of bismuth sodium titanate bismuth laminated piezoelectric ceramic
CN115894021B (en) High mechanical quality factor hard piezoelectric ceramic material and preparation method thereof
CN115093212B (en) High-performance bismuth ferrite-barium titanate ceramic with use temperature exceeding 300 ℃ and low-temperature liquid phase sintering preparation method thereof
CN115504783B (en) KNN-based leadless piezoelectric ceramic and preparation method thereof
CN114262225B (en) High-purity nano electronic ceramic and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant