CN117865672A - Low-hysteresis high-temperature-resistant lead-based piezoelectric ceramic applied to driver and preparation method thereof - Google Patents
Low-hysteresis high-temperature-resistant lead-based piezoelectric ceramic applied to driver and preparation method thereof Download PDFInfo
- Publication number
- CN117865672A CN117865672A CN202311684787.3A CN202311684787A CN117865672A CN 117865672 A CN117865672 A CN 117865672A CN 202311684787 A CN202311684787 A CN 202311684787A CN 117865672 A CN117865672 A CN 117865672A
- Authority
- CN
- China
- Prior art keywords
- ceramic
- ball milling
- powder
- temperature
- piezoelectric ceramic
- 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.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 169
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000005266 casting Methods 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims description 75
- 238000001035 drying Methods 0.000 claims description 36
- 235000015895 biscuits Nutrition 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 22
- 238000007599 discharging Methods 0.000 claims description 20
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 13
- 239000003292 glue Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 7
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 6
- 238000005056 compaction Methods 0.000 claims description 5
- 238000004080 punching Methods 0.000 claims description 5
- 238000009461 vacuum packaging Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 238000003746 solid phase reaction Methods 0.000 claims description 4
- 238000011282 treatment Methods 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000462 isostatic pressing Methods 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 4
- 230000002238 attenuated effect Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000009472 formulation Methods 0.000 abstract description 2
- 239000000306 component Substances 0.000 description 53
- 238000005498 polishing Methods 0.000 description 15
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000010344 co-firing Methods 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910002059 quaternary alloy Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/49—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
- C04B35/491—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT
- C04B35/493—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT containing also other lead 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N2/00—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction
- H02N2/0005—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction producing non-specific motion; Details common to machines covered by H02N2/02 - H02N2/16
- H02N2/001—Driving devices, e.g. vibrators
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N2/00—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction
- H02N2/22—Methods relating to manufacturing, e.g. assembling, calibration
-
- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide 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
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
-
- 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
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates 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
- C04B2235/3296—Lead oxides, plumbates or oxide forming salts thereof, e.g. silver plumbate
-
- 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
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
-
- 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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/442—Carbonates
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- 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
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
-
- 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
- C04B2235/94—Products characterised by their shape
-
- 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
- C04B2235/95—Products characterised by their size, e.g. microceramics
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention provides a low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to a driver and a preparation method thereof, wherein the hysteresis of a material is finally reduced by multiplying the grain size of the PZT piezoelectric ceramic and reducing the grain boundary effect, so that the prepared low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to the driver has the characteristics of low hysteresis and high temperature resistance, the hysteresis is 5.8 percent, and T is the same as that of the low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to the driver c The temperature is 342 ℃, the strain can not be attenuated within the room temperature to 250 ℃, the application range is wider than that of the traditional soft ceramic, the service temperature range is wider, and the stability is stronger. The ceramic powder and the casting slurry prepared by the method have low sintering temperature, simple preparation flow and low manufacturing cost, and can be directly used for preparing the multilayer cofiring piezoelectric ceramic driver. It is apparent that the actuator prepared by the piezoelectric ceramic formulation provided by the invention can be manufactured without causingHigh-precision direct driving and quick response are realized under the condition of using a feedback circuit and a strain gauge sensor, and the design difficulty of a driver control circuit and the manufacturing cost of the driver are effectively reduced.
Description
Technical Field
The invention belongs to the technical field of multilayer cofiring piezoelectric ceramic drivers, and particularly relates to low-hysteresis high-temperature-resistant lead-based piezoelectric ceramic applied to a driver and a preparation method thereof.
Background
The multilayer cofiring piezoelectric ceramic driver is a core component in an ultra-high precision positioning and displacement control system and has extremely wide application in the fields of semiconductors, optics, advanced machine tools, weaponry, automobiles, aerospace and the like. The strain hysteresis and curie temperature of the piezoelectric ceramic are core parameters for determining the performance of the multilayer cofired piezoelectric ceramic driver, wherein the strain hysteresis influences the displacement precision of the driver, and the curie temperature determines the service temperature range of the driver. The prior commercial multilayer cofired piezoelectric ceramic driver generally adopts soft lead-based piezoelectric ceramics, has large strain hysteresis (about 15 percent) and low service temperature (less than 100 ℃). The larger hysteresis can deteriorate the precision of the device, and the application scene of the device is limited if the service temperature is low.
In order to meet the precision requirement of practical application, a closed-loop control method with a feedback circuit is generally adopted to improve the displacement precision of the device. However, the optimization effect of closed loop control on accuracy is still limited. In addition, the closed loop control requires additional displacement sensor and control circuitry, which not only increases the volume and cost of the entire device, but also significantly reduces the response speed of the device. Therefore, developing low hysteresis piezoceramic materials is a fundamental measure for improving the displacement accuracy of drivers, and can avoid negative effects of additional displacement sensors and control circuits on device performance. In addition, with the rapid development of the fields of deep space exploration, resource exploration, weapon equipment and the like in recent years, the service temperature of the existing device is low, and the actual application requirements cannot be met. In summary, developing a novel low hysteresis high temperature resistant piezoelectric ceramic material and a preparation method thereof are the problems to be solved in industry and academia.
At present, piezoelectric materials with low hysteresis characteristics comprise monocrystalline materials and textured ceramics represented by PMN-PT, PNN-PT and the like, the materials have ultralow hysteresis characteristics, the hysteresis is as low as 4-7%, and the materials are ideal materials for preparing high-precision multilayer piezoelectric drivers. However, the materials have harsh preparation conditions and high cost, and the Curie temperature is low (less than 150 ℃), so that the application requirements of the materials on high service temperature in new scenes cannot be met.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a low-hysteresis high-temperature-resistant lead-based piezoelectric ceramic applied to a driver and a preparation method thereof. The technical problems to be solved by the invention are realized by the following technical scheme:
the beneficial effects are that:
in a first aspect, the present invention provides a low hysteresis high temperature resistant lead-based piezoelectric ceramic for use in a driver, comprising: two components, wherein the first component has the formula:
(1-x-y)(0.48PbTiO 3 -0.52PbZrO 3 )-x(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -y(La 0.1 Sr 0.8 )TiO 2.95 wherein x and y represent molar ratio, x is more than or equal to 0.01 and less than or equal to 0.03,0.02, and y is more than or equal to 0.05;
the chemical formula of the second component is: zPbO/CuO; the mass percentage of the second component is z, and z is more than or equal to 1 and less than or equal to 2.5; wherein, the mol ratio of PbO to CuO is 0.72:0.28.
in a second aspect, the present invention provides a method for preparing the low hysteresis high temperature resistant lead-based piezoelectric ceramic for use in a driver according to the first aspect, which is characterized by comprising:
step 1, pbO and TiO are mixed 2 、ZrO 2 、Bi 2 O 3 、La 2 O 3 、SrCO 3 Putting ZnO powder into a ball milling tank according to the stoichiometric ratio of the first component for ball milling and high-temperature solid phase reaction to obtain prefabricated powder with a perovskite structure;
step 2, adding PbO and CuO powder in the stoichiometric ratio of the second component in the prefabricated powder, and performing ball milling and drying to obtain ceramic powder;
step 3, preparing the ceramic powder into casting slurry, and preparing a ceramic thick film through casting molding;
step 4, cutting the ceramic thick film into round ceramic films, and preparing a plurality of round ceramic films into ceramic biscuit by warm isostatic compaction;
and 5, performing glue discharging and high-temperature solid-phase sintering on the ceramic biscuit to obtain the low-hysteresis high-temperature-resistant piezoelectric ceramic.
In a third aspect, the present invention provides a driver, which is characterized in that the driver is prepared from the low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to the driver in the first aspect.
The invention provides a low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to a driver and a preparation method thereof, wherein the hysteresis of a material is finally reduced by multiplying the grain size of the PZT piezoelectric ceramic and reducing the grain boundary effect, so that the prepared low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to the driver has the characteristics of low hysteresis and high temperature resistance, the hysteresis is 5.8 percent, and T is the same as that of the low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to the driver c The temperature is 342 ℃, the strain can not be attenuated within the room temperature to 250 ℃, the application range is wider than that of the traditional soft ceramic, the service temperature range is wider, and the stability is stronger. The ceramic powder and the casting slurry prepared by the method have low sintering temperature, simple preparation flow and low manufacturing cost, and can be directly used for preparing the multilayer cofiring piezoelectric ceramic driver. Obviously, the driver prepared by the piezoelectric ceramic formula provided by the invention can realize high-precision direct driving and quick response without using a feedback circuit and a strain gauge sensor, and effectively reduces the design difficulty of a driver control circuit and the manufacturing cost of the driver.
The present invention will be described in further detail with reference to the drawings and embodiments.
Drawings
FIG. 1 is a diagram showing a state in which triangular wave signals act on front and rear internal electric domains of a piezoelectric ceramic single crystal material represented by PNN-PT and PMN-PT;
FIG. 2 is a schematic flow chart of a method for preparing low hysteresis high temperature resistant lead-based piezoelectric ceramic for use in a driver according to the present invention;
FIG. 3 is a SEM comparison of grains of PZT-5 with examples 1-3 of the present invention;
FIG. 4 is a graph comparing the unidirectional strain of PZT-5 with examples 1-3 of the present invention;
FIG. 5 is a graph comparing the temperature spectra of PZT-5 and examples 1-3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments, but embodiments of the present invention are not limited thereto.
In a first aspect, the present invention provides a low hysteresis high temperature resistant lead-based piezoelectric ceramic for use in a driver comprising: two components, wherein the first component has the formula:
(1-x-y)(0.48PbTiO 3 -0.52PbZrO 3 )-x(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -y(La 0.1 Sr 0.8 )TiO 2.95 wherein x and y represent molar ratio, x is more than or equal to 0.01 and less than or equal to 0.03,0.02, and y is more than or equal to 0.05;
the chemical formula of the second component is: zPbO/CuO; the mass percentage of the second component is z, and z is more than or equal to 1 and less than or equal to 2.5; wherein, the mol ratio of PbO to CuO is 0.72:0.28.
specific values of the chemical formulas of the first component and the second component of the present invention are described below by way of embodiments.
In one embodiment, the first component has a chemical formula of (1-0.01-0.02) (0.48 PbTiO 3 -0.52PbZrO 3 )-0.01(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -0.02(La 0.1 Sr 0.8 )TiO 2.95 The chemical formula of the second component is: 1PbO/CuO.
In embodiment two, the first component has a chemical formula of (1-0.01-0.05) (0.48 PbTiO 3 -0.52PbZrO 3 )-0.01(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -0.05(La 0.1 Sr 0.8 )TiO 2.95 The chemical formula of the second component is: 1PbO/CuO.
In embodiment III, the first component has a chemical formula of (1-0.01-0.02) (0.48 PbTiO) 3 -0.52PbZrO 3 )-0.01(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -0.02(La 0.1 Sr 0.8 )TiO 2.95 The chemical formula of the second component is: 2.5PbO/CuO.
In embodiment IV, the first component has a chemical formula of (1-0.01-0.05) (0.48 PbTiO) 3 -0.52PbZrO 3 )-0.01(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -0.05(La 0.1 Sr 0.8 )TiO 2.95 The chemical formula of the second component is: 2.5PbO/CuO.
In embodiment five, the first component has a chemical formula of (1-0.03-0.01) (0.48 PbTiO 3 -0.52PbZrO 3 )-0.03(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -0.02(La 0.1 Sr 0.8 )TiO 2.95 The chemical formula of the second component is: 1PbO/CuO.
In embodiment six, the first component has a chemical formula of (1-0.03-0.05) (0.48 PbTiO) 3 -0.52PbZrO 3 )-0.03(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -0.05(La 0.1 Sr 0.8 )TiO 2.95 The chemical formula of the second component is: 1PbO/CuO.
In embodiment seven, the first component has a chemical formula of (1-0.03-0.02) (0.48 PbTiO 3 -0.52PbZrO 3 )-0.03(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -0.02(La 0.1 Sr 0.8 )TiO 2.95 The chemical formula of the second component is: 2.5PbO/CuO.
In embodiment eight, the first component has a chemical formula of (1-0.03-0.05) (0.48 PbTiO 3 -0.52PbZrO 3 )-0.03(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -0.05(La 0.1 Sr 0.8 )TiO 2.95 The chemical formula of the second component is: 2.5PbO/CuO.
In embodiment nine, the first component has a chemical formula of (1-0.02-0.03) (0.48 PbTiO 3 -0.52PbZrO 3 )-0.02(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -0.03(La 0.1 Sr 0.8 )TiO 2.95 The chemical formula of the second component is: 1.5PbO/CuO.
Noteworthy are: piezoelectric ceramic single crystal materials represented by PNN-PT and PMN-PT have extremely low hysteresis (4-7%). This is because the single crystal material has a uniform orientation of all internal domains after poling, and the degree of domain orientation uniformity is extremely high. The single crystal material has little electric domain overturning movement under the action of unidirectional triangular wave signals, and friction damping action is not needed to be overcome, so that hysteresis is extremely small. The internal electric domains of the polycrystalline piezoelectric ceramic material are not completely the same in orientation after polarization due to the existence of the grain boundary effect, the electric domains are low in orientation consistency, deflection still occurs under the action of a triangular wave signal, and friction damping still needs to be overcome at the moment, so that hysteresis is large. Fig. 1 compares the states of the internal domains before and after the triangular wave signal acts. It can be seen that the degree of orientation of the electrical domains after the poling process largely determines the magnitude of the hysteresis.
The idea of the invention is to reduce the grain boundary effect and finally reduce the hysteresis of the material by multiplying the grain size of the PZT piezoelectric ceramic.
Research shows that the material with small tolerance factor (t) is combined with PbTiO 3 The solid solution of the composition tends to have a higher curie temperature, t, is calculated by the following formula:
from the definition of the tolerance factor of the crystal structure, the stability of the perovskite structure can be judged by the size thereof. When the material is in a cubic phase (paraelectric phase), the tolerance factor of the material is 1, and the smaller the tolerance factor is, the larger the structural distortion of the material is, the more the crystal structure deviates from the cubic phase, and the curie temperature (ferroelectric phase-paraelectric phase transition temperature point) of the material is increased due to the larger structural distortion.
The invention designs two different components based on tolerance factors, namely (Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 Component A and (La) 0.1 Sr 0.8 )TiO 2.95 And (3) a component. Wherein, (Bi) 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 The components can reduce mass transfer activation energy of the ceramic in the sintering process, multiply the grain size of the piezoelectric ceramic, reduce the grain boundary density, weaken the clamping effect of grain boundaries on electric domains, improve the consistency of electric domain orientation of the piezoelectric ceramic after polarization, and finally play a role in reducing hysteresis. (La) 0.1 Sr 0.8 )TiO 2.95 Is a third component with weak relaxation, can enhance the relaxation and dispersion of ceramics after entering a ceramic system, reduce the size of electric domains, reduce the coercive field of the material and promote the uniform orientation of the electric domains. In addition, the tolerance factors of the two components are lower, the Curie temperature of the system is not greatly reduced after the two components and the PZT material form a quasi-quaternary system, and the high temperature resistance of the prepared ceramic is ensured. In addition, pbO/CuO is added into a ceramic system as an auxiliary material, so that the sintering temperature of the ceramic is reduced to 900-950 ℃, and low-temperature co-firing of the ceramic layer and the silver electrode layer can be realized.
In a second aspect, referring to fig. 2, the present invention provides a method for preparing a low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to a driver, comprising:
step 1, pbO and TiO are mixed 2 、ZrO 2 、Bi 2 O 3 、La 2 O 3 、SrCO 3 Putting ZnO powder into a ball milling tank according to the stoichiometric ratio of the first component for ball milling and high-temperature solid phase reaction to obtain prefabricated powder with a perovskite structure;
step 2, adding PbO and CuO powder in the stoichiometric ratio of the second component into the prefabricated powder, and performing ball milling and drying to obtain ceramic powder;
step 3, preparing the ceramic powder into casting slurry, and preparing a ceramic thick film through casting molding;
step 4, cutting the ceramic thick film into round ceramic films, and preparing a plurality of round ceramic films into ceramic biscuit by warm isostatic compaction;
and 5, performing glue discharging and high-temperature solid-phase sintering on the ceramic biscuit to obtain the low-hysteresis high-temperature-resistant piezoelectric ceramic.
The invention provides a preparation method of low-hysteresis high-temperature-resistant lead-based piezoelectric ceramic applied to a driver. The piezoelectric ceramic is prepared from two different components designed based on tolerance factors, wherein the two components are (Bi) 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 Component A and (La) 0.1 Sr 0.8 )TiO 2.95 And (3) a component. Wherein, (Bi) 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 The components can reduce mass transfer activation energy of the ceramic in the sintering process, multiply the grain size of the piezoelectric ceramic, reduce the grain boundary density, weaken the clamping effect of grain boundaries on electric domains, improve the consistency of electric domain orientation of the piezoelectric ceramic after polarization, and finally play a role in reducing hysteresis. (La) 0.1 Sr 0.8 )TiO 2.95 Is a third component with weak relaxation, can enhance the relaxation and dispersion of ceramics after entering a ceramic system, reduce the size of electric domains, reduce the coercive field of the material and promote the uniform orientation of the electric domains. In addition, the tolerance factors of the two components are lower, the Curie temperature of the system is not greatly reduced after the two components and the PZT material form a quasi-quaternary system, and the high temperature resistance of the prepared ceramic is ensured.
Preferably, the step 1 of the present invention includes:
step 1.1, pbO and TiO are mixed 2 、ZrO 2 、Bi 2 O 3 、La 2 O 3 、SrCO 3 The ZnO powder raw materials are weighed and mixed according to the stoichiometric ratio of the chemical formula of the first component, and then the raw material mixed powder is put into a tank of Ni Long Qiumo;
step 1.2, performing ball milling, drying and sieving treatment on raw material mixed powder put into a nylon ball milling tank to obtain a pre-powder; the rotating speed in the ball milling process is set to be 250-300r/min, the ball milling time is set to be 8-13 hours, absolute ethyl alcohol is used as a ball milling medium, and the grinding balls are zirconium balls with the size of 5 mm; wherein, the mass ratio of the powder, the absolute ethyl alcohol and the zirconium balls is 100:40:150, the drying temperature is 80-100 ℃ and the drying time is 1-2h; the number of the separation sieves used for sieving is 80-120 meshes;
step 1.3, placing the prefabricated powder in a high-temperature furnace, and calcining at high temperature in the atmosphere, wherein the calcining temperature is 800-850 ℃, and the heat preservation time is 4-6 h; the temperature rising rate is 5 ℃/min; cooling along with the furnace to obtain high-temperature synthetic powder;
step 1.4, ball milling and drying the high-temperature synthesized powder again to obtain uniformly dispersed perovskite-structured prefabricated powder; the rotating speed in the ball milling process is set to be 250-300r/min, the ball milling time is set to be 8-13 hours, absolute ethyl alcohol is used as a ball milling medium, and the grinding balls are zirconium balls with the size of 5 mm; wherein, the mass ratio of the powder, the absolute ethyl alcohol and the zirconium balls is 100:40:150, the drying temperature is 80-100 ℃ and the drying time is 1-2h.
Preferably, the step 2 of the present invention includes:
step 2.1, adding PbO/CuO auxiliary materials into the pre-prepared powder according to the stoichiometric ratio of the chemical formula of the second component to obtain mixed powder, and putting the mixed powder into a ball milling tank;
step 2.2, ball milling, drying and sieving the mixed powder in the ball milling tank to obtain ceramic powder; the rotating speed in the ball milling process is set to be 250-300r/min, the ball milling time is set to be 8-13 hours, absolute ethyl alcohol is used as a ball milling medium, and the grinding balls are zirconium balls with the size of 5 mm; wherein, the mass ratio of the powder, the absolute ethyl alcohol and the zirconium balls is 100:40:150, the drying temperature is 80-100 ℃ and the drying time is 1-2h; the number of the separation sieves used for sieving is 80-120 meshes.
Noteworthy are: according to the invention, pbO/CuO is added into a ceramic system as an auxiliary material, the sintering temperature of the ceramic is reduced to 900-950 ℃, and low-temperature co-firing of the ceramic layer and the silver electrode layer can be realized.
Preferably, the step 3 of the present invention includes:
step 3.1, weighing the ceramic powder, the film forming agent, the solvent and the additive according to the proportion, and then pouring the ceramic powder, the film forming agent, the solvent and the additive into a ball milling tank for ball milling; setting the rotating speed in the ball milling process to be 250-300r/min, setting the ball milling time to be 8-13 hours, and finally obtaining casting slurry; wherein, the mass ratio of the ceramic powder to the film forming agent to the solvent to the additive is 100:5:24:3, a step of;
the film forming agent used in the step is polyvinyl butyral PVB; the solvent is ethyl acetate, butyl acetate and n-butyl alcohol, and the proportion is 8:4:7, preparing a base material; the additive is triethanolamine TEA, dibutyl phthalate DBP and polyethylene glycol PEG, the additive plays a role of a dispersing agent and a plasticizing agent, and the proportion of the triethanolamine TEA, the dibutyl phthalate DBP and the polyethylene glycol PEG is 1:1:1.
step 3.2, putting the ceramic powder into a roll ball mill for slow roll ball milling to obtain finished slurry, wherein the ball milling rotating speed is set to be 4-12 revolutions per minute, and the ball milling time is set to be 6-12 hours;
the purpose of the slow roll ball milling is to eliminate bubbles in the casting slurry and make the slurry more uniform. After slow rolling, the finished slurry is obtained.
And 3.3, placing the finished slurry into a hopper of a casting machine to carry out casting film formation to obtain a casting film, setting a clearance between a doctor blade of the casting machine to be 300-500 mu m, setting a forward speed of the doctor blade to be 2-6cm/s, and then drying the casting film to obtain a ceramic thick film, wherein the drying temperature is 60-80 ℃, and the drying time is 20-60min to obtain the ceramic thick film.
Preferably, the step 4 of the present invention includes:
step 4.1, punching the casting film into a plurality of circular or square ceramic diaphragms by using a punching cutting die according to test requirements or product application requirements;
step 4.2, according to the test requirement or the product application requirement, aligning and laminating the ceramic membranes together, and prepressing the ceramic membranes into a biscuit by using a press, wherein the prepressing pressure is set to be 1-5MPa; then vacuum packaging the pre-pressed biscuit by using a rubber film;
step 4.3, placing the vacuum packaged biscuit into a warm isostatic pressing cylinder, setting the temperature of the cylinder to be 80-90 ℃, the pressure of the cylinder to be 100-150MPa, and the pressure maintaining time to be 30min; and then taking out the biscuit and removing the rubber film to obtain the ceramic biscuit.
Preferably, the step 5 of the present invention includes:
step 5.1, placing the ceramic biscuit into a high-temperature furnace, and discharging glue to obtain a glue-discharging biscuit, wherein the glue-discharging temperature is 600 ℃; the glue discharging process of the step is as follows: heating the high-temperature furnace to 450 ℃ at the speed of 0.3 ℃/min, preserving heat for 4 hours, then continuously heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 6 hours, and finally obtaining a glue discharging biscuit;
and 5.2, placing the gelatin discharging biscuit into a high-temperature furnace, and performing high-temperature sintering under the atmosphere to obtain the PT-PZ-BLZT-LST-PC piezoelectric ceramic. The specific process of high-temperature sintering in the step is as follows: heating the high-temperature furnace to 950 ℃ at a speed of 5 ℃/min, and preserving heat for 4 hours to obtain square PT-PZ-BLZT-LST-PC piezoelectric ceramics with a side length of about 6mm and a height of about 1.2 mm.
In a third aspect, the invention provides a driver prepared from low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to the driver.
The performance of the low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to the driver prepared by the invention is verified by experimental data.
Table 1 specific performance parameters of the examples
The preparation process according to the invention is described below with particular reference to Table 1.
Let x=0.01, y=0.03, z=1.5 be example 1, x=0.02, y=0.04, z=1.5 be example 2, x=0.03, y=0.05, z=1.5 be example 3. Examples 1 to 3 were carried out in particular according to the following steps:
step 1, pbO and TiO are mixed 2 、ZrO 2 、Bi 2 O 3 、La 2 O 3 、SrCO 3 Putting ZnO powder into a ball milling tank according to the stoichiometric ratio of the first component for ball milling and high-temperature solid phase reaction to obtain the prefabricated powder with a perovskite structure, and specifically implementing the following steps:
step a1, according to the formula (1-x-y) of the first component (0.48 PbTiO 3 -0.52PbZrO 3 )-x(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -y(La 0.1 Sr 0.8 )TiO 2.95 And a second component of oxide starting material required for stoichiometric weighing of formula zPbO/CuO, including PbO, tiO 2 、ZrO 2 、Bi 2 O 3 、La 2 O 3 、SrCO 3 And ZnO; then putting the raw material mixed powder into a tank of Ni Long Qiumo;
and a2, putting the selected raw material mixed powder, zirconium balls and absolute ethyl alcohol into a nylon ball milling tank, performing ball milling, drying and sieving treatment, and then obtaining a pre-powder body. The rotational speed in the ball milling process was set to 280r/min and the ball milling time was set to 10 hours. Wherein, the mass ratio of the powder, the absolute ethyl alcohol and the zirconium balls is 100:40:150.
and a3, placing the prefabricated powder in a high-temperature furnace, and calcining at high temperature in the atmosphere, wherein the drying temperature is 80 ℃ and the time is 1h. Cooling along with the furnace to obtain high-temperature synthetic powder;
and a4, sieving the dried raw material powder, wherein the number of the sorting meshes is 100 meshes.
And a5, placing the obtained screened powder into a crucible for compaction and sealing by using a cover. And then placing the crucible into a high-temperature furnace for high-temperature calcination, wherein the calcination temperature is 850 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 4 hours. And after the calcination is finished, cooling along with the furnace, and then taking out the powder in the crucible to obtain the calcined powder.
And a step a6, ball milling and drying the calcined powder in the step a5 again to obtain the uniformly dispersed prefabricated ceramic powder. The ball milling and drying process is the same as step a 2.
And 2, adding PbO and CuO powder into the prefabricated powder in stoichiometric ratio, and performing ball milling and drying to obtain ceramic powder. The method is implemented according to the following steps:
and b1, weighing the required prefabricated ceramic PbO and CuO powder in proportion, and then pouring the prefabricated ceramic PbO and CuO powder into a ball milling tank for ball milling to obtain ceramic slurry. The ball milling process is the same as step a 2.
And b2, drying the ceramic powder slurry. The drying process is the same as step a 3.
And b3, screening the dried powder to obtain the ceramic powder required by the embodiment with uniform granularity. The sieving process is the same as step a 4.
And 3, preparing the ceramic powder into casting slurry, and preparing a ceramic thick film through casting molding. The method is implemented according to the following steps:
and c1, weighing ceramic powder, PVB, a solvent and an additive according to a proportion, and pouring the ceramic powder, the PVB, the solvent and the additive into a ball milling tank, wherein the ceramic powder is 100g, the PVB is 5g, the solvent is 24g, and the additive is 3g. The solvent is ethyl acetate, butyl acetate and n-butyl alcohol, and the proportion is 8:4:7. the additives are TEA (triethanolamine), DBP (dibutyl phthalate) and PEG (polyethylene glycol), and the proportion is 1:1:1.
and c2, adding 150g of 8mm zirconium balls into the ball milling tank, and then putting the balls into a planetary ball mill for ball milling. The rotational speed in the ball milling process was set to 280r/min and the ball milling time was set to 10 hours. And (5) fully ball milling to obtain the ceramic casting slurry.
And c3, putting the casting slurry into a roll ball mill for slow ball milling, wherein the ball milling rotating speed is set to be 6 revolutions per minute, and the ball milling time is set to be 8 hours, so that bubbles in the casting slurry can be fully removed in the process, and the slurry is more uniform. Finally, the standby slurry is obtained.
And c4, placing the standby slurry into a casting machine hopper for casting and forming a film, wherein toughened glass is used as a casting film carrier, the gap of a scraper is set to 400 mu m, and the advancing speed of the scraper is set to 5cm/s. And then drying the casting film at 80 ℃ for 30min. Finally, the finished casting film is obtained.
And 4, cutting the ceramic thick film into round ceramic films with a certain size, and preparing a plurality of round ceramic films into ceramic biscuit through warm isostatic compaction. The method is implemented according to the following steps:
and d1, punching the finished casting film obtained in the step c4 into a square ceramic film sheet with the thickness of 7X 7mm by using a square cutting die with the thickness of 7X 7mm for later use.
And d2, aligning and laminating 15 ceramic membranes together, prepressing the membranes into square ceramic blocks by using a press, and setting the prepressing pressure to be 5MPa.
And d3, wrapping the pre-pressed ceramic blocks with a rubber film, and then vacuum packaging the ceramic blocks by using a vacuum packaging machine.
And d4, placing the ceramic blocks subjected to vacuum packaging into a temperature isostatic pressing oil cylinder, setting the temperature of the oil cylinder to 90 ℃, setting the pressure of the oil cylinder to 150MPa, and maintaining the pressure for 30min. And then taking out the biscuit and removing the rubber film to finally obtain the ceramic block biscuit.
And 5, performing glue discharging and high-temperature solid-phase sintering on the ceramic biscuit to obtain the low-hysteresis high-temperature-resistant piezoelectric ceramic. The method is implemented according to the following steps:
and e1, placing the ceramic block biscuit obtained in the step 4.4 into a high-temperature furnace for discharging glue, wherein the glue discharging temperature is 600 ℃. The specific process is as follows: heating the muffle furnace to 450 ℃ at the speed of 0.3 ℃/min, preserving heat for 4 hours, then continuously heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 6 hours, and finally obtaining the gelatin discharging biscuit.
And e2, placing the gelatin discharging biscuit into a crucible, covering the crucible with ceramic powder with the same components, and covering the crucible with a cover to keep the crucible in a sealed state. The crucible is then placed in a high temperature furnace and high temperature sintering is performed in an atmospheric atmosphere. The specific process is as follows: heating the high-temperature furnace to 950 ℃ at a speed of 5 ℃/min, and preserving heat for 4 hours to obtain the square PT-PZ-BLZT-LST-PC piezoelectric ceramic block with the side length of about 6mm and the height of about 1.2 mm.
The piezoelectric ceramic blocks prepared in examples 1 to 3 were subjected to grinding thinning, polishing and silver firing treatments, respectively, and finally subjected to performance testing and characterization. The test procedure was as follows:
s1, placing the prepared piezoelectric ceramic block into an automatic polishing machine, and polishing the upper and lower surfaces of the ceramic block by using a 400-mesh diamond polishing disc until the thickness is 0.4mm to obtain a polished and leveled ceramic block to be tested.
S2, placing the ceramic block to be tested into an automatic polishing machine, and polishing one side of the ceramic block by using 9 mu m polishing solution, 3 mu m polishing solution and 1 mu m polishing solution respectively, wherein the 9 mu m polishing solution is used for polishing for 10 minutes, the 3 mu m polishing solution is used for polishing for 15 minutes and the 1 mu m polishing solution is used for polishing for 20 minutes. And then placing the polished ceramic wafer into a high-temperature furnace, and preserving the heat at 800 ℃ for 30 minutes at a heating rate of 5 ℃/min. The ceramic block after hot corrosion can be obtained and then SEM testing can be performed and the grain size analyzed.
And S3, coating silver paste on the upper and lower surfaces of the ceramic block to be tested obtained in the step S1, and then putting the ceramic block into an oven for drying, wherein the temperature of the oven is 80 ℃.
S4, placing the sample coated with silver in the step S3 into a high-temperature furnace, and preserving heat for 20 minutes at 700 ℃ with a heating rate of 5 ℃/min. Finally, the ceramic block with the electrodes on both sides is obtained.
S5, putting the silver-fired sample obtained in the step S4 into silicone oil at 120 ℃ for polarization for 5min, wherein the polarization electric field is 30kV/cm.
And S6, testing the polarized sample in the step S5 to obtain a dielectric thermogram, and analyzing to obtain the Curie temperature.
S7, testing the polarized sample in the S5 to obtain a unidirectional strain diagram, and analyzing to obtain hysteresis.
The test results are shown in FIGS. 3-5, FIG. 3 is a SEM comparison of PZT-5 with grains of examples 1-3 of the present invention, FIG. 4 is a comparison of PZT-5 with unidirectional strains of examples 1-3 of the present invention, where (a) is the unidirectional strain of PZT-5, (b) is the unidirectional strain of example 1, (c) is the unidirectional strain of example 2, and (d) is the unidirectional strain of example 3; FIG. 5 is a graph comparing the temperature spectra of PZT-5 and examples 1-3 of the present invention, wherein (a) is the temperature spectrum of PZT-5, (b) is the temperature spectrum of example 1, (c) is the temperature spectrum of example 2, and (d) is the temperature spectrum of example 3. As can be seen from fig. 3-5, PT-PZ-BLZT-LST-PC ceramic blocks obtained using the formulation and preparation method of the present invention have an average grain size of up to 30 μm with a hysteresis of up to 5.8% at minimum and a curie temperature of up to 342 ℃.
Therefore, the low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to the driver has the characteristics of low hysteresis and high temperature resistance, the hysteresis is 5.8 percent,T c the temperature is 342 ℃, the strain can not be attenuated within the room temperature to 250 ℃, the application range is wider than that of the traditional soft ceramic, the service temperature range is wider, and the stability is stronger. The ceramic powder prepared by the method has the advantages of low sintering temperature, simple preparation method and low manufacturing cost, and can be directly used for preparing the multilayer cofiring piezoelectric ceramic driver. Obviously, the driver prepared by the piezoelectric ceramic formula provided by the invention can realize high-precision direct driving and quick response without using a feedback circuit and a strain gauge sensor, and effectively reduces the design difficulty of a driver control circuit and the manufacturing cost of the driver.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
Although the present application has been described herein in connection with various embodiments, other variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed application, from a review of the figures, the disclosure, and the appended claims. In the claims, the word "comprising" does not exclude other elements or steps, and the "a" or "an" does not exclude a plurality.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (10)
1. A low hysteresis high temperature resistant lead-based piezoelectric ceramic for use in a driver, comprising: two components, wherein the first component has the formula:
(1-x-y)(0.48PbTiO 3 -0.52PbZrO 3 )-x(Bi 0.3 La 0.7 )(Zn 0.5 Ti 0.5 )O 3 -y(La 0.1 Sr 0.8 )TiO 2.95 wherein x and y represent molar ratio, x is more than or equal to 0.01 and less than or equal to 0.03,0.02, and y is more than or equal to 0.05;
the chemical formula of the second component is: zPbO/CuO; the mass percentage of the second component is z, and z is more than or equal to 1 and less than or equal to 2.5; wherein, the mol ratio of PbO to CuO is 0.72:0.28.
2. a method of preparing the low hysteresis high temperature resistant lead-based piezoelectric ceramic for use in a driver of claim 1, comprising:
step 1, pbO and TiO are mixed 2 、ZrO 2 、Bi 2 O 3 、La 2 O 3 、SrCO 3 Putting ZnO powder into a ball milling tank according to the stoichiometric ratio of the first component for ball milling and high-temperature solid phase reaction to obtain prefabricated powder with a perovskite structure;
step 2, adding PbO and CuO powder in the stoichiometric ratio of the second component in the prefabricated powder, and performing ball milling and drying to obtain ceramic powder;
step 3, preparing the ceramic powder into casting slurry, and preparing a ceramic thick film through casting molding;
step 4, cutting the ceramic thick film into round ceramic films, and preparing a plurality of round ceramic films into ceramic biscuit by warm isostatic compaction;
and 5, performing glue discharging and high-temperature solid-phase sintering on the ceramic biscuit to obtain the low-hysteresis high-temperature-resistant piezoelectric ceramic.
3. The method for preparing low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to driver according to claim 2, wherein the step 1 comprises:
step 1.1, pbO and TiO are mixed 2 、ZrO 2 、Bi 2 O 3 、La 2 O 3 、SrCO 3 The ZnO powder raw materials are weighed and mixed according to the stoichiometric ratio of the chemical formula of the first component, and then the raw material mixed powder is put into a tank of Ni Long Qiumo;
step 1.2, performing ball milling, drying and sieving treatment on raw material mixed powder put into a nylon ball milling tank to obtain a pre-powder; the rotating speed in the ball milling process is set to be 250-300r/min, the ball milling time is set to be 8-13 hours, absolute ethyl alcohol is used as a ball milling medium, and the grinding balls are zirconium balls with the size of 5 mm; wherein, the mass ratio of the powder, the absolute ethyl alcohol and the zirconium balls is 100:40:150, the drying temperature is 80-100 ℃ and the drying time is 1-2h; the number of the separation sieves used for sieving is 80-120 meshes;
step 1.3, placing the prefabricated powder in a high-temperature furnace, and calcining at high temperature in the atmosphere, wherein the calcining temperature is 800-850 ℃, and the heat preservation time is 4-6 h; the temperature rising rate is 5 ℃/min; cooling along with the furnace to obtain high-temperature synthetic powder;
step 1.4, ball milling and drying the high-temperature synthesized powder again to obtain uniformly dispersed perovskite-structured prefabricated powder; the rotating speed in the ball milling process is set to be 250-300r/min, the ball milling time is set to be 8-13 hours, absolute ethyl alcohol is used as a ball milling medium, and the grinding balls are zirconium balls with the size of 5 mm; wherein, the mass ratio of the powder, the absolute ethyl alcohol and the zirconium balls is 100:40:150, the drying temperature is 80-100 ℃ and the drying time is 1-2h.
4. The method for preparing low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to driver according to claim 2, wherein the step 2 comprises:
step 2.1, adding PbO/CuO auxiliary materials into the pre-prepared powder according to the stoichiometric ratio of the chemical formula of the second component to obtain mixed powder, and putting the mixed powder into a ball milling tank;
step 2.2, ball milling, drying and sieving the mixed powder in the ball milling tank to obtain ceramic powder; the rotating speed in the ball milling process is set to be 250-300r/min, the ball milling time is set to be 8-13 hours, absolute ethyl alcohol is used as a ball milling medium, and the grinding balls are zirconium balls with the size of 5 mm; wherein, the mass ratio of the powder, the absolute ethyl alcohol and the zirconium balls is 100:40:150, the drying temperature is 80-100 ℃ and the drying time is 1-2h; the number of the separation sieves used for sieving is 80-120 meshes.
5. The method for preparing low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to driver according to claim 2, wherein the step 3 comprises:
step 3.1, weighing the ceramic powder, the film forming agent, the solvent and the additive according to the proportion, and then pouring the ceramic powder, the film forming agent, the solvent and the additive into a ball milling tank for ball milling; setting the rotating speed in the ball milling process to be 250-300r/min, setting the ball milling time to be 8-13 hours, and finally obtaining casting slurry; wherein, the mass ratio of the ceramic powder to the film forming agent to the solvent to the additive is 100:5:24:3, a step of;
step 3.2, putting the ceramic powder into a roll ball mill for slow roll ball milling to obtain finished slurry, wherein the ball milling rotating speed is set to be 4-12 revolutions per minute, and the ball milling time is set to be 6-12 hours;
and 3.3, placing the finished slurry into a hopper of a casting machine to carry out casting film formation to obtain a casting film, setting a clearance between a doctor blade of the casting machine to be 300-500 mu m, setting a forward speed of the doctor blade to be 2-6cm/s, and then drying the casting film to obtain a ceramic thick film, wherein the drying temperature is 60-80 ℃, and the drying time is 20-60min to obtain the ceramic thick film.
6. The method for preparing low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to driver according to claim 5, wherein the film forming agent used in the step 3.1 is polyvinyl butyral PVB; the solvent is ethyl acetate, butyl acetate and n-butyl alcohol, and the proportion is 8:4:7, preparing a base material; the additive is triethanolamine TEA, dibutyl phthalate DBP and polyethylene glycol PEG, the additive plays a role of a dispersing agent and a plasticizing agent, and the proportion of the triethanolamine TEA, the dibutyl phthalate DBP and the polyethylene glycol PEG is 1:1:1.
7. the method for preparing low hysteresis high temperature resistant lead-based piezoelectric ceramic for use in driver according to claim 5, wherein said step 4 comprises:
step 4.1, punching the casting film into a plurality of circular or square ceramic diaphragms by using a punching cutting die according to test requirements or product application requirements;
step 4.2, according to the test requirement or the product application requirement, aligning and laminating the ceramic membranes together, and prepressing the ceramic membranes into a biscuit by using a press, wherein the prepressing pressure is set to be 1-5MPa; then vacuum packaging the pre-pressed biscuit by using a rubber film;
step 4.3, placing the vacuum packaged biscuit into a warm isostatic pressing cylinder, setting the temperature of the cylinder to be 80-90 ℃, the pressure of the cylinder to be 100-150MPa, and the pressure maintaining time to be 30min; and then taking out the biscuit and removing the rubber film to obtain the ceramic biscuit.
8. The method for preparing low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to driver according to claim 2, wherein the step 5 comprises:
step 5.1, placing the ceramic biscuit into a high-temperature furnace, and discharging glue to obtain a glue-discharging biscuit, wherein the glue-discharging temperature is 600 ℃;
and 5.2, placing the gelatin discharging biscuit into a high-temperature furnace, and performing high-temperature sintering under the atmosphere to obtain the PT-PZ-BLZT-LST-PC piezoelectric ceramic.
9. The method for preparing the low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to the driver according to claim 8, wherein the glue discharging process in the step 5.1 is as follows: heating the high-temperature furnace to 450 ℃ at the speed of 0.3 ℃/min, preserving heat for 4 hours, then continuously heating to 600 ℃ at the speed of 1 ℃/min, preserving heat for 6 hours, and finally obtaining a glue discharging biscuit;
the specific process of high-temperature sintering in the step 5.2 is as follows: heating the high-temperature furnace to 950 ℃ at a speed of 5 ℃/min, and preserving heat for 4 hours to obtain square PT-PZ-BLZT-LST-PC piezoelectric ceramics with a side length of about 6mm and a height of about 1.2 mm.
10. A driver prepared from the low hysteresis high temperature resistant lead-based piezoelectric ceramic applied to the driver of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311684787.3A CN117865672A (en) | 2023-12-08 | 2023-12-08 | Low-hysteresis high-temperature-resistant lead-based piezoelectric ceramic applied to driver and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311684787.3A CN117865672A (en) | 2023-12-08 | 2023-12-08 | Low-hysteresis high-temperature-resistant lead-based piezoelectric ceramic applied to driver and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117865672A true CN117865672A (en) | 2024-04-12 |
Family
ID=90587383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311684787.3A Pending CN117865672A (en) | 2023-12-08 | 2023-12-08 | Low-hysteresis high-temperature-resistant lead-based piezoelectric ceramic applied to driver and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117865672A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016103515A1 (en) * | 2014-12-26 | 2016-06-30 | セイコーエプソン株式会社 | Method for producing piezoelectric material, piezoelectric element using piezoelectric material produced using same, and device using piezoelectric element |
| CN113307619A (en) * | 2021-05-15 | 2021-08-27 | 西安外事学院 | Preparation method of bismuth ferrite-lead titanate-bismuth magnesium niobate ternary system high-temperature piezoelectric ceramic |
| CN115321979A (en) * | 2022-08-01 | 2022-11-11 | 苏州思若梅克电子科技有限公司 | Multi-element doped lead-based piezoelectric ceramic and preparation method thereof |
| CN115321978A (en) * | 2022-08-01 | 2022-11-11 | 苏州思若梅克电子科技有限公司 | Multilayer lead-based piezoelectric ceramic and preparation method thereof |
| CN116916732A (en) * | 2023-05-15 | 2023-10-20 | 西安外事学院 | Preparation method of barium titanate-based texture electrostriction multilayer ceramic driver |
-
2023
- 2023-12-08 CN CN202311684787.3A patent/CN117865672A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016103515A1 (en) * | 2014-12-26 | 2016-06-30 | セイコーエプソン株式会社 | Method for producing piezoelectric material, piezoelectric element using piezoelectric material produced using same, and device using piezoelectric element |
| CN113307619A (en) * | 2021-05-15 | 2021-08-27 | 西安外事学院 | Preparation method of bismuth ferrite-lead titanate-bismuth magnesium niobate ternary system high-temperature piezoelectric ceramic |
| CN115321979A (en) * | 2022-08-01 | 2022-11-11 | 苏州思若梅克电子科技有限公司 | Multi-element doped lead-based piezoelectric ceramic and preparation method thereof |
| CN115321978A (en) * | 2022-08-01 | 2022-11-11 | 苏州思若梅克电子科技有限公司 | Multilayer lead-based piezoelectric ceramic and preparation method thereof |
| CN116916732A (en) * | 2023-05-15 | 2023-10-20 | 西安外事学院 | Preparation method of barium titanate-based texture electrostriction multilayer ceramic driver |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109626988B (en) | Piezoelectric ceramic material with high piezoelectric response and high Curie temperature and preparation method thereof | |
| CN108929112B (en) | Tin-doped lead lanthanum zirconate titanate thick film ceramic and preparation and application thereof | |
| CN105869887B (en) | A kind of X9R high-temperature stables multilayer ceramic capacitor porcelain slurry and its device preparation method | |
| CN111533556B (en) | Preparation method of grain-oriented strontium sodium niobate leadless ferroelectric ceramic | |
| CN104402432A (en) | Textured piezoelectric ceramic material and preparation method thereof | |
| CN110981468B (en) | Preparation method of sodium bismuth titanate-based piezoelectric ceramic | |
| CN113213918B (en) | Strontium bismuth titanate-bismuth scandium acid-lead titanate series high-temperature piezoelectric ceramic material with high piezoelectric performance and low loss and preparation method thereof | |
| CN109608194B (en) | Lead zirconate titanate thick film ceramic and preparation method and application thereof | |
| CN106938929B (en) | Method for preparing room temperature high electric card effect leadless relaxation ferroelectric ceramic | |
| CN115321978B (en) | Multilayer lead-based piezoelectric ceramic and preparation method thereof | |
| CN114621004A (en) | High-entropy ceramic material with high energy storage density and preparation method thereof | |
| CN103011805B (en) | BaTiO3 based leadless X8R type ceramic capacitor dielectric material and preparation method thereof | |
| CN110357624B (en) | High-dielectric-constant glass frit modified strontium zirconate doped potassium-sodium niobate lead-free transparent ceramic material and preparation method thereof | |
| CN107903055A (en) | A kind of grade doping bismuth-sodium titanate Quito layer leadless piezoelectric ceramics | |
| CN114478006A (en) | KNNS-BNZ + CuO piezoceramic material and preparation method and application thereof | |
| CN113024250B (en) | Sb with high energy storage density and energy storage efficiency 5+ Strontium sodium silver tungsten bronze doped ferroelectric ceramic material and preparation method thereof | |
| CN111533555B (en) | Preparation method of layered compact strontium potassium niobate leadless piezoelectric ceramic | |
| CN113773078A (en) | High-power piezoelectric ceramic material and preparation method thereof | |
| CN110981480A (en) | High Tr-tAnd TcLead base of<001>CTextured piezoelectric ceramic material and preparation method thereof | |
| CN112408977A (en) | High-quality ceramic dielectric material and preparation method thereof | |
| CN111574198A (en) | High-energy-storage lead zirconate-based antiferroelectric multilayer ceramic capacitor and preparation method thereof | |
| CN117865672A (en) | Low-hysteresis high-temperature-resistant lead-based piezoelectric ceramic applied to driver and preparation method thereof | |
| CN106986629B (en) | Preparation method of bismuth titanate-based bismuth laminated structure ferroelectric ceramic target material | |
| CN115894020B (en) | PMNZT-based piezoelectric ceramic with high piezoelectric coefficient and preparation method and application thereof | |
| WO2006093043A1 (en) | Multilayer piezoelectric element |
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 |