CN113105236B - Preparation method of lead-free piezoelectric ceramic based on femtosecond laser processing and lead-free piezoelectric ceramic - Google Patents

Preparation method of lead-free piezoelectric ceramic based on femtosecond laser processing and lead-free piezoelectric ceramic Download PDF

Info

Publication number
CN113105236B
CN113105236B CN202110407888.0A CN202110407888A CN113105236B CN 113105236 B CN113105236 B CN 113105236B CN 202110407888 A CN202110407888 A CN 202110407888A CN 113105236 B CN113105236 B CN 113105236B
Authority
CN
China
Prior art keywords
lead
free piezoelectric
piezoelectric ceramic
wafer
ball milling
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
CN202110407888.0A
Other languages
Chinese (zh)
Other versions
CN113105236A (en
Inventor
王媛玉
李安江
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.)
Guizhou University
Original Assignee
Guizhou University
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 Guizhou University filed Critical Guizhou University
Priority to CN202110407888.0A priority Critical patent/CN113105236B/en
Publication of CN113105236A publication Critical patent/CN113105236A/en
Application granted granted Critical
Publication of CN113105236B publication Critical patent/CN113105236B/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/38—Removing material by boring or cutting
    • B23K26/382—Removing material by boring or cutting by boring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/40—Removing material taking account of the properties of the material involved
    • B23K26/402—Removing material taking account of the properties of the material involved involving non-metallic material, e.g. isolators
    • 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
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5036—Ferrites
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5049—Zinc or bismuth oxides
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/50—Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26
    • B23K2103/52—Ceramics
    • 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
    • C04B2235/3201—Alkali metal oxides 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/612—Machining
    • 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
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Optics & Photonics (AREA)
  • Physics & Mathematics (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention discloses a method for preparing lead-free piezoelectric ceramics based on femtosecond laser processing and the lead-free piezoelectric ceramics. The piezoelectric constant d of the lead-free piezoelectric ceramic prepared by the method33The lead-free piezoelectric ceramic reaches 128pC/N, is improved by about 35 percent compared with a lead-free piezoelectric ceramic matrix, and is improved by about 16 percent compared with the reported lead-free piezoelectric ceramic synthesized by a one-step method and having the same composition; the electromechanical coupling coefficient k of the lead-free piezoelectric ceramic prepared by the methodpAbout 41% compared to the reported one-step synthesis with phaseThe lead-free piezoelectric ceramic with the same composition is improved by about 15 percent.

Description

Preparation method of lead-free piezoelectric ceramic based on femtosecond laser processing and lead-free piezoelectric ceramic
Technical Field
The invention relates to the technical field of piezoelectric ceramics, in particular to a method for preparing lead-free piezoelectric ceramics based on femtosecond laser processing and the lead-free piezoelectric ceramics.
Background
The piezoelectric ceramic is an important functional material, has occupied most of the functional ceramic market due to the advantages of good comprehensive performance, mature preparation technology, low price and the like, and is widely applied to the civil and military fields. Lead zirconate titanate (PZT) based ceramics are the most widely used piezoelectric ceramics at present, but the "unleaded" piezoelectric materials are a necessary trend for future development due to the requirement of human sustainable development. Potassium sodium niobate (KNN) leadless piezoelectric ceramics has high Curie temperature (T)cAbout 420 c) is one of the preferred materials that can replace lead-based ceramics. At present, the performance of the ceramic of the system is enhanced through doping modification, but the performance improvement meets the bottleneck. In addition, the KNN-doped modified ceramic has complex formula, which causes the problems of high production cost, poor performance repeatability and the like.
Disclosure of Invention
The invention provides a method for preparing lead-free piezoelectric ceramic based on femtosecond laser processing and the lead-free piezoelectric ceramic, which are used for overcoming the defects of complex doping means, poor performance repeatability and the like in the prior art.
In order to achieve the purpose, the invention provides a method for preparing lead-free piezoelectric ceramics based on femtosecond laser processing, which comprises the following steps:
s1: weighing K according to the molar ratio of 1:1:22CO3、Na2CO3And Nb2O5Mixing, carrying out first ball milling, presintering, carrying out second ball milling, drying, granulating and pressing to obtain a wafer;
s2: respectively carrying out laser drilling on the upper surface and the lower surface of the wafer by using a femtosecond laser so as to form holes with the diameter of 8-12 mu m on the upper surface and the lower surface of the wafer;
s3: spin coating ZnO solution or BiFeO on the upper surface and the lower surface of the wafer passing through S23A solution;
s4: and sintering the wafer subjected to S3 in an air atmosphere, and cooling the wafer along with the furnace to obtain the lead-free piezoelectric ceramic.
In order to achieve the purpose, the invention also provides the lead-free piezoelectric ceramic based on femtosecond laser processing, and the lead-free piezoelectric ceramic is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the lead-free piezoelectric ceramic based on femtosecond laser processing, the upper surface and the lower surface of the wafer are subjected to laser drilling and filling treatment by using the femtosecond laser on the basis of the traditional lead-free piezoelectric ceramic preparation, so that the performance superior to that of the traditional doped modified ceramic is obtained, the ceramic modification means is simplified, and the repeatability of the ceramic performance is improved. Spin coating ZnO solution or BiFeO on the upper surface and the lower surface of the wafer3Solution of ZnO and BiFeO3The characteristic energy band structure can reduce polarization activation energy, increase the efficiency of thermal ion relaxation polarization and obviously improve the dielectric constant of the ceramic. In addition, ZnO and BiFeO pass through3And the energy band at the KNN interface interacts with the energy band, so that an internal electric field favorable for ceramic electric domain deflection can be formed.
The piezoelectric constant d of the lead-free piezoelectric ceramic prepared by the preparation method provided by the invention33Up to 128pC/N, compared with a lead-free piezoelectric ceramic matrix (d)33About 95pC/N) by about 35%, compared with the reported one-step synthesis of lead-free piezoelectric ceramics (d) with the same composition33About 110pC/N) by about 16%.
The electromechanical coupling coefficient k of the lead-free piezoelectric ceramic prepared by the preparation method provided by the inventionpAbout 41%, compared with the reported lead-free piezoelectric ceramics synthesized by one-step method and having the same composition (d)33About 110pC/N) by about 16%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1a is a surface topography of holes in a lead-free piezoelectric ceramic prepared in comparative example 1;
FIG. 1b is a graph showing the surface morphology of a lead-free piezoelectric ceramic prepared in example 1;
FIG. 2a is a hysteresis loop of the lead-free piezoelectric ceramic prepared in comparative example 1;
FIG. 2b is a hysteresis loop of a lead-free piezoelectric ceramic prepared in example 1;
FIG. 2c is a hysteresis loop of a lead-free piezoelectric ceramic prepared in example 2;
FIG. 3a is a unipolar strain curve of the lead-free piezoelectric ceramic prepared in comparative example 1;
FIG. 3b is a unipolar strain curve of the lead-free piezoelectric ceramic prepared in example 1;
FIG. 3c is a unipolar strain curve of the lead-free piezoelectric ceramic prepared in example 2;
FIG. 4a is a graph showing the impedance and phase angle of the lead-free piezoelectric ceramic prepared in comparative example 1 as a function of frequency;
FIG. 4b is a graph showing the impedance and phase angle of the lead-free piezoelectric ceramic prepared in example 1 as a function of frequency;
FIG. 4c is a graph showing the impedance and phase angle of the lead-free piezoelectric ceramic prepared in example 2 as a function of frequency;
FIG. 4d is a graph showing the variation of impedance and phase angle with frequency of the lead-free piezoelectric ceramic prepared in comparative example 2;
FIG. 5 is a dielectric property diagram of lead-free piezoelectric ceramics prepared in examples 1 to 2 and comparative examples 1 to 2;
FIG. 6 is a graph showing piezoelectric properties of lead-free piezoelectric ceramics prepared in examples 1 to 2 and comparative examples 1 to 2.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The drugs/reagents used are all commercially available without specific mention.
The invention provides a method for preparing lead-free piezoelectric ceramics based on femtosecond laser processing, which comprises the following steps:
s1: weighing K according to the molar ratio of 1:1:22CO3、Na2CO3And Nb2O5Mixing, carrying out first ball milling, presintering, carrying out second ball milling, drying, granulating and pressing to obtain a wafer;
s2: respectively carrying out laser drilling on the upper surface and the lower surface of the wafer by using a femtosecond laser so as to form holes with the diameter of 8-12 mu m on the upper surface and the lower surface of the wafer;
s3: spin coating ZnO solution or BiFeO on the upper surface and the lower surface of the wafer passing through S23A solution;
s4: and sintering the wafer subjected to S3 in an air atmosphere, and cooling the wafer along with the furnace to obtain the lead-free piezoelectric ceramic.
Preferably, in step S1, the pre-firing temperature is 850 ℃ and the time is 6 h. After pre-sintering, the raw material powder reacts to synthesize a main crystal phase, and after granulation, pressing and molding, the main crystal phase is sintered into compact ceramics.
Preferably, in step S1, the first ball milling and the second ball milling are specifically:
in an agate tank, agate balls are used as ball milling media, and ball milling is carried out in absolute ethyl alcohol for 12 hours. Grinding and mixing the initial raw materials by the first ball milling; and the second ball milling finishes the grinding of the pre-sintered powder to reach the uniform size required by granulation.
Preferably, in step S1, the pressing is performed under 10MPa to form a disc with a diameter of 10mm and a thickness of 1.2 mm.
Preferably, in step S2, the laser drilling process conditions are: the laser output repetition frequency is 200kHz, the peak power is 1.51GW, the path is in one-way parallel scanning, the scanning is carried out for 2 times, and the distance is 0.003 mm. The process selection is made according to the hardness and size of the wafer.
Preferably, in step S3, the concentration of ZnO in the ZnO solution is 1g/100 mL;
the BiFeO3BiFeO in solution3The concentration of (2) is 1g/100 mL.
ZnO solution and BiFeO3The concentration of the solution affects the dispersibility of the powder, and further affects the filling effect.
Preferably, in step S4, the sintering temperature is 1090-1130 ℃ and the sintering time is 3 h.
The invention also provides the lead-free piezoelectric ceramic based on femtosecond laser processing, which is prepared by the preparation method.
Example 1
The embodiment provides a method for preparing lead-free piezoelectric ceramics based on femtosecond laser processing, which comprises the following steps:
s1: weighing K according to the molar ratio of 1:1:22CO3、Na2CO3And Nb2O5Mixing, ball milling in absolute ethyl alcohol for 12h by taking agate balls as ball milling media in an agate tank, presintering for 6h at 850 ℃, ball milling in the agate tank for 12h by taking the agate balls as ball milling media in the absolute ethyl alcohol, drying, granulating, pressing and molding, and pressing under 10MPa to prepare wafers with the diameter of 10mm and the thickness of 1.2 mm.
S2: respectively carrying out laser drilling on the upper surface and the lower surface of the wafer by using a femtosecond laser so as to form quasi-conical holes with the diameter of 8-12 microns on the upper surface and the lower surface of the wafer;
the laser drilling process conditions are as follows: the output repetition frequency of the laser is 200kHz, the peak power is 1.51GW, the path is a unidirectional parallel scanning path, the path is unidirectional parallel scanning, the scanning is carried out for 2 times, and the distance is 0.003 mm.
S3: ZnO solutions (1 g/100mL in concentration) were spin-coated on both the upper and lower surfaces of the wafer passed through S2.
S4: and sintering the wafer subjected to S3 in an air atmosphere (at 1100 ℃ for 3 hours), and cooling the wafer along with a furnace to obtain the lead-free piezoelectric ceramic.
Example 2
Compared with the embodiment 1, the step S3 of the present embodiment is: respectively spin-coating BiFeO on the upper surface and the lower surface of the wafer passing through S23The solution (concentration 1g/100mL) was otherwise the same as in example 1.
Comparative example 1
This comparative example, which provides a method for preparing a lead-free piezoelectric ceramic based on femtosecond laser processing, is similar to example 1 except that steps S2 and S3 are not performed, compared to example 1.
Comparative example 2
The present comparative example provides a method for preparing a lead-free piezoelectric ceramic based on femtosecond laser processing, and compared with example 1, step S3 of this example is: respectively spin-coating Al on the upper surface and the lower surface of the wafer passing through S22O3The solution (concentration 1g/100mL) was otherwise the same as in example 1.
Silver pastes were coated on the upper and lower surfaces of the lead-free piezoelectric ceramics prepared in examples 1 to 2 and comparative examples 1 to 2, respectively, and calcined at 700 ℃ for 10min to form top and bottom electrodes. And (3) putting the sample with the electrode into silicon oil at 50 ℃ for polarization, namely applying a direct current electric field of 3-4 kV/mm, and keeping for 25-40 min. Then, relevant tests of piezoelectric, dielectric and ferroelectric properties are carried out. The results are as follows:
fig. 1a is a surface topography of a hole in the lead-free piezoelectric ceramic prepared in comparative example 1, and fig. 1b is a surface topography of the lead-free piezoelectric ceramic prepared in example 1. It can be seen from the figure that the lead-free piezoelectric ceramics in comparative example 1 and example 1 have pores distributed on the surface, whereas the pores in comparative example 1 are not filled, and the pores in example 1 are filled.
Fig. 2a is a hysteresis loop of a lead-free piezoelectric ceramic prepared in comparative example 1, fig. 2b is a hysteresis loop of a lead-free piezoelectric ceramic prepared in example 1, and fig. 2c is a hysteresis loop of a lead-free piezoelectric ceramic prepared in example 2. From the figure, the phasesThe lead-free piezoelectric ceramics prepared in examples 1 and 2 had an increased remanent polarization compared to comparative example 1, i.e., due to the filling of ZnO or BiFeO3So that the residual polarization strength of the lead-free piezoelectric ceramic is increased.
Fig. 3a is a unipolar strain curve of the lead-free piezoelectric ceramic prepared in comparative example 1, fig. 3b is a unipolar strain curve of the lead-free piezoelectric ceramic prepared in example 1, and fig. 3c is a unipolar strain curve of the lead-free piezoelectric ceramic prepared in example 2. As can be seen from the figure, the lead-free piezoelectric ceramics prepared in examples 1 and 2 are filled with ZnO or BiFeO as compared with comparative example 13The strain of the monopole at 30kV/cm is increased.
Fig. 4a is a graph showing the impedance and phase angle of the lead-free piezoelectric ceramic prepared in comparative example 1 as a function of frequency, fig. 4b is a graph showing the impedance and phase angle of the lead-free piezoelectric ceramic prepared in example 1 as a function of frequency, fig. 4c is a graph showing the impedance and phase angle of the lead-free piezoelectric ceramic prepared in example 2 as a function of frequency, and fig. 4d is a graph showing the impedance and phase angle of the lead-free piezoelectric ceramic prepared in comparative example 2 as a function of frequency. As can be seen from the figure, in the present invention, ZnO or BiFeO is used as the material3The phase angle of the lead-free piezoelectric ceramic is changed, which shows that the lead-free piezoelectric ceramic prepared in the embodiment 1 and the embodiment 2 has higher polarization deflection efficiency under the action of an external electric field.
FIG. 5 is a dielectric property diagram of the lead-free piezoelectric ceramics prepared in examples 1-2 and comparative examples 1-2, and it can be seen that the dielectric constant of the lead-free piezoelectric ceramics prepared by the preparation method of the present invention is significantly increased and the dielectric loss is significantly reduced compared to comparative examples 1-2.
Fig. 6 is a piezoelectric performance graph of the lead-free piezoelectric ceramics prepared in examples 1 to 2 and comparative examples 1 to 2, and it can be seen that the piezoelectric constant and the electromechanical coupling coefficient of the lead-free piezoelectric ceramics prepared by the preparation method of the present invention are significantly increased compared to those of comparative examples 1 and 2. Further, as can be seen from fig. 5 and 6, the lead-free piezoelectric ceramic of comparative example 2 is inferior in performance to that of comparative example 1, and it is important to explain the selection of the doping material.
Note: in the figure, KNN denotes the lead-free piezoelectric ceramic of comparative example 1, KNN + ZN denotes the lead-free piezoelectric ceramic of example 1, KNN + BF denotes the lead-free piezoelectric ceramic of example 2, and KNN + AL denotes the lead-free piezoelectric ceramic of comparative example 2.
Table 1 shows polarization activation energy and relaxation time table of the lead-free piezoelectric ceramics prepared in examples 1 to 2 and comparative examples 1 to 2, and it can be seen from table 1 that the polarization activation energy and the relaxation time are significantly reduced in examples 1 and 2 compared to comparative examples 1 and 2, which shows that the lead-free piezoelectric ceramics prepared in examples 1 and 2 are more likely to undergo thermal relaxation polarization and thus have significantly increased dielectric constants.
TABLE 1 tables of polarization activation energy and relaxation time of lead-free piezoelectric ceramics prepared in examples 1 to 2 and comparative examples 1 to 2
KNN KNN+ZN
Relaxation time/. times.10-4s 2.235 1.762
Ea/eV 21.425 10.25
KNN+BF KNN+AL
Relaxation time/. times.10-4s 1.747 2.782
Ea/eV 15.275 14.525
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (8)

1. A preparation method of lead-free piezoelectric ceramic based on femtosecond laser processing is characterized by comprising the following steps:
s1: weighing K according to the molar ratio of 1:1:22CO3、Na2CO3And Nb2O5Mixing, carrying out first ball milling, presintering, carrying out second ball milling, drying, granulating and pressing to obtain a wafer;
s2: respectively carrying out laser drilling on the upper surface and the lower surface of the wafer by using a femtosecond laser so as to form holes with the diameter of 8-12 mu m on the upper surface and the lower surface of the wafer;
s3: spin coating ZnO solution or BiFeO on the upper surface and the lower surface of the wafer passing through S23A solution;
s4: and sintering the wafer subjected to S3 in an air atmosphere, and cooling the wafer along with the furnace to obtain the lead-free piezoelectric ceramic.
2. The method of claim 1, wherein the pre-firing is performed at 850 ℃ for 6 hours in step S1.
3. The preparation method according to claim 1, wherein in step S1, the first ball milling and the second ball milling are specifically:
in an agate tank, agate balls are used as ball milling media, and ball milling is carried out in absolute ethyl alcohol for 12 hours.
4. The production method according to claim 1, wherein in step S1, the pressing is performed to press a disc having a diameter of 10mm and a thickness of 1.2mm at 10 MPa.
5. The method of claim 1, wherein in step S2, the laser drilling process conditions are: the laser output repetition frequency is 200kHz, the peak power is 1.51GW, the path is in one-way parallel scanning, the scanning is carried out for 2 times, and the distance is 0.003 mm.
6. The production method according to claim 1, wherein in step S3, the concentration of ZnO in the ZnO solution is 1g/100 mL;
the BiFeO3BiFeO in solution3The concentration of (2) is 1g/100 mL.
7. The method of claim 1, wherein in step S4, the sintering temperature is 1090-1130 ℃ and the sintering time is 3 h.
8. A lead-free piezoelectric ceramic based on femtosecond laser processing, which is characterized by being prepared by the preparation method of any one of claims 1 to 7.
CN202110407888.0A 2021-04-15 2021-04-15 Preparation method of lead-free piezoelectric ceramic based on femtosecond laser processing and lead-free piezoelectric ceramic Active CN113105236B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110407888.0A CN113105236B (en) 2021-04-15 2021-04-15 Preparation method of lead-free piezoelectric ceramic based on femtosecond laser processing and lead-free piezoelectric ceramic

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110407888.0A CN113105236B (en) 2021-04-15 2021-04-15 Preparation method of lead-free piezoelectric ceramic based on femtosecond laser processing and lead-free piezoelectric ceramic

Publications (2)

Publication Number Publication Date
CN113105236A CN113105236A (en) 2021-07-13
CN113105236B true CN113105236B (en) 2022-06-14

Family

ID=76717445

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110407888.0A Active CN113105236B (en) 2021-04-15 2021-04-15 Preparation method of lead-free piezoelectric ceramic based on femtosecond laser processing and lead-free piezoelectric ceramic

Country Status (1)

Country Link
CN (1) CN113105236B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101037332A (en) * 2007-04-20 2007-09-19 四川大学 Multi constituent niobate lead-free piezoelectric ceramics
CN103553605A (en) * 2013-10-15 2014-02-05 陕西科技大学 KNN-BF leadless piezoelectric ceramic and preparation method thereof
CN104973863A (en) * 2014-04-11 2015-10-14 日本特殊陶业株式会社 Lead-free piezo-electric porcelain composition, piezo-electric element using the same, and method for producing lead-free piezo-electric porcelain composition
CN108137375A (en) * 2015-10-09 2018-06-08 康宁股份有限公司 The base material and its formation process of glass sensor with through-hole

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101037332A (en) * 2007-04-20 2007-09-19 四川大学 Multi constituent niobate lead-free piezoelectric ceramics
CN103553605A (en) * 2013-10-15 2014-02-05 陕西科技大学 KNN-BF leadless piezoelectric ceramic and preparation method thereof
CN104973863A (en) * 2014-04-11 2015-10-14 日本特殊陶业株式会社 Lead-free piezo-electric porcelain composition, piezo-electric element using the same, and method for producing lead-free piezo-electric porcelain composition
CN108137375A (en) * 2015-10-09 2018-06-08 康宁股份有限公司 The base material and its formation process of glass sensor with through-hole

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
Excellent piezoelectric performance of KNNS-based lead-free piezoelectric ceramics through powder pretreatment by hydrothermal method;Tan, Liumao;《JOURNAL OF ALLOYS AND COMPOUNDS》;20210414;第874卷;第1-9页 *
Improved electrical properties of potassium-sodium niobate piezoceramics owing to micron-sized non-uniform structure;Li, Anjiang等;《JOURNAL OF ALLOYS AND COMPOUNDS》;20210826;第889卷;第1-8页 *
ZnO掺杂对KNN无铅压电陶瓷性能的研究;皇甫熠等;《中小企业管理与科技》;20150815;第253-254页 *
压电陶瓷的Nd∶YAG准脉冲激光打孔研究;郭栋等;《压电与声光》;20020428;第104-106+138页 *
用于压力传感的无铅压电厚膜研究进展;张占文;《材料科学与工程学报》;20180831(第05期);第165-173页 *
聚偏氟乙烯及其共聚物基压电复合材料的研究进展;张小芳等;《复合材料学报》;20201210;第997-1019页 *
铌酸钠钾基无铅压电陶瓷制备技术的比较研究;孙勇等;《功能材料》;20080720;第1067-1070页 *
铌酸钾钠基无铅压电陶瓷的制备及其性能研究;刘奕君;《中国优秀硕士学位论文全文数据库 (工程科技Ⅱ辑)》;20160815;C042-33页 *

Also Published As

Publication number Publication date
CN113105236A (en) 2021-07-13

Similar Documents

Publication Publication Date Title
CN104291817B (en) PZT piezoceramic material of high-curie temperature and preparation method thereof
CN109796205B (en) Bismuth-layer-structured bismuth titanium tantalate high-temperature piezoelectric ceramic material and preparation method thereof
CN103172374B (en) Piezoelectric ceramics and piezoelectric element
CN109437895B (en) Preparation method of lead zirconate titanate-lead magnesium niobate piezoelectric ceramic
CN111087238B (en) Sodium bismuth titanate based leadless piezoelectric ceramic and preparation method thereof
CN113105236B (en) Preparation method of lead-free piezoelectric ceramic based on femtosecond laser processing and lead-free piezoelectric ceramic
KR101333793B1 (en) Bismuth-based piezoelectric ceramics and method of fabricating the same
CN101244930A (en) Low-temperature melt piezoelectric ceramic and preparation technique
CN114455944A (en) Bismuth layer-structured piezoelectric ceramic material and preparation method thereof
CN110372372B (en) Preparation method of sodium bismuth titanate-based lead-free piezoelectric ceramic with low dielectric loss at high temperature
CN111807838B (en) Na (Na) 0.25 K 0.25 Bi 2.5 Nb 2 O 9 Ceramic preparation method and product thereof
CN109320244A (en) A kind of low-temperature melt piezoelectric ceramic material and preparation method thereof
CN103524129B (en) Piezoceramic material for ultrasonic emission-type transducers and preparation method
CN107056281B (en) High-strain sodium bismuth titanate-based ceramic and preparation method thereof
CN115385675B (en) Bismuth ferrite based lead-free ferroelectric ceramic material with high Curie temperature and energy storage characteristic and preparation method thereof
CN101265115A (en) Method for fast sintering Sr1.86Ca0.14NaNb5O15 piezoelectric ceramic by laser
CN103435346B (en) Piezoceramic material for ultrasonic receiver-type transducer
CN103539447B (en) Low-temperature sintered piezoelectric ceramic material and preparation method thereof
CN103435344B (en) Piezoceramic material for high-frequency ceramic filter
CN101239825A (en) Method for increasing Ba0.5Sr1.5Na0.6K0.4Nb5O15 ceramic piezoelectric constant
CN112457008A (en) Large-strain piezoelectric ceramic material and preparation method thereof
CN114736015B (en) Intercalation barium calcium zirconate titanate based lead-free piezoelectric ceramic prepared by adopting vacuum hot-pressing sintering furnace and preparation method thereof
CN113292340B (en) High-piezoelectricity low-loss donor-acceptor co-doped piezoelectric ceramic, and preparation method and application thereof
CN115504783B (en) KNN-based leadless piezoelectric ceramic and preparation method thereof
CN116606143B (en) Piezoelectric ceramic material 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