CN108546124B - Preparation method of BCZT-based lead-free piezoelectric ceramic - Google Patents
Preparation method of BCZT-based lead-free piezoelectric ceramic Download PDFInfo
- Publication number
- CN108546124B CN108546124B CN201810412230.7A CN201810412230A CN108546124B CN 108546124 B CN108546124 B CN 108546124B CN 201810412230 A CN201810412230 A CN 201810412230A CN 108546124 B CN108546124 B CN 108546124B
- Authority
- CN
- China
- Prior art keywords
- powder
- bczt
- nano
- solution
- 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.)
- Active
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000000843 powder Substances 0.000 claims abstract description 51
- 239000006247 magnetic powder Substances 0.000 claims abstract description 50
- 239000011858 nanopowder Substances 0.000 claims abstract description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 24
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 22
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 239000011258 core-shell material Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910001172 neodymium magnet Inorganic materials 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 74
- 238000001035 drying Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 229940044175 cobalt sulfate Drugs 0.000 claims description 9
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 9
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 9
- 238000004939 coking Methods 0.000 claims description 9
- 238000005187 foaming Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000696 magnetic material Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 3
- JXDXDSKXFRTAPA-UHFFFAOYSA-N calcium;barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[Ca+2].[Ti+4].[Ba+2] JXDXDSKXFRTAPA-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 11
- 239000006260 foam Substances 0.000 description 9
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 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 4
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002059 diagnostic imaging Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000004094 surface-active agent Substances 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8536—Alkaline earth metal based oxides, e.g. barium titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/405—Iron group metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of electronic component preparation, in particular to a preparation method of BCZT-based lead-free piezoelectric ceramic. Dissolving citric acid in ethylene glycol, adding butyl titanate diluted by absolute ethyl alcohol to obtain a composite solution, dropwise adding a barium acetate solution, a calcium nitrate solution and a zirconium nitrate solution into the composite solution, uniformly mixing to obtain a BCZT-based polymer precursor, mixing nano NdFeB powder and nano iron powder to obtain magnetic powder slurry, mixing hard magnetic powder and iron/cobalt nano powder with a core-shell structure, performing high-speed dispersion treatment, performing die filling, discharge plasma sintering and demoulding to obtain piezoelectric ceramic and compact cobalt powder particles, can protect iron powder from being oxidized, tetrabutyl titanate and citric acid react to form a network structure, the zirconium high barium calcium titanate-based material does not contain Pb, has little harm to human body and environment, the cobalt simple substance can be slightly softened at high temperature, the binding power of the magnetic material is enhanced, and the heat conductivity coefficient of the magnetic material is reduced, the magnetic material can stably work in a high-temperature environment, and the application prospect is wide.
Description
Technical Field
The invention relates to the technical field of electronic component preparation, in particular to a preparation method of BCZT-based lead-free piezoelectric ceramic.
Background
The piezoelectric ceramic is an information functional ceramic material capable of converting mechanical energy and electric energy into each other. Piezoelectric ceramics have dielectric properties, elasticity, and the like in addition to piezoelectricity, and have been widely used in medical imaging, acoustic sensors, acoustic transducers, ultrasonic motors, and the like.
The piezoelectric ceramic is manufactured by utilizing the piezoelectric effect that the material causes the relative displacement of the centers of positive and negative charges in the material under the action of mechanical stress to generate polarization, so that bound charges with opposite signs appear on the surfaces of two ends of the material, and the piezoelectric ceramic has sensitive characteristics. At present, the piezoelectric ceramics which can be produced by piezoelectric ceramics manufacturers in China mainly comprise binary system and ternary system materials which mainly comprise lead zirconate titanate. Because the Curie temperature of the undoped lead zirconate titanate ceramic material is only 380 ℃ near the morphotropic phase boundary, the Curie temperature of the system can be further reduced after doping with donor and acceptor ions, and the requirement that the temperature of the working environment is higher than 300 ℃ or above is difficult to meet. The piezoelectric ceramic material which can stably work in a high-temperature environment has the following requirements on the performance: 1. has a certain piezoelectric constant at high temperature (d 33>15 pC/N); 2. the high direct current resistivity is realized at high temperature; 3. the electrical properties (dielectric constant and piezoelectric constant) are small in change with temperature, and the temperature stability is good.
Piezoelectric ceramics are metal oxides typically having a perovskite structure, such as lead zirconate titanate (referred to as PZT-based piezoelectric ceramics), but PZT contains lead which affects the environment, and PZT-based piezoelectric ceramics contain Pb in an amount of 60wt.% or more, which can be harmful to human health and the living environment during their preparation, use and disposal. In addition, since piezoelectric ceramic devices are often used under severe conditions, sintered ceramics are required to have excellent weather resistance, particularly excellent moisture resistance.
Therefore, the research and development of the lead-free piezoelectric ceramic with excellent piezoelectric performance and environmental friendliness is an urgent subject with important social significance.
Disclosure of Invention
The invention mainly solves the technical problem that most of the existing piezoelectric ceramics are PZT-based piezoelectric ceramics, the Pb content of the PZT-based piezoelectric ceramics is more than 60 wt%, the PZT-based piezoelectric ceramics can cause harm to human health and living environment in the processes of preparation, use and abandonment, the Curie temperature of the existing undoped lead zirconate titanate ceramic material is only 380 ℃, the Curie temperature of a system can be further reduced after donor and acceptor ions are doped, and the defect that the temperature of a working environment is higher than 300 ℃ and more, and the stable working can not be realized in a high-temperature environment is difficultly met, and the preparation method of the BCZT-based lead-free piezoelectric ceramics is provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of BCZT-based leadless piezoelectric ceramics is characterized by comprising the following specific preparation steps:
(1) dissolving 3-4 parts by weight of citric acid in 10-12 parts by weight of ethylene glycol, heating to raise the temperature to obtain a mixed solution, diluting 0.5-1.0 part by weight of tetrabutyl titanate with 5-7 parts by weight of absolute ethyl alcohol, adding the diluted solution into the mixed solution, stirring and reacting to obtain a composite solution, cooling the composite solution, continuously dropwise adding 13-15 parts by weight of barium acetate solution into the composite solution, stirring and reacting, sequentially adding 3-4 parts by weight of calcium nitrate solution and 0.5-0.8 part by weight of zirconium nitrate solution, and uniformly mixing to obtain a BCZT-based polymer precursor;
(2) placing the BCZT-based polymer precursor into a blast drier, drying to obtain BCZT-based gel, coking the BCZT-based gel in a muffle furnace to obtain black foaming material, grinding the black foaming material, and calcining in the muffle furnace to obtain BCZT-based nano powder;
(3) dispersing 30-35 g of nano iron powder in 100-120 mL of cyclohexane, placing the mixture in an ultrasonic vibrator for ultrasonic treatment, filtering and separating to obtain ultrasonic treated iron powder, dispersing the ultrasonic treated iron powder in a beaker filled with 120-150 mL of cobalt sulfate solution, adding 60-80 mL of sodium borohydride solution into the beaker, stirring and dispersing by using a magnetic stirrer until no bubble is generated, filtering and separating to obtain wet powder, and placing the wet powder in an oven for drying to obtain iron/cobalt nano powder with a core-shell structure;
(4) mixing nano NdFeB powder and nano iron powder to obtain 200-300 g of mixed magnetic powder, adding the prepared mixed magnetic powder, 35-40 mL of oleic acid and 30-35 mL of cyclohexane into a planetary ball mill, and performing ball milling to obtain magnetic powder slurry;
(5) cleaning the magnetic powder slurry in an ultrasonic cleaning machine, transferring the magnetic powder slurry to a high-speed centrifuge for centrifugal treatment, removing supernatant to obtain lower layer powder, and drying the lower layer powder in a vacuum drying oven to obtain hard magnetic powder;
(6) mixing hard magnetic powder, iron/cobalt nano powder with a core-shell structure and BCZT-based nano powder, placing the mixture in a high-speed dispersion machine for high-speed dispersion to obtain nano piezoelectric ceramic powder, pouring 200-250 g of the nano piezoelectric ceramic powder into a carbon mold, placing the carbon mold into a discharge plasma instrument, vacuumizing and pressurizing, discharging, heating to raise the temperature, preserving the temperature, naturally cooling to room temperature, and demolding to obtain the BCZT-based lead-free piezoelectric ceramic.
Heating and raising the temperature to 80-90 ℃ in the step (1), stirring and reacting for 2.0-2.5 h, cooling the composite liquid to 40-50 ℃, adding a barium acetate solution, stirring and reacting for 1.0-1.5 h, wherein the mass fraction of the calcium nitrate solution is 10% and the mass fraction of the zirconium nitrate solution is 20%.
Setting the temperature of the blast dryer in the step (2) to be 100-120 ℃, drying for 7-8 hours, coking at the muffle furnace temperature of 450-500 ℃ for 4-5 hours, grinding the black foaming material to the particle size of 20-25 mu m, calcining at the temperature of 600-800 ℃ for 2-3 hours.
And (3) carrying out ultrasonic treatment at the frequency of 30-32 kHz for 15-20 min, wherein the mass fraction of the cobalt sulfate solution is 5%, the mass fraction of the sodium borohydride solution is 20%, the set temperature of the oven is 60-70 ℃, and the drying time is 20-24 h.
And (3) mixing the nano NdFeB powder and the nano iron powder in the step (4) according to a mass ratio of 2: 1, controlling the ball-material mass ratio to be 15: 1, and performing ball milling at a ball milling speed of 380-420 r/min for 3-4 h.
And (5) carrying out ultrasonic cleaning at the frequency of 30-35 kHz, for 10-15 min, at the centrifugal rotation speed of 7000-8000 r/min for 18-20 min, at the set temperature of 80-90 ℃ in a vacuum drying oven for 4-5 h.
And (3) mixing the hard magnetic powder, the iron/cobalt nano powder with the core-shell structure and the BCZT-based nano powder at a mass ratio of 1: 5, a high-speed dispersion rotating speed of 3000-4000 r/min, a high-speed dispersion time of 10-12 min, a pressurization pressure of 50-60 MPa, a temperature of 1260-1300 ℃ after discharge heating, and a heat preservation time of 40-50 min.
The invention has the beneficial effects that:
(1) dissolving citric acid in ethylene glycol, heating, adding butyl titanate diluted by absolute ethyl alcohol to obtain a composite solution, dropwise adding a barium acetate solution, a calcium nitrate solution and a zirconium nitrate solution into the composite solution, uniformly mixing to obtain a BCZT-based polymer precursor, performing forced air drying, coking and calcining on the BCZT-based polymer precursor to obtain BCZT-based nano powder, dispersing nano iron powder in cyclohexane, performing ultrasonic treatment, adding a sodium borohydride solution, stirring, filtering and drying to obtain iron/cobalt nano powder with a core-shell structure, mixing nano NdFeB powder and nano iron powder according to a certain mass ratio, adding a dispersion medium and a surface active substance, performing ball milling by using a cleaning agent to obtain magnetic powder slurry, cleaning the magnetic powder slurry in ultrasonic waves, performing high-speed centrifugation and drying to obtain hard magnetic powder, mixing the hard magnetic powder with the iron/cobalt nano powder with the core-shell structure, and performing high-speed dispersion treatment, the invention separates out cobalt on the surface of iron powder under the reducing action of sodium borohydride by cobalt sulfate solution to form compact cobalt powder particles to obtain iron/cobalt nano powder with a core-shell structure, the cobalt simple substance has low reaction activity relative to the iron simple substance and oxygen under the high-temperature working condition, the cobalt powder on the surface is not easy to be oxidized and corroded, and the iron powder can be protected from being oxidized, the piezoelectric ceramic is put into a carbon mould and sintered by discharge plasma, inorganic elements and metal elements on the surface of the piezoelectric ceramic are uniformly electrified in the material in the moist environment, positive and negative charges are dispersed at two ends in the working process of the piezoelectric ceramic, electric energy can be dissipated by changing a micro magnetic field in the piezoelectric ceramic, the direct current resistivity of the piezoelectric ceramic under high temperature is improved, and the piezoelectric ceramic can keep a relatively stable current state under high voltage, the influence of high-temperature environment change caused by high-voltage current is small;
(2) the invention forms a network structure with the passage of time by the complexation reaction of tetrabutyl titanate and citric acid, and adds barium acetate solution, calcium nitrate solution and zirconium nitrate solution to form zirconium high barium calcium titanate-based material, compared with PZT-based piezoelectric ceramics, the zirconium high barium calcium titanate-based material does not contain Pb and has little harm to human body and environment, the doped magnetic material takes hard magnetic powder as hard magnetic phase, iron/cobalt nano powder with a core-shell structure as soft magnetic phase, the cobalt nano powder is arranged at the combination of soft and hard phases, the cobalt simple substance can be slightly softened at high temperature, the cohesive force of the magnetic material is enhanced, the heat conductivity coefficient of the magnetic material is reduced, the thermal shock resistance of the magnetic material is improved, the expansion coefficient of NdFeB powder is smaller under the high-temperature working condition, the filling density is improved on the contrary under the expansion and extrusion of other materials, the saturation magnetic flux density of the magnetic material is improved, and the Curie temperature of the piezoelectric ceramics is improved, can stably work in a high-temperature environment and has wide application prospect.
Detailed Description
Dissolving 3-4 parts by weight of citric acid in 10-12 parts by weight of ethylene glycol, heating to 80-90 ℃ to obtain a mixed solution, diluting 0.5-1.0 part by weight of tetrabutyl titanate with 5-7 parts by weight of absolute ethyl alcohol, adding the diluted solution into the mixed solution, stirring and reacting for 2.0-2.5 hours to obtain a composite solution, cooling the composite solution to 40-50 ℃, continuously dropwise adding 13-15 parts by weight of a 25% barium acetate solution into the composite solution, stirring and reacting for 1.0-1.5 hours, sequentially adding 3-4 parts by weight of a 10% calcium nitrate solution and 0.5-0.8 part by weight of a 20% zirconium nitrate solution, and uniformly mixing to obtain a BCZT-based polymer precursor; placing the BCZT-based polymer precursor in a blast dryer with the set temperature of 100-120 ℃, drying for 7-8 hours to obtain BCZT-based gel, coking the BCZT-based gel in a muffle furnace with the temperature of 450-500 ℃ for 4-5 hours to obtain black foam, grinding the black foam to the granularity of 20-25 microns, placing the black foam in the muffle furnace, and calcining at the temperature of 600-800 ℃ for 2-3 hours to obtain BCZT-based nano powder; dispersing 30-35 g of nano iron powder in 100-120 mL of cyclohexane, placing the mixture in an ultrasonic oscillator for ultrasonic treatment for 15-20 min at the frequency of 30-32 kHz, filtering and separating to obtain ultrasonic treated iron powder, dispersing the ultrasonic treated iron powder in a beaker filled with 120-150 mL of a 5% cobalt sulfate solution, adding 60-80 mL of a 20% sodium borohydride solution into the beaker, stirring and dispersing the mixture by using a magnetic stirrer at the rotating speed of 700-800 r/min until no bubbles are generated, filtering and separating to obtain wet powder, placing the wet powder in an oven with the set temperature of 60-70 ℃, and drying the wet powder for 20-24 h to obtain iron/cobalt nano powder with a core-shell structure; mixing nano NdFeB powder and nano iron powder according to the mass ratio of 2: 1 to obtain 200-300 g of mixed magnetic powder, adding the prepared mixed magnetic powder, 35-40 mL of oleic acid and 30-35 mL of cyclohexane into a planetary ball mill, controlling the mass ratio of balls to materials to be 15: 1, controlling the ball milling speed to be 380-420 r/min, and performing ball milling for 3-4 hours to obtain magnetic powder slurry; putting the magnetic powder slurry into an ultrasonic cleaning machine, cleaning for 10-15 min at the frequency of 30-35 kHz, transferring the magnetic powder slurry into a high-speed centrifuge, centrifuging for 18-20 min at the rotating speed of 7000-8000 r/min, removing supernatant to obtain lower layer powder, putting the lower layer powder into a vacuum drying oven with the set temperature of 80-90 ℃, and drying for 4-5 h to obtain hard magnetic powder; mixing hard magnetic powder, iron/cobalt nano powder with a core-shell structure and BCZT-based nano powder according to the mass ratio of 1: 5, placing the mixture in a high-speed dispersion machine, dispersing the mixture at a high speed of 3000-4000 r/min for 10-12 min to obtain nano piezoelectric ceramic powder, pouring 200-250 g of the nano piezoelectric ceramic powder into a carbon mold, placing the carbon mold into a discharge plasma instrument, vacuumizing, pressurizing to 50-60 MPa, heating to 1260-1300 ℃ through discharge heating, preserving heat for 40-50 min, naturally cooling to room temperature, and demolding to obtain the BCZT-based lead-free piezoelectric ceramic.
Dissolving 3 parts by weight of citric acid in 10 parts by weight of ethylene glycol, heating to 80 ℃ to obtain a mixed solution, diluting 0.5 part by weight of tetrabutyl titanate with 5 parts by weight of absolute ethyl alcohol, adding the diluted solution into the mixed solution, stirring and reacting for 2.0 hours to obtain a composite solution, continuing to dropwise add 13 parts by weight of a 25% barium acetate solution into the composite solution when the composite solution is cooled to 40 ℃, stirring and reacting for 1.0 hour, sequentially adding 3 parts by weight of a 10% calcium nitrate solution and 0.5 part by weight of a 20% zirconium nitrate solution, and uniformly mixing to obtain a BCZT-based polymer precursor; placing the BCZT-based polymer precursor in a blast dryer with the set temperature of 100 ℃, drying for 7h to obtain BCZT-based gel, carrying out coking treatment on the BCZT-based gel in a muffle furnace with the temperature of 450 ℃ for 4h to obtain black foam, grinding the black foam to the granularity of 20 mu m, placing the black foam in the muffle furnace, and calcining for 2h at the temperature of 600 ℃ to obtain BCZT-based nano powder; dispersing 30g of nano iron powder in 100mL of cyclohexane, placing the mixture in an ultrasonic oscillator to perform ultrasonic treatment for 15min at the frequency of 30kHz, filtering and separating to obtain ultrasonic treated iron powder, dispersing the ultrasonic treated iron powder in a beaker filled with 120mL of a 5% cobalt sulfate solution, adding 60mL of a 20% sodium borohydride solution into the beaker, stirring and dispersing the mixture by using a magnetic stirrer at the rotating speed of 700r/min until no bubbles are generated, filtering and separating to obtain wet powder, placing the wet powder in an oven at the set temperature of 60 ℃, and drying the wet powder for 20h to obtain iron/cobalt nano powder with a core-shell structure; mixing nano NdFeB powder and nano iron powder according to the mass ratio of 2: 1 to obtain 200g of mixed magnetic powder, adding the prepared mixed magnetic powder, 35mL of oleic acid and 30mL of cyclohexane into a planetary ball mill, controlling the mass ratio of ball materials to be 15: 1, the ball milling speed to be 380r/min, and performing ball milling for 3 hours to obtain magnetic powder slurry; putting the magnetic powder slurry into an ultrasonic cleaning machine, cleaning for 10min at the frequency of 30kHz, transferring the magnetic powder slurry into a high-speed centrifuge, centrifuging for 18min at the rotating speed of 7000r/min, removing the supernatant to obtain lower-layer powder, putting the lower-layer powder into a vacuum drying oven with the set temperature of 80 ℃, and drying for 4h to obtain hard magnetic powder; mixing hard magnetic powder, iron/cobalt nano powder with a core-shell structure and BCZT-based nano powder according to the mass ratio of 1: 5, placing the mixture in a high-speed dispersion machine, dispersing the mixture at a high speed of 3000r/min for 10min to obtain nano piezoelectric ceramic powder, pouring 200g of the nano piezoelectric ceramic powder into a carbon mold, placing the carbon mold into a discharge plasma instrument, vacuumizing, pressurizing to 50MPa, heating to 1260 ℃ by discharge, preserving the temperature for 40min, naturally cooling to room temperature, and demolding to obtain the BCZT-based lead-free piezoelectric ceramic.
Dissolving 3 parts by weight of citric acid in 11 parts by weight of ethylene glycol, heating to 85 ℃ to obtain a mixed solution, diluting 0.7 part by weight of tetrabutyl titanate with 6 parts by weight of absolute ethyl alcohol, adding the diluted solution into the mixed solution, stirring and reacting for 2.3 hours to obtain a composite solution, continuing to dropwise add 14 parts by weight of a 25% barium acetate solution into the composite solution when the composite solution is cooled to 45 ℃, stirring and reacting for 1.3 hours, sequentially adding 3 parts by weight of a 10% calcium nitrate solution and 0.7 part by weight of a 20% zirconium nitrate solution, and uniformly mixing to obtain a BCZT-based polymer precursor; placing the BCZT-based polymer precursor into a blast dryer with the set temperature of 110 ℃, drying for 7.5h to obtain BCZT-based gel, carrying out coking treatment on the BCZT-based gel in a muffle furnace with the temperature of 475 ℃ for 4.5h to obtain black foaming matter, grinding the black foaming matter to the granularity of 23 mu m, placing the black foaming matter into the muffle furnace, and calcining for 2.3h at the temperature of 700 ℃ to obtain BCZT-based nano powder; dispersing 33g of nano iron powder in 110mL of cyclohexane, placing the mixture in an ultrasonic oscillator to perform ultrasonic treatment at the frequency of 31kHz for 18min, filtering and separating to obtain ultrasonic treated iron powder, dispersing the ultrasonic treated iron powder in a beaker filled with 135mL of a 5% cobalt sulfate solution, adding 70mL of a 20% sodium borohydride solution into the beaker, stirring and dispersing the mixture by using a magnetic stirrer at the rotating speed of 750r/min until no bubbles are generated, filtering and separating to obtain wet powder, placing the wet powder in an oven with the set temperature of 65 ℃, and drying the wet powder for 22h to obtain iron/cobalt nano powder with a core-shell structure; mixing nano NdFeB powder and nano iron powder according to the mass ratio of 2: 1 to obtain 250g of mixed magnetic powder, adding the prepared mixed magnetic powder, 38mL of oleic acid and 33mL of cyclohexane into a planetary ball mill, controlling the mass ratio of ball materials to be 15: 1, the ball milling speed to be 400r/min, and performing ball milling for 3.5 hours to obtain magnetic powder slurry; putting the magnetic powder slurry into an ultrasonic cleaning machine, cleaning for 13min at the frequency of 33kHz, transferring to a high-speed centrifuge, centrifuging for 19min at the rotating speed of 7500r/min, removing the supernatant to obtain lower-layer powder, putting the lower-layer powder into a vacuum drying oven with the set temperature of 85 ℃, and drying for 4.5h to obtain hard magnetic powder; mixing hard magnetic powder, iron/cobalt nano powder with a core-shell structure and BCZT-based nano powder according to the mass ratio of 1: 5, placing the mixture in a high-speed dispersion machine, dispersing the mixture at a high speed of 3500r/min for 11min to obtain nano piezoelectric ceramic powder, pouring 225g of the nano piezoelectric ceramic powder into a carbon mold, placing the carbon mold into a discharge plasma instrument, vacuumizing, pressurizing to 55MPa, heating to 1280 ℃ by discharge, preserving the temperature for 45min, naturally cooling to room temperature, and demolding to obtain the BCZT-based lead-free piezoelectric ceramic.
Dissolving 4 parts by weight of citric acid in 12 parts by weight of ethylene glycol, heating to 90 ℃ to obtain a mixed solution, diluting 1.0 part by weight of tetrabutyl titanate with 7 parts by weight of absolute ethyl alcohol, adding the diluted solution into the mixed solution, stirring and reacting for 2.5 hours to obtain a composite solution, continuing to dropwise add 15 parts by weight of a 25% barium acetate solution into the composite solution when the composite solution is cooled to 50 ℃, stirring and reacting for 1.5 hours, sequentially adding 4 parts by weight of a 10% calcium nitrate solution and 0.8 part by weight of a 20% zirconium nitrate solution, and uniformly mixing to obtain a BCZT-based polymer precursor; placing the BCZT-based polymer precursor in a blast dryer with the set temperature of 120 ℃, drying for 8h to obtain BCZT-based gel, carrying out coking treatment on the BCZT-based gel in a muffle furnace with the temperature of 500 ℃ for 5h to obtain black foam, grinding the black foam to the granularity of 25 mu m, placing the black foam in the muffle furnace, and calcining for 3h at the temperature of 800 ℃ to obtain BCZT-based nano powder; dispersing 35g of nano iron powder in 120mL of cyclohexane, placing the mixture in an ultrasonic oscillator to perform ultrasonic treatment at the frequency of 32kHz for 20min, filtering and separating to obtain ultrasonic-treated iron powder, dispersing the ultrasonic-treated iron powder in a beaker filled with 150mL of a 5% cobalt sulfate solution, adding 80mL of a 20% sodium borohydride solution into the beaker, stirring and dispersing the mixture by using a magnetic stirrer at the rotating speed of 700-800 r/min until no bubbles are generated, filtering and separating to obtain wet powder, placing the wet powder in an oven with the set temperature of 70 ℃, and drying the wet powder for 24h to obtain the iron/cobalt nano powder with the core-shell structure; mixing nano NdFeB powder and nano iron powder according to the mass ratio of 2: 1 to obtain 300g of mixed magnetic powder, adding the prepared mixed magnetic powder, 40mL of oleic acid and 35mL of cyclohexane into a planetary ball mill, controlling the mass ratio of ball materials to be 15: 1, the ball milling speed to be 420r/min, and performing ball milling for 4 hours to obtain magnetic powder slurry; putting the magnetic powder slurry into an ultrasonic cleaning machine, cleaning for 15min at the frequency of 35kHz, transferring the magnetic powder slurry into a high-speed centrifuge, centrifuging for 20min at the rotating speed of 8000r/min, removing the supernatant to obtain lower-layer powder, putting the lower-layer powder into a vacuum drying oven with the set temperature of 90 ℃, and drying for 5h to obtain hard magnetic powder; mixing hard magnetic powder, iron/cobalt nano powder with a core-shell structure and BCZT-based nano powder according to the mass ratio of 1: 5, placing the mixture in a high-speed dispersion machine, dispersing the mixture at a high speed of 4000r/min for 12min to obtain nano piezoelectric ceramic powder, pouring 250g of the nano piezoelectric ceramic powder into a carbon mold, placing the carbon mold into a discharge plasma instrument, vacuumizing, pressurizing to 60MPa, heating to 1300 ℃ by discharge, preserving the temperature for 50min, naturally cooling to room temperature, and demolding to obtain the BCZT-based lead-free piezoelectric ceramic.
Comparative example piezoelectric ceramics produced by a company of Zhaoqing City was used as a comparative example
The BCZT-based lead-free piezoelectric ceramic prepared by the invention and the piezoelectric ceramic in the comparative example are detected, and the detection results are shown in Table 1:
the electromechanical coupling coefficient Kp, the mechanical quality factor Qm, the dielectric loss tg δ, and the relative dielectric constant were measured in accordance with the requirements in GB/T2414.1.
The Curie temperature Tc was tested in accordance with the relevant requirements in GB/T3389.3.
TABLE 1 measurement results of Properties
As can be seen from the data in Table 1, the BCZT-based lead-free piezoelectric ceramic prepared by the invention has the advantages of excellent piezoelectric property, high-temperature aging resistance, high sensitivity, long service life, simple preparation method steps, easily obtained raw materials and obvious superiority to comparative products. Therefore, the method has wide application prospect.
Claims (7)
1. A preparation method of BCZT-based leadless piezoelectric ceramics is characterized by comprising the following specific preparation steps:
(1) dissolving 3-4 parts by weight of citric acid in 10-12 parts by weight of ethylene glycol, heating to raise the temperature to obtain a mixed solution, diluting 0.5-1.0 part by weight of tetrabutyl titanate with 5-7 parts by weight of absolute ethyl alcohol, adding the diluted solution into the mixed solution, stirring and reacting to obtain a composite solution, cooling the composite solution, continuously dropwise adding 13-15 parts by weight of barium acetate solution into the composite solution, stirring and reacting, sequentially adding 3-4 parts by weight of calcium nitrate solution and 0.5-0.8 part by weight of zirconium nitrate solution, and uniformly mixing to obtain a BCZT-based polymer precursor;
(2) placing the BCZT-based polymer precursor into a blast drier, drying to obtain BCZT-based gel, coking the BCZT-based gel in a muffle furnace to obtain black foaming material, grinding the black foaming material, and calcining in the muffle furnace to obtain BCZT-based nano powder;
(3) dispersing 30-35 g of nano iron powder in 100-120 mL of cyclohexane, placing the mixture in an ultrasonic vibrator for ultrasonic treatment, filtering and separating to obtain ultrasonic treated iron powder, dispersing the ultrasonic treated iron powder in a beaker filled with 120-150 mL of cobalt sulfate solution, adding 60-80 mL of sodium borohydride solution into the beaker, stirring and dispersing by using a magnetic stirrer until no bubble is generated, filtering and separating to obtain wet powder, and placing the wet powder in an oven for drying to obtain iron/cobalt nano powder with a core-shell structure;
(4) mixing nano NdFeB powder and nano iron powder to obtain 200-300 g of mixed magnetic powder, adding the prepared mixed magnetic powder, 35-40 mL of oleic acid and 30-35 mL of cyclohexane into a planetary ball mill, and performing ball milling to obtain magnetic powder slurry;
(5) cleaning the magnetic powder slurry in an ultrasonic cleaning machine, transferring the magnetic powder slurry to a high-speed centrifuge for centrifugal treatment, removing supernatant to obtain lower layer powder, and drying the lower layer powder in a vacuum drying oven to obtain hard magnetic powder;
(6) mixing hard magnetic powder, iron/cobalt nano powder with a core-shell structure and BCZT-based nano powder, placing the mixture in a high-speed dispersion machine for high-speed dispersion to obtain nano piezoelectric ceramic powder, pouring 200-250 g of the nano piezoelectric ceramic powder into a carbon mold, placing the carbon mold into a discharge plasma instrument, vacuumizing and pressurizing, discharging, heating to raise the temperature, preserving the temperature, naturally cooling to room temperature, and demolding to obtain the BCZT-based lead-free piezoelectric ceramic.
2. The method for preparing a BCZT-based lead-free piezoelectric ceramic according to claim 1, wherein: heating and raising the temperature to 80-90 ℃ in the step (1), stirring and reacting for 2.0-2.5 h, cooling the composite liquid to 40-50 ℃, adding a barium acetate solution, stirring and reacting for 1.0-1.5 h, wherein the mass fraction of the calcium nitrate solution is 10% and the mass fraction of the zirconium nitrate solution is 20%.
3. The method for preparing a BCZT-based lead-free piezoelectric ceramic according to claim 1, wherein: setting the temperature of the blast dryer in the step (2) to be 100-120 ℃, drying for 7-8 hours, coking at the muffle furnace temperature of 450-500 ℃ for 4-5 hours, grinding the black foaming material to the particle size of 20-25 mu m, calcining at the temperature of 600-800 ℃ for 2-3 hours.
4. The method for preparing a BCZT-based lead-free piezoelectric ceramic according to claim 1, wherein: and (3) carrying out ultrasonic treatment at the frequency of 30-32 kHz for 15-20 min, wherein the mass fraction of the cobalt sulfate solution is 5%, the mass fraction of the sodium borohydride solution is 20%, the set temperature of the oven is 60-70 ℃, and the drying time is 20-24 h.
5. The method for preparing a BCZT-based lead-free piezoelectric ceramic according to claim 1, wherein: and (3) mixing the nano NdFeB powder and the nano iron powder in the step (4) according to a mass ratio of 2: 1, controlling the ball-material mass ratio to be 15: 1, and performing ball milling at a ball milling speed of 380-420 r/min for 3-4 h.
6. The method for preparing a BCZT-based lead-free piezoelectric ceramic according to claim 1, wherein: and (5) carrying out ultrasonic cleaning at the frequency of 30-35 kHz, for 10-15 min, at the centrifugal rotation speed of 7000-8000 r/min for 18-20 min, at the set temperature of 80-90 ℃ in a vacuum drying oven for 4-5 h.
7. The method for preparing a BCZT-based lead-free piezoelectric ceramic according to claim 1, wherein: and (3) mixing the hard magnetic powder, the iron/cobalt nano powder with the core-shell structure and the BCZT-based nano powder at a mass ratio of 1: 5, a high-speed dispersion rotating speed of 3000-4000 r/min, a high-speed dispersion time of 10-12 min, a pressurization pressure of 50-60 MPa, a temperature of 1260-1300 ℃ after discharge heating, and a heat preservation time of 40-50 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810412230.7A CN108546124B (en) | 2018-05-03 | 2018-05-03 | Preparation method of BCZT-based lead-free piezoelectric ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810412230.7A CN108546124B (en) | 2018-05-03 | 2018-05-03 | Preparation method of BCZT-based lead-free piezoelectric ceramic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108546124A CN108546124A (en) | 2018-09-18 |
| CN108546124B true CN108546124B (en) | 2021-07-30 |
Family
ID=63513315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810412230.7A Active CN108546124B (en) | 2018-05-03 | 2018-05-03 | Preparation method of BCZT-based lead-free piezoelectric ceramic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108546124B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041069B (en) * | 2019-05-31 | 2021-11-30 | 河南科技大学 | Microwave dielectric ceramic material and preparation method thereof |
| CN110803923B (en) * | 2019-11-14 | 2022-04-05 | 陕西师范大学 | Preparation method of titanium dioxide-based ceramic with high resistivity, giant dielectric constant and low loss in reducing atmosphere |
| CN113979744B (en) * | 2021-10-26 | 2022-10-18 | 西南科技大学 | Magnesium-calcium-titanium microwave dielectric ceramic powder and preparation method and application thereof |
| CN115650722B (en) * | 2022-05-09 | 2023-06-27 | 西南科技大学 | Gel and application thereof in circulator composite substrate |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6969287B1 (en) * | 2001-07-05 | 2005-11-29 | Motsenbocker Marvin A | Electronic shut off systems |
| WO2009058759A3 (en) * | 2007-10-29 | 2009-08-06 | Humdinger Wind Energy Llc | Energy converter with transducers for converting fluid-induced movements or stress to electricity |
| CN101913867A (en) * | 2010-07-15 | 2010-12-15 | 上海大学 | Low-frequency multiferroic particle magnetic-electric composite material and preparation method thereof |
| CN102000816A (en) * | 2010-10-27 | 2011-04-06 | 华南理工大学 | Exchange coupling dual-phase nano composite permanent magnet particles and preparation method thereof |
| CN105884350A (en) * | 2016-04-08 | 2016-08-24 | 江苏大学 | Barium calcium zirconate titanate leadless piezoelectric ceramic material and preparation method thereof |
| CN106128668A (en) * | 2016-08-15 | 2016-11-16 | 深圳市威富多媒体有限公司 | A kind of preparation method of Nanocomposite rare earth permanent-magnetic material |
| CN106478095A (en) * | 2016-09-28 | 2017-03-08 | 陕西科技大学 | Ba0.9Ca0.1Ti0.9Zr0.1O3/CoFe2O4Layered electromagnetic composite and preparation method thereof |
| CN106986634A (en) * | 2017-04-28 | 2017-07-28 | 信阳师范学院 | A kind of calcium barium zirconate titanate base piezoceramics and preparation method thereof |
| CN107189286A (en) * | 2016-03-14 | 2017-09-22 | 深圳先进技术研究院 | A kind of oxidation resistant hybrid particulates and its polymer matrix composite |
| CN107382309A (en) * | 2017-08-03 | 2017-11-24 | 中南大学 | A kind of unleaded Bi0.5Na0.5TiO3Base magnetoelectric ceramic and preparation method thereof |
| CN107488839A (en) * | 2017-08-23 | 2017-12-19 | 河北工业大学 | (Fe‑Co)‑BaTiO3The preparation method of core pipe complex phase multi-iron material |
| CN107867856A (en) * | 2016-09-27 | 2018-04-03 | 青岛东浩软件科技有限公司 | A kind of high tension performance ceramic material and preparation method thereof |
-
2018
- 2018-05-03 CN CN201810412230.7A patent/CN108546124B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6969287B1 (en) * | 2001-07-05 | 2005-11-29 | Motsenbocker Marvin A | Electronic shut off systems |
| WO2009058759A3 (en) * | 2007-10-29 | 2009-08-06 | Humdinger Wind Energy Llc | Energy converter with transducers for converting fluid-induced movements or stress to electricity |
| CN101913867A (en) * | 2010-07-15 | 2010-12-15 | 上海大学 | Low-frequency multiferroic particle magnetic-electric composite material and preparation method thereof |
| CN102000816A (en) * | 2010-10-27 | 2011-04-06 | 华南理工大学 | Exchange coupling dual-phase nano composite permanent magnet particles and preparation method thereof |
| CN107189286A (en) * | 2016-03-14 | 2017-09-22 | 深圳先进技术研究院 | A kind of oxidation resistant hybrid particulates and its polymer matrix composite |
| CN105884350A (en) * | 2016-04-08 | 2016-08-24 | 江苏大学 | Barium calcium zirconate titanate leadless piezoelectric ceramic material and preparation method thereof |
| CN106128668A (en) * | 2016-08-15 | 2016-11-16 | 深圳市威富多媒体有限公司 | A kind of preparation method of Nanocomposite rare earth permanent-magnetic material |
| CN107867856A (en) * | 2016-09-27 | 2018-04-03 | 青岛东浩软件科技有限公司 | A kind of high tension performance ceramic material and preparation method thereof |
| CN106478095A (en) * | 2016-09-28 | 2017-03-08 | 陕西科技大学 | Ba0.9Ca0.1Ti0.9Zr0.1O3/CoFe2O4Layered electromagnetic composite and preparation method thereof |
| CN106986634A (en) * | 2017-04-28 | 2017-07-28 | 信阳师范学院 | A kind of calcium barium zirconate titanate base piezoceramics and preparation method thereof |
| CN107382309A (en) * | 2017-08-03 | 2017-11-24 | 中南大学 | A kind of unleaded Bi0.5Na0.5TiO3Base magnetoelectric ceramic and preparation method thereof |
| CN107488839A (en) * | 2017-08-23 | 2017-12-19 | 河北工业大学 | (Fe‑Co)‑BaTiO3The preparation method of core pipe complex phase multi-iron material |
Non-Patent Citations (2)
| Title |
|---|
| magneto-electric properties of in-situ prepared xCoFe(2)O(4)-(1-x)(Ba-0.Ca-85(0.15)))(Zr0.1Ti0.9)0-3 particulate composites;Reddy,MV;《CERAMICS INTERNATIONAL》;20161115(第42期);17827-17833 * |
| 复合型多铁薄膜制备及性能研究;邓洋琴;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20180315;B020-409 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108546124A (en) | 2018-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108546124B (en) | Preparation method of BCZT-based lead-free piezoelectric ceramic | |
| CN113698204B (en) | Potassium-sodium niobate-based lead-free piezoelectric textured ceramic with high piezoelectric response and high Curie temperature and preparation method thereof | |
| CN108046789B (en) | Preparation method of electromagnetic shielding composite material | |
| CN112225186B (en) | Preparation method of spherical boron nitride | |
| JP2021011421A (en) | Preparation method of low loss garnet ferrite material | |
| CN101648807A (en) | Calcium barium zirconate titanate base piezoceramics and preparation method thereof | |
| Xu et al. | Piezoelectric properties of a pioneering 3‐1 type PZT/epoxy composites based on freeze‐casting processing | |
| CN102299254B (en) | Method for preparing large-size thick-film piezoelectric composite material by using casting method | |
| CN112174663A (en) | High-performance piezoelectric ceramic and preparation method thereof | |
| CN110615956A (en) | Preparation method of nano sandwich structure composite material based on high breakdown and high energy storage | |
| JPH07297461A (en) | Piezoelectric ceramics-polymer composite material and its manufacture | |
| CN112063085A (en) | Composite flexible high-dielectric film and preparation method and application thereof | |
| CN114436654B (en) | Relaxor ferroelectric lead-based ceramic material with high phase transition temperature, excellent fatigue resistance and high electromechanical performance, and preparation method and application thereof | |
| CN115093211A (en) | Bismuth ferrite-strontium titanate-based ceramic material with high energy storage and high breakdown and preparation method thereof | |
| Jiang et al. | Preparation of high performance AlN/Hydantion composite by gelcasting and infiltration processes | |
| CN101215168A (en) | Doping modifying method for lead magnesio-tantalate lead zirconate lead titanate | |
| Wang et al. | Preparation technology of 3–3 composite piezoelectric material and its influence on performance | |
| CN116283251B (en) | Alumina ceramic and preparation method and application thereof | |
| CN100530737C (en) | A high-frequency 3-3 compound piezoelectricity porcelain component | |
| CN113149640B (en) | Preparation method of high-temperature high-energy efficient vehicle inverter capacitor core material | |
| CN114292102A (en) | Bismuth ferrite-barium titanate-based lead-free piezoelectric ceramic material and preparation method thereof | |
| CN113735569A (en) | Preparation method of magnesium oxide and boron nitride composite microspheres | |
| TW572866B (en) | Centrifugal sintering method and use thereof | |
| CN111620611A (en) | Carbon-synergistic lead-free cement-based piezoelectric composite material and preparation method and application thereof | |
| CN118324526B (en) | High-dielectric low-loss 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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210707 Address after: 333000 in Jinghua Industrial Park, Chaoyang East Road, Zhushan District, Jingdezhen City, Jiangxi Province Applicant after: SAVACON ELECTRONICS Co.,Ltd. Address before: 528000 No.7, xiaowugang garden ceramics factory, Shiwan, Chancheng District, Foshan City, Guangdong Province (room 111-1, first floor) Applicant before: FOSHAN JIUMO TECHNOLOGY INFORMATION CONSULTING Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |