CN116253563A - [111] oriented barium calcium titanate leadless piezoelectric textured ceramic and preparation method thereof - Google Patents
[111] oriented barium calcium titanate leadless piezoelectric textured ceramic and preparation method thereof Download PDFInfo
- Publication number
- CN116253563A CN116253563A CN202310130880.3A CN202310130880A CN116253563A CN 116253563 A CN116253563 A CN 116253563A CN 202310130880 A CN202310130880 A CN 202310130880A CN 116253563 A CN116253563 A CN 116253563A
- Authority
- CN
- China
- Prior art keywords
- calcium titanate
- template
- barium calcium
- oriented
- preparation
- 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.)
- Granted
Links
- 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 title claims abstract description 66
- 239000000919 ceramic Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 58
- 238000000498 ball milling Methods 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- 238000005266 casting Methods 0.000 claims abstract description 21
- 239000003292 glue Substances 0.000 claims abstract description 19
- 238000000462 isostatic pressing Methods 0.000 claims abstract description 18
- 239000011268 mixed slurry Substances 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000007599 discharging Methods 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- 241000276425 Xiphophorus maculatus Species 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 52
- 239000002994 raw material Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000004321 preservation Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 238000009694 cold isostatic pressing Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000007731 hot pressing Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 230000010287 polarization Effects 0.000 claims description 11
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000010030 laminating Methods 0.000 abstract description 7
- 229910002113 barium titanate Inorganic materials 0.000 abstract 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 229910001961 silver nitrate Inorganic materials 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000001514 detection method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- CASOXAYOCHCWQU-UHFFFAOYSA-N butan-2-one;ethanol Chemical compound CCO.CCC(C)=O CASOXAYOCHCWQU-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- LJQKCYFTNDAAPC-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O LJQKCYFTNDAAPC-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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
- C04B35/46—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
-
- 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
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5116—Ag or Au
-
- 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
- C04B41/88—Metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
- C04B2235/3234—Titanates, not containing zirconia
- C04B2235/3236—Alkaline earth 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
- C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The invention discloses a [111]]The preparation method of the oriented barium calcium titanate leadless piezoelectric textured ceramic comprises the following steps: preparation [111]]Oriented flake BaTiO 3 A template; preparing barium calcium titanate matrix powder; mixing and ball milling barium calcium titanate matrix powder, a platy template, an organic solvent, a binder, a dispersing agent and a plasticizer to prepare mixed slurry; wherein the organic solvent, the binder, the dispersant, the plasticizer and the flaky template respectively occupy the total mass of the matrix powder50 to 70 percent of the weight, 3.2 to 10 percent of the weight, 1.5 to 4.5 percent of the weight, and 2 to 30 percent of the weight; casting, laminating cut pieces, discharging glue, isostatic pressing, sintering, silver coating and polarizing the mixed slurry to obtain [111]]Oriented barium calcium titanate leadless piezoelectric textured ceramics; by [111]]The oriented flaky BaTiO3 template is an oriented template, and the adjustable range of the grain size is large; barium calcium titanate based leadless ceramic grain edge [111] prepared by using the template]Highly preferred orientation, [111]]Texture degree is as high as 97%, piezoelectric constant d 15 Up to 673pC/N.
Description
Technical Field
The invention belongs to the technical field of piezoelectric ceramics, and particularly relates to [111] oriented barium calcium titanate leadless piezoelectric textured ceramics and a preparation method thereof.
Background
The piezoelectric ceramic is an important information functional material capable of realizing the mutual conversion of mechanical energy and electric energy, and has wide application range from household electronic fire engines, electronic watches, alarm devices to medical ultrasonic diagnostic apparatuses and ultrasonic flaw detectors, and plays an important role in various fields such as aerospace vehicles, naval sonar, high-speed trains and the like applied to national defense science and technology. However, most of the lead-based piezoelectric ceramics are practically used for production, and aluminum oxide in the lead-based ceramics can cause serious harm to the environment and human health in the production, processing, use and discarding processes, so that the research and development of the leadless piezoelectric ceramics become an important and urgent task along with the restriction and prohibition of lead-based materials in various countries.
Lead-free piezoelectric ceramics, i.e. piezoelectric ceramics which do not contain lead in the material itself, generally refer to novel piezoelectric materials which have high piezoelectric properties and good environmental coordination. Currently, lead-free piezoelectric material systems mainly include BNT (Na 0.5 Bi 0.5 Ti0 3 )、BT(BaTiO 3 )、KNN(Ka 0.5 Na 0.5 NbO 3 ) And bismuth layered structure lead-free piezoelectric system, however, a lead-free piezoelectric ceramic which can truly replace lead-based ceramic in terms of electromechanical properties and temperature stability has not been found yet. The electrical property of the piezoelectric single crystal is greatly superior to that of the piezoelectric ceramic, but the piezoelectric single crystal material has a series of problems, the large-size piezoelectric single crystal has complex growth process and high preparation and processing costsThe uniformity of the product is poor, and the large-scale application of the single crystal material is limited. Therefore, finding a method for preparing lead-free piezoelectric ceramics with performance comparable to that of single crystals is still another challenge.
A great number of experimental researches show that the anisotropic crystal grains in the microstructure of the piezoelectric ceramic material are regularly arranged along certain specific directions by utilizing the piezoelectric anisotropy of the piezoelectric crystal, so that the polycrystalline ceramic with a 'monocrystal-like' structure is prepared, and the leadless piezoelectric textured ceramic with performance comparable to that of single crystals, uniform components, simple preparation and harmless material is obtained. Template Grain Growth (TGG) is one common method for preparing textured ceramics. According to the method, the directional arrangement of the shape-opposite template seed crystals is introduced into the ceramic matrix, and the directional arrangement of the seed crystals guides the ceramic powder to epitaxially grow along the surface of the template in the sintering process, so that the overall preferred orientation of crystal grains is formed, and the textured ceramic is formed.
Currently, most reports focus on the preparation of the edge [001 ]]Oriented BaTiO 3 On the template, only a small part is the preparation edge [111]]Oriented BaTiO 3 Template, and reported [111]]Oriented BaTiO 3 The template seed crystal has small particle size and narrow adjustable range.
Disclosure of Invention
The invention aims to provide a method for producing a metal alloy by [111]]Oriented flake BaTiO 3 The lead-free piezoelectric ceramic is a directional template, and takes barium calcium titanate as a matrix, and has high texture and high piezoelectric constant.
In order to achieve the above purpose, the invention is realized by the following technical scheme: a preparation method of [111] oriented barium calcium titanate leadless piezoelectric textured ceramic comprises the following steps:
preparation [111]]Oriented flake BaTiO 3 A template;
preparing barium calcium titanate matrix powder;
mixing and ball milling barium calcium titanate matrix powder, a platy template, an organic solvent, a binder, a dispersing agent and a plasticizer to prepare mixed slurry; wherein, the organic solvent, the binder, the dispersant, the plasticizer and the flaky template respectively account for 50 to 70 percent, 3.2 to 10 percent, 1.5 to 4.5 percent and 2 to 30 percent of the total mass of the matrix powder;
casting, laminating cut pieces, isostatic pressing with warm water, discharging glue, isostatic pressing, sintering, silver coating and polarizing the mixed slurry to obtain [111] oriented barium calcium titanate leadless piezoelectric textured ceramic; wherein, the isostatic pressing time of the warm water is 20-80 min, the temperature is 70-95 ℃ and the pressure is 30-50 MPa.
Preparation [111]]Oriented flake BaTiO 3 The specific steps of the template are as follows:
s11: baTiO with the weighing molar ratio of 6:8-11 3 And TiO 2 Mixing the dried raw materials, adding molten salt NaCl-KCl with the same mass as the raw materials, ball milling, drying, presintering, and ultrasonically cleaning and drying by deionized water to obtain Ba 6 Ti 17 O 40 The precursor is used for preparing the precursor,
s12: weighing Ba with the molar ratio of 1:12-15 6 Ti 17 O 40 Precursor and BaCO 3 Mixing the dried raw materials, adding molten salt NaCl-KCl with the same mass as the raw materials, ball milling, drying, roasting, and ultrasonically cleaning and drying with hot deionized water to obtain [111]]Oriented flake BaTiO 3 And (5) a template.
S11, presintering at 900-1150 ℃ for 1-8 h; in S12, the roasting temperature is 1000-1250 ℃, and the heat preservation time is 6-12 h.
Prepared [111]]Oriented flake BaTiO 3 The size of the template crystal grain is 2-50 mu m, and the diameter-thickness ratio is>10。
The preparation method of the barium calcium titanate matrix powder comprises the following specific steps:
s21: weighing BaCO in stoichiometric ratio 3 、CaCO 3 、TiO 2 Ball milling is carried out by taking absolute ethyl alcohol and zirconia balls as media, and then drying and roasting are carried out, thus obtaining powder;
s22: and (3) performing secondary ball milling on the roasted powder, and drying to obtain the barium calcium titanate matrix powder.
In S22, the roasting temperature is 750-1000 ℃ and the heat preservation time is 1-5 h.
The organic solvent in the step 3 is one or more of ethanol, dimethylbenzene, butanone and ethyl acetate; the binder is one of polyvinyl alcohol, polyvinyl butyral and ethyl cellulose; the dispersing agent is one of polyvinyl butyral, triethanolamine and phosphate; the plasticizer is one of polyethylene glycol, dibutyl phthalate and polyalkylene glycol.
The ball milling time in the step 3 is 12 to 24 hours, and the sheet-shaped [111]]BaTiO 3 The template is added 0.5 to 2 hours before ball milling is finished.
The specific technological parameters for preparing [111] oriented barium calcium titanate leadless piezoelectric textured ceramics are as follows: the height of the casting scraper is 200-450 mu m, and the casting speed is 40-80 cm/min; the lamination hot-pressing temperature is 70-100 ℃ and the pressure is 1-20 MPa; the temperature rise program of the adhesive discharging is as follows: 3h, heating to 100 ℃ from room temperature, preserving heat for 1h, heating to 300 ℃ for 8h, preserving heat for 3h, heating to 700 for 10h, preserving heat for 5h, and cooling along with a furnace after the heat preservation is finished; the maximum isostatic pressure is 200-300 MPa, the time is 1-30 min, the sintering temperature is 1400-1600 ℃, and the heat preservation is carried out for 5-10 h; the polarization temperature is 80-120 ℃, the polarization voltage is 1-10 kV/mm, and the polarization time is 10-60 min.
The barium calcium titanate leadless piezoelectric textured ceramic obtained based on the preparation method of the invention is [111]]Oriented barium calcium titanate leadless piezoelectric textured ceramic with texture degree of 91-97% and piezoelectric constant d 15 616-673 pC/N.
Compared with the prior art, the invention has at least the following beneficial effects:
the preparation method has low cost and short production period, and is suitable for industrialized mass production; in the preparation process, pb and other substances harmful to the environment are not used, so that the environmental pollution is greatly reduced; the invention is described in [111]]Oriented sheet BaTiO 3 On the basis of the template as a directional template, barium calcium titanate with the same structure is used as matrix powder, and the texture degree of the prepared barium calcium titanate texture ceramic reaches 97% and the piezoelectric constant d by a template grain growth method 15 As high as 673pC/N, the warm water isostatic pressing process is also carried out in the preparation process, the material density and texture degree are improved, the material layering is obviously reduced, and the yield is improved.
Drawings
FIG. 1 is [111] of example 1]Oriented flakesBaTiO 3 X-ray diffraction pattern of template.
FIG. 2 is [111] of example 1]Oriented flake BaTiO 3 SEM image of template.
FIG. 3 is an X-ray diffraction pattern of the [111] oriented barium calcium titanate leadless piezoelectric textured ceramic finally obtained in example 2.
FIG. 4 is an SEM image of a [111] oriented barium calcium titanate leadless piezoelectric textured ceramic sample finally obtained in example 2.
Detailed description of the preferred embodiments
The invention provides [111] oriented barium calcium titanate leadless piezoelectric textured ceramic and a preparation method thereof, wherein the method comprises the following steps:
step 1: preparation [111]]Oriented flake BaTiO 3 The template specifically comprises the following steps:
s1: baTiO with the weighing molar ratio of 6:8-11 3 、TiO 2 Mixing the dried raw materials, adding molten salt NaCl-KCl with the total mass ratio of 1:1 to the raw material mixture, mixing, ball milling and drying, presintering at 900-1150 ℃, preserving heat for 1-8 hours, ultrasonically cleaning the powder after the heat preservation by hot deionized water until no white precipitate exists in silver nitrate detection, and drying to obtain Ba 6 Ti 17 O 40 A precursor.
S2: ba obtained by S1 6 Ti 17 O 40 Precursor and BaCO 3 Mixing the dry raw materials according to a molar ratio of 1:12-15, adding molten salt NaCl-KCl with a total mass ratio of 1:1 with the raw material mixture, mixing, ball milling and drying, roasting at 1000-1250 ℃, preserving heat for 6-12 h, ultrasonically cleaning the powder after the heat preservation by using hot deionized water until no white precipitate is detected by silver nitrate, and drying to obtain [111]]Oriented flake BaTiO 3 And (5) a template.
Step 2: the preparation method of the barium calcium titanate matrix powder specifically comprises the following steps:
s1: weighing BaCO in stoichiometric ratio 3 、CaCO 3 、TiO 2 Drying raw materials, mixing, ball milling and drying absolute ethyl alcohol and zirconia balls as media, roasting the dried powder at 750-1000 ℃ and preserving heat for 1-5 hours;
s2: and (3) performing secondary ball milling and drying on the roasted synthetic powder to obtain the barium calcium titanate matrix powder.
Step 3: barium calcium titanate base powder [111]]Oriented flake BaTiO 3 Mixing and ball milling a template, an organic solvent, a binder, a dispersing agent and a plasticizer to prepare mixed slurry;
and 4, carrying out tape casting, sheet lamination, warm water isostatic pressing, glue discharging, isostatic pressing, sintering, silver coating and polarization on the obtained mixed slurry to obtain the [111] oriented barium calcium titanate leadless piezoelectric textured ceramic.
Preferably, the [111] is prepared]Oriented flake BaTiO 3 The size of the template crystal grain is 2-50 mu m, and the diameter-thickness ratio is>10, the obtained BaTiO 3 The X-ray diffraction pattern of the template is shown in fig. 1 and the sem is shown in fig. 2.
Preferably, the organic solvent is one or more of ethanol, xylene, butanone and ethyl acetate; the binder is one of polyvinyl alcohol, polyvinyl butyral and ethyl cellulose; the dispersing agent is one of polyvinyl butyral, triethanolamine and phosphate; the plasticizer is one of polyethylene glycol, dibutyl phthalate and polyalkylene glycol. Wherein, the organic solvent, the binder, the dispersant, the plasticizer and the flaky template respectively account for 50 to 70 percent, 3.2 to 10 percent, 1.5 to 4.5 percent and 2 to 30 percent of the total mass of the matrix powder.
Preferably, the ball milling time in the step 3 is 12-24 hours, and the platy BaTiO 3 The template is added 0.5 to 2 hours before ball milling is finished.
Preferably, the specific steps for preparing the [111] oriented barium calcium titanate leadless piezoelectric textured ceramic in the step 4 are as follows:
s1: uniformly casting the prepared mixed slurry on a substrate by using a casting scraper under the action of mechanical force, and drying to form a uniform membrane, wherein the height of the scraper is 200-450 mu m, and the casting speed is 40-80 cm/min;
s2: peeling the membrane from the substrate, laminating the cut pieces, and performing hot pressing treatment at 70-100 ℃ and 1-20 MPa;
s3: placing the blank after hot pressing into a warm water isostatic pressing machine, wherein the temperature is 70-95 ℃, the pressure is 30-50 MPa, and the pressure maintaining time is 20-80 min;
s4: and (3) carrying out glue discharging after warm water isostatic pressing, wherein the temperature rise program of the glue discharging is as follows: 3h, heating to 100 ℃ from room temperature, preserving heat for 1h, heating to 300 ℃ for 8h, preserving heat for 3h, heating to 700 for 10h, preserving heat for 5h, and cooling along with a furnace after the heat preservation is finished;
s5: carrying out cold isostatic pressing on the sample after glue discharge, and sintering the sample after cold isostatic pressing in a muffle furnace, wherein the maximum isostatic pressure is 200-300 MPa, the time is 1-30 min, the sintering temperature is 1400-1600 ℃, and the temperature is kept for 5-10 h;
s6: and polishing the surfaces of two sides of the sintered sample, and polarizing the sample by silver and high pressure to obtain the [111] oriented barium calcium titanate leadless piezoelectric textured ceramic, wherein the polarization temperature is 80-120 ℃, the polarization voltage is 1-10 kV/mm, and the polarization time is 10-60 min.
Preferably, the [111] is prepared]Oriented barium calcium titanate leadless piezoelectric textured ceramic with texture degree of 91-97% and piezoelectric constant d 15 Can reach 616-673 pC/N.
The invention will now be described in detail by means of specific examples which are given for illustrative purposes only and are not intended to limit the invention.
Example 1:
step 1: preparation [111]]Oriented flake BaTiO 3 The template specifically comprises the following steps:
s1: baTiO was weighed in a molar ratio of 6:11 3 、TiO 2 Mixing the dried raw materials, adding molten salt NaCl-KCl with the total mass ratio of 1:1 with the raw material mixture, mixing, ball milling and drying, presintering at 900 ℃, preserving heat for 3 hours, ultrasonically cleaning the powder after the heat preservation by hot deionized water until silver nitrate is detected to be free of white precipitate, and drying to obtain Ba 6 Ti 17 O 40 A precursor.
S2: ba obtained by S1 6 Ti 17 O 40 Precursor and BaCO 3 Mixing the dry raw materials according to a molar ratio of 1:13.6, adding molten salt NaCl-KCl with a total mass ratio of 1:1 to the raw material mixture, mixing, ball milling and drying, roasting at 1000 ℃, preserving heat for 5h, and carrying out ultrasonic treatment on the powder after heat preservation by using hot deionized waterWashing until no white precipitate exists in silver nitrate detection, and drying to obtain [111]]Oriented flake BaTiO 3 And (5) a template.
Step 2: the preparation method of the barium calcium titanate matrix powder specifically comprises the following steps:
s1: weighing BaCO in stoichiometric ratio 3 、CaCO 3 、TiO 2 Drying raw materials, mixing, ball milling and drying absolute ethyl alcohol and zirconia balls as media, roasting the dried powder at 850 ℃ and preserving heat for 3 hours;
s2: and (3) performing secondary ball milling and drying on the roasted synthetic powder to obtain the barium calcium titanate matrix powder.
Step 3: gradually adding an organic solvent (ethanol-butanone mixture with the mass ratio of 1:2) accounting for 40 percent of the total mass of the barium calcium titanate matrix powder, a binder polyvinyl alcohol accounting for 5.7 percent of the total mass, a dispersing agent polyvinyl butyral accounting for 3 percent of the total mass and a plasticizer polyethylene glycol accounting for 3 percent of the total mass into the barium calcium titanate matrix powder, mixing and ball milling for 10 hours, and then adding [111] accounting for 11 percent of the total mass]Oriented flake BaTiO 3 Ball milling the template for 2h to prepare mixed slurry.
Step 4, preparing [111] orientation barium calcium titanate leadless piezoelectric textured ceramics, which specifically comprises the following steps:
s1: uniformly casting the prepared mixed slurry on a substrate by using a casting scraper under the action of mechanical force, and drying to form a uniform membrane, wherein the height of the scraper is 350 mu m, and the casting speed is 65cm/min;
s2: peeling the membrane from the substrate, laminating the cut pieces, and performing hot pressing treatment at 80 ℃ and 8 MPa; hot pressing, and then carrying out warm water isostatic pressing at 80 ℃ and 50 Mpa;
s3: and (3) performing glue discharging on the blank body subjected to warm water isostatic pressing, wherein the temperature rise program of the glue discharging is as follows: 3h, heating to 100 ℃ from room temperature, preserving heat for 1h, heating to 300 ℃ for 8h, preserving heat for 3h, heating to 700 for 10h, preserving heat for 5h, and cooling along with a furnace after the heat preservation is finished;
s4: carrying out cold isostatic pressing on the sample after glue discharge, and sintering the sample after cold isostatic pressing in a muffle furnace, wherein the maximum pressure of the cold isostatic pressing is 200MPa, the time is 25min, the sintering temperature is 1400 ℃, and the temperature is kept for 8h;
s5: and polishing the surfaces on two sides of the sintered sample, and polarizing the sample by silver and high pressure at the temperature of 80 ℃, the polarizing voltage of 4kV/mm and the polarizing time of 30min to obtain the [111] oriented barium calcium titanate leadless piezoelectric textured ceramic.
Prepared [111]]Oriented flake BaTiO 3 The size of the template crystal grain is 36 mu m, and the diameter-thickness ratio is>10。
Prepared [111]]Oriented barium calcium titanate leadless piezoelectric textured ceramic has texture degree of 91% and piezoelectric constant d 15 635pC/N.
Example 2:
step 1: preparation [111]]Oriented flake BaTiO 3 The template specifically comprises the following steps:
s1: baTiO was weighed in a molar ratio of 6.5:11 3 、TiO 2 Mixing the dried raw materials, adding molten salt NaCl-KCl with the total mass ratio of 1:1 with the raw material mixture, mixing, ball milling and drying, presintering at 1000 ℃, preserving heat for 8 hours, ultrasonically cleaning the powder after heat preservation by hot deionized water until silver nitrate is detected to be free of white precipitate, and drying to obtain Ba 6 Ti 17 O 40 A precursor.
S2: ba obtained by S1 6 Ti 17 O 40 Precursor and BaCO 3 Mixing the dry raw materials according to a molar ratio of 1:12, adding molten salt NaCl-KCl with a total mass ratio of 1:1 to the raw material mixture, mixing, ball milling and drying, roasting at 1050 ℃, preserving heat for 10 hours, ultrasonically cleaning the powder after the heat preservation by using hot deionized water until no white precipitate exists in silver nitrate detection, and drying to obtain [111]]Directional flake BaTiO 3 And (5) a template.
Step 2: the preparation method of the barium calcium titanate matrix powder specifically comprises the following steps:
s1: weighing BaCO in stoichiometric ratio 3 、CaCO 3 、TiO 2 Drying raw materials, mixing, ball milling and drying absolute ethyl alcohol and zirconia balls as media, roasting the dried powder at 750 ℃ and preserving heat for 1h;
s2: and (3) performing secondary ball milling and drying on the roasted synthetic powder to obtain the barium calcium titanate matrix powder.
Step (a)3: gradually adding an organic solvent ethyl acetate accounting for 50 percent of the total mass of the matrix powder, a binder ethyl cellulose accounting for 3.2 percent of the total mass, a dispersant phosphate accounting for 2.5 percent of the total mass and a plasticizer polyalkylene glycol accounting for 1.5 percent of the total mass into the barium calcium titanate matrix powder, mixing and ball milling for 14 hours, and then adding [111] accounting for 30 percent of the total mass]Oriented flake BaTiO 3 Ball milling the template for 1h to prepare mixed slurry.
Step 4, preparing [111] orientation barium calcium titanate leadless piezoelectric textured ceramics, which specifically comprises the following steps:
s1: uniformly casting the prepared mixed slurry on a substrate by using a casting scraper under the action of mechanical force, and drying to form a uniform membrane, wherein the height of the scraper is 450 mu m, and the casting speed is 80cm/min;
s2: peeling the membrane from the substrate, laminating the cut pieces, and performing hot pressing treatment at 90 ℃ and 1 MPa; hot pressing, and then carrying out warm water isostatic pressing at 80 ℃ and 50 Mpa;
s3: and (3) performing glue discharging on the blank body subjected to warm water isostatic pressing, wherein the temperature rise program of the glue discharging is as follows: 3h, heating to 100 ℃ from room temperature, preserving heat for 1h, heating to 300 ℃ for 8h, preserving heat for 3h, heating to 700 for 10h, preserving heat for 5h, and cooling along with a furnace after the heat preservation is finished;
s4: carrying out cold isostatic pressing on the sample after glue discharge, and sintering the sample after cold isostatic pressing in a muffle furnace, wherein the maximum isostatic pressure is 275MPa, the time is 1min, the sintering temperature is 1450 ℃, and the temperature is kept for 6.5h;
s5: and polishing the surfaces on two sides of the sintered sample, and polarizing the sample by silver and high pressure at a temperature of 100 ℃, a polarizing voltage of 3kV/mm and a polarizing time of 10min to obtain the [111] oriented barium calcium titanate leadless piezoelectric textured ceramic.
Prepared [111]]Oriented flake BaTiO 3 The size of the template crystal grain is 50 mu m, and the diameter-thickness ratio is>10。
Prepared [111]]Oriented barium calcium titanate leadless piezoelectric textured ceramic has texture degree of 95% and piezoelectric constant d 15 673pC/N;
[111] the X-ray diffraction pattern of the oriented barium calcium titanate leadless piezoelectric textured ceramic is shown in fig. 3, and the sem image is shown in fig. 4.
Example 3:
step 1: preparation [111]]Oriented flake BaTiO 3 The template specifically comprises the following steps:
s1: baTiO was weighed in a molar ratio of 8:11 3 、TiO 2 Mixing the dried raw materials, adding molten salt NaCl-KCl with the total mass ratio of 1:1 with the raw material mixture, mixing, ball milling and drying, presintering at 1150 ℃, preserving heat for 5 hours, ultrasonically cleaning the powder after heat preservation by hot deionized water until silver nitrate detection has no white precipitate, and drying to obtain Ba 6 Ti 17 O 40 A precursor.
S2: ba obtained by S1 6 Ti 17 O 40 Precursor and BaCO 3 Mixing the dry raw materials according to a molar ratio of 1:15, adding molten salt NaCl-KCl with a total mass ratio of 1:1 to the raw material mixture, mixing, ball milling, drying, roasting at 1250 ℃, preserving heat for 6 hours, ultrasonically cleaning the powder after the heat preservation by using hot deionized water until no white precipitate exists in silver nitrate detection, and drying to obtain [111]]Oriented flake BaTiO 3 And (5) a template.
Step 2: the preparation method of the barium calcium titanate matrix powder specifically comprises the following steps:
s1: weighing BaCO in stoichiometric ratio 3 、CaCO 3 、TiO 2 Drying raw materials, mixing, ball milling and drying absolute ethyl alcohol and zirconia balls as media, roasting the dried powder at 900 ℃ and preserving heat for 2 hours;
s2: and (3) performing secondary ball milling and drying on the roasted synthetic powder to obtain the barium calcium titanate matrix powder.
Step 3: gradually adding an organic solvent (ethanol-ethyl acetate with the mass ratio of 3:2) accounting for 70 percent of the total mass of the barium calcium titanate matrix powder, binder polyvinyl butyral accounting for 10 percent of the total mass, dispersant triethanolamine accounting for 1.5 percent of the total mass and plasticizer dibutyl phthalate accounting for 2.5 percent of the total mass into the barium calcium titanate matrix powder, mixing and ball milling for 20 hours, and then adding [111] accounting for 2 percent of the total mass]Oriented flake BaTiO 3 Ball milling the template for 0.5h to prepare mixed slurry.
Step 4, preparing [111] orientation barium calcium titanate leadless piezoelectric textured ceramics, which specifically comprises the following steps:
s1: uniformly casting the prepared mixed slurry on a substrate by using a casting scraper under the action of mechanical force, and drying to form a uniform membrane, wherein the height of the scraper is 200 mu m, and the casting speed is 40cm/min;
s2: peeling the membrane from the substrate, laminating the cut pieces, and performing hot pressing treatment at 70 ℃ and 20MPa; hot pressing, and then carrying out warm water isostatic pressing at 70 ℃ and 50 Mpa;
s3: and (3) performing glue discharging on the blank body subjected to warm water isostatic pressing, wherein the temperature rise program of the glue discharging is as follows: 3h, heating to 100 ℃ from room temperature, preserving heat for 1h, heating to 300 ℃ for 8h, preserving heat for 3h, heating to 700 for 10h, preserving heat for 5h, and cooling along with a furnace after the heat preservation is finished;
s4: carrying out cold isostatic pressing on the sample after glue discharge, and sintering the sample after cold isostatic pressing in a muffle furnace, wherein the maximum pressure of the cold isostatic pressing is 300MPa, the time is 15min, the sintering temperature is 1550 ℃, and the temperature is kept for 5h;
s5: and polishing the surfaces on two sides of the sintered sample, and polarizing the sample by silver and high pressure at 120 ℃ under the polarizing voltage of 10kV/mm for 60min to obtain the [111] oriented barium calcium titanate leadless piezoelectric textured ceramic.
Prepared [111]]Oriented flake BaTiO 3 The size of the template crystal grain is 2 mu m, and the diameter-thickness ratio is>10。
Prepared [111]]Oriented barium calcium titanate leadless piezoelectric textured ceramic has texture degree of 97% and piezoelectric constant d 15 662pC/N.
Example 4:
step 1: preparation [111]]Oriented flake BaTiO 3 The template specifically comprises the following steps:
s1: baTiO was weighed in a molar ratio of 3.7:11 3 、TiO 2 Mixing the dried raw materials, adding molten salt NaCl-KCl with the total mass ratio of 1:1 with the raw material mixture, mixing, ball milling and drying, presintering at 1100 ℃, preserving heat for 1h, ultrasonically cleaning the powder after the heat preservation by hot deionized water until silver nitrate is detected to be free of white precipitate, and drying to obtain Ba 6 Ti 17 O 40 A precursor.
S2: ba obtained by S1 6 Ti 17 O 40 Precursor and BaCO 3 Mixing the dry raw materials according to a molar ratio of 1:14.4, adding molten salt NaCl-KCl with a total mass ratio of 1:1 to the raw material mixture, mixing, ball milling and drying, roasting at 1150 ℃, preserving heat for 12 hours, ultrasonically cleaning the powder after the heat preservation by using hot deionized water until no white precipitate is detected by silver nitrate, and drying to obtain [111]]Oriented flake BaTiO 3 And (5) a template.
Step 2: the preparation method of the barium calcium titanate matrix powder specifically comprises the following steps:
s1: weighing BaCO in stoichiometric ratio 3 、CaCO 3 、TiO 2 Drying raw materials, mixing, ball milling and drying absolute ethyl alcohol and zirconia balls as media, roasting the dried powder at 1000 ℃ and preserving heat for 5 hours;
s2: and (3) performing secondary ball milling and drying on the roasted synthetic powder to obtain the barium calcium titanate matrix powder.
Step 3: gradually adding organic solvent ethanol accounting for 55 percent of the total mass of the matrix powder, binder polyvinyl butyral accounting for 8.7 percent of the total mass, dispersant polyvinyl butyral accounting for 4.5 percent of the total mass and plasticizer polyethylene glycol accounting for 4.5 percent of the total mass into the barium calcium titanate matrix powder, mixing and ball milling for 15 hours, and then adding [111] accounting for 24 percent of the total mass]Oriented flake BaTiO 3 Ball milling the template for 1h to prepare mixed slurry.
Step 4, preparing [111] orientation barium calcium titanate leadless piezoelectric textured ceramics, which specifically comprises the following steps:
s1: uniformly casting the prepared mixed slurry on a substrate by using a casting scraper under the action of mechanical force, and drying to form a uniform membrane, wherein the height of the scraper is 270 mu m, and the casting speed is 53cm/min;
s2: peeling the membrane from the substrate, laminating the cut pieces, and performing hot pressing treatment at 90 ℃ and 16 MPa; hot pressing, and then carrying out warm water isostatic pressing at 95 ℃ and 50 Mpa;
s3: and (3) performing glue discharging on the hot-pressed blank, wherein the temperature rise program of the glue discharging is as follows: 3h, heating to 100 ℃ from room temperature, preserving heat for 1h, heating to 300 ℃ for 8h, preserving heat for 3h, heating to 700 for 10h, preserving heat for 5h, and cooling along with a furnace after the heat preservation is finished;
s4: carrying out cold isostatic pressing on the sample after glue discharge, and sintering the sample after cold isostatic pressing in a muffle furnace, wherein the maximum pressure of the cold isostatic pressing is 229MPa, the time is 30min, the sintering temperature is 1600 ℃, and the temperature is kept for 10h;
s5: and polishing the surfaces on two sides of the sintered sample, and polarizing the sample by silver and high pressure at the temperature of 100 ℃, the polarizing voltage of 1kV/mm and the polarizing time of 45min to obtain the [111] oriented barium calcium titanate leadless piezoelectric textured ceramic.
Prepared [111]]Oriented flake BaTiO 3 The size of the template crystal grain is 16 mu m, and the diameter-thickness ratio is>10。
Prepared [111]]Oriented barium calcium titanate leadless piezoelectric textured ceramic has texture degree of 93% and piezoelectric constant d 15 616pC/N.
The invention uses the [111] with the grain size of 2-50 mu m]Oriented sheet BaTiO 3 The lead-free piezoelectric textured ceramic with high texture and high piezoelectric constant is prepared by a template grain growth method for a directional template.
Claims (10)
1. The preparation method of [111] oriented barium calcium titanate leadless piezoelectric textured ceramic is characterized by comprising the following steps:
preparation [111]]Oriented flake BaTiO 3 A template;
preparing barium calcium titanate matrix powder;
mixing and ball milling barium calcium titanate matrix powder, a platy template, an organic solvent, a binder, a dispersing agent and a plasticizer to prepare mixed slurry; wherein, the organic solvent, the binder, the dispersant, the plasticizer and the flaky template respectively account for 50 to 70 percent, 3.2 to 10 percent, 1.5 to 4.5 percent and 2 to 30 percent of the total mass of the matrix powder;
and (3) carrying out tape casting, sheet lamination, warm water isostatic pressing, glue discharging, cold isostatic pressing, sintering, silver coating and polarization on the mixed slurry to obtain the [111] oriented barium calcium titanate leadless piezoelectric textured ceramic, wherein the warm water isostatic pressing time is 20-80 min, the temperature is 70-95 ℃ and the pressure is 30-50 MPa.
2. The method of claim 1, wherein [111]Oriented flake BaTiO 3 The specific steps of the template are as follows:
s11: baTiO with the weighing molar ratio of 6:8-11 3 And TiO 2 Mixing the dried raw materials, adding molten salt NaCl-KCl with the same mass as the raw materials, ball milling, drying, presintering, and ultrasonically cleaning and drying by deionized water to obtain Ba 6 Ti 17 O 40 The precursor is used for preparing the precursor,
s12: weighing Ba with the molar ratio of 1:12-15 6 Ti 17 O 40 Precursor and BaCO 3 Mixing the dried raw materials, adding molten salt NaCl-KCl with the same mass as the raw materials, ball milling, drying, roasting, and ultrasonically cleaning and drying with hot deionized water to obtain [111]]Oriented flake BaTiO 3 And (5) a template.
3. The preparation method according to claim 2, wherein in S11, the presintering temperature is 900-1150 ℃ and the heat preservation time is 1-8 h; in S12, the roasting temperature is 1000-1250 ℃, and the heat preservation time is 6-12 h.
4. The method of claim 2, wherein the [111] is]Oriented flake BaTiO 3 The size of the template crystal grain is 2-50 mu m, and the diameter-thickness ratio is>10。
5. The preparation method according to claim 1, wherein the specific steps of preparing the barium calcium titanate matrix powder are:
s21: weighing BaCO in stoichiometric ratio 3 、CaCO 3 、TiO 2 Ball milling is carried out by taking absolute ethyl alcohol and zirconia balls as media, and then drying and roasting are carried out, thus obtaining powder;
s22: and (3) performing secondary ball milling on the roasted powder, and drying to obtain the barium calcium titanate matrix powder.
6. The method according to claim 5, wherein in S22, the baking temperature is 750-1000 ℃ and the holding time is 1-5 hours.
7. The preparation method according to claim 1, wherein the organic solvent in the step 3 is one or more of ethanol, xylene, butanone and ethyl acetate; the binder is one of polyvinyl alcohol, polyvinyl butyral and ethyl cellulose; the dispersing agent is one of polyvinyl butyral, triethanolamine and phosphate; the plasticizer is one of polyethylene glycol, dibutyl phthalate and polyalkylene glycol.
8. The preparation method according to claim 1, wherein the ball milling time in the step 3 is 12-24 hours, and the sheet-like [111]]BaTiO 3 The template is added 0.5 to 2 hours before ball milling is finished.
9. The preparation method according to claim 1, wherein specific process parameters for preparing [111] oriented barium calcium titanate leadless piezoelectric textured ceramics are as follows: the height of the casting scraper is 200-450 mu m, and the casting speed is 40-80 cm/min; the lamination hot-pressing temperature is 70-100 ℃ and the pressure is 1-20 MPa; the temperature rise program of the adhesive discharging is as follows: 3h, heating to 100 ℃ from room temperature, preserving heat for 1h, heating to 300 ℃ for 8h, preserving heat for 3h, heating to 700 for 10h, preserving heat for 5h, and cooling along with a furnace after the heat preservation is finished; the maximum isostatic pressure is 200-300 MPa, the time is 1-30 min, the sintering temperature is 1400-1600 ℃, and the heat preservation is carried out for 5-10 h; the polarization temperature is 80-120 ℃, the polarization voltage is 1-10 kV/mm, and the polarization time is 10-60 min.
10. The barium calcium titanate leadless piezoelectric textured ceramic obtained by the preparation method of any one of claims 1 to 9, characterized in that it is [111]]Oriented barium calcium titanate leadless piezoelectric textured ceramic with texture degree of 91-97% and piezoelectric constant d 15 616-673 pC/N.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310130880.3A CN116253563B (en) | 2023-02-17 | 2023-02-17 | [111] oriented barium calcium titanate leadless piezoelectric textured ceramic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310130880.3A CN116253563B (en) | 2023-02-17 | 2023-02-17 | [111] oriented barium calcium titanate leadless piezoelectric textured ceramic and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116253563A true CN116253563A (en) | 2023-06-13 |
| CN116253563B CN116253563B (en) | 2024-01-12 |
Family
ID=86683818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310130880.3A Active CN116253563B (en) | 2023-02-17 | 2023-02-17 | [111] oriented barium calcium titanate leadless piezoelectric textured ceramic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116253563B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459346A (en) * | 2017-08-11 | 2017-12-12 | 哈尔滨工业大学 | Leadless piezoelectric barium phthalate base textured ceramic of high electric property and its preparation method and application |
| CN110128133A (en) * | 2019-05-23 | 2019-08-16 | 歌尔股份有限公司 | Barium titanate calcium based leadless piezoelectric ceramics and preparation method thereof |
| CN110615467A (en) * | 2019-11-06 | 2019-12-27 | 哈尔滨工业大学 | Barium titanate substrate flaky template seed crystal with preferred orientation along <111> and A-site composition and preparation method thereof |
| CN113830829A (en) * | 2021-09-30 | 2021-12-24 | 西安交通大学 | Flaky bismuth titanate strontium barium template crystal grain and preparation method thereof |
| CN114105190A (en) * | 2021-12-02 | 2022-03-01 | 清华大学 | Barium calcium titanate nanocrystalline dielectric material and preparation method thereof |
| US20220344574A1 (en) * | 2021-04-25 | 2022-10-27 | Hunan Meicheng Ceramic Technology Co., Ltd | Lead-free piezoelectric ceramic sensor material and a preparation method thereof |
-
2023
- 2023-02-17 CN CN202310130880.3A patent/CN116253563B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459346A (en) * | 2017-08-11 | 2017-12-12 | 哈尔滨工业大学 | Leadless piezoelectric barium phthalate base textured ceramic of high electric property and its preparation method and application |
| CN110128133A (en) * | 2019-05-23 | 2019-08-16 | 歌尔股份有限公司 | Barium titanate calcium based leadless piezoelectric ceramics and preparation method thereof |
| CN110615467A (en) * | 2019-11-06 | 2019-12-27 | 哈尔滨工业大学 | Barium titanate substrate flaky template seed crystal with preferred orientation along <111> and A-site composition and preparation method thereof |
| US20220344574A1 (en) * | 2021-04-25 | 2022-10-27 | Hunan Meicheng Ceramic Technology Co., Ltd | Lead-free piezoelectric ceramic sensor material and a preparation method thereof |
| CN113830829A (en) * | 2021-09-30 | 2021-12-24 | 西安交通大学 | Flaky bismuth titanate strontium barium template crystal grain and preparation method thereof |
| CN114105190A (en) * | 2021-12-02 | 2022-03-01 | 清华大学 | Barium calcium titanate nanocrystalline dielectric material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116253563B (en) | 2024-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100455538C (en) | Lead-less piezoelectric sodium bismuth titanate-bariumtitanate ceramic and its prepn process | |
| EP1972606A1 (en) | Crystallographically-oriented ceramic | |
| CN110615467B (en) | Barium titanate substrate-shaped template seed crystal with preferred orientation along <111> and A-site composition | |
| CN109626988B (en) | Piezoelectric ceramic material with high piezoelectric response and high Curie temperature and preparation method thereof | |
| CN102311266A (en) | Preparation method of (K05Na05) NbO3 (KNN) lead-free piezoelectric ceramic material | |
| CN111533556B (en) | Preparation method of grain-oriented strontium sodium niobate leadless ferroelectric ceramic | |
| CN104961455A (en) | Texturing piezoelectric ceramic material and preparation method thereof | |
| Gao et al. | Microstructure and piezoelectric properties of textured (Na0. 84K0. 16) 0.5 Bi0. 5TiO3 lead-free ceramics | |
| CN102167585B (en) | Multielement-doped bismuth titanate group lead-free piezoceramic material and preparation method thereof | |
| CN107840655B (en) | Preparation method of bismuth potassium titanate-based lead-free relaxation ferroelectric ceramic with morphotropic phase boundary | |
| CN110668493B (en) | Nano-micron sodium bismuth titanate-based low-dimensional crystal | |
| CN104628379A (en) | Highly-oriented lead-free piezoelectric textured ceramic material and preparation method and application thereof | |
| CN112745117A (en) | Textured piezoelectric ceramic laminated driver and preparation method thereof | |
| CN108373329A (en) | The preparation method of laminated film of the one kind based on PLZST/P (VDF-co-TrFE) | |
| CN106673648A (en) | Ytterbium oxide doped low-temperature prepared PZT (Piezoe-lectric Transducer) based piezoelectric ceramic | |
| CN114315346A (en) | Preparation method of large-strain lead-free piezoelectric textured ceramic with double-template texture | |
| CN111533555B (en) | Preparation method of layered compact strontium potassium niobate leadless piezoelectric ceramic | |
| CN116253563B (en) | [111] oriented barium calcium titanate leadless piezoelectric textured ceramic and preparation method thereof | |
| CN111072065B (en) | (111) oriented strontium titanate template material and preparation method thereof | |
| CN106518058A (en) | Lead-free compound ferroelectric ceramic composed of potassium-bismuth titanate and zinc oxide and preparation thereof | |
| CN107586129B (en) | Preparation method of [100] direction textured barium titanate piezoelectric ceramic | |
| CN115321980A (en) | Preparation method of potassium-sodium niobate (KNN) based lead-free piezoelectric ceramic | |
| CN104098328A (en) | Low-electric-field large-strain-response lead-free piezoelectric texture ceramic material as well as preparation method and application thereof | |
| CN115196961A (en) | Sodium bismuth titanate-based lead-free piezoelectric textured ceramic with high texture degree and high electrostrictive strain performance and preparation method thereof | |
| CN112851336A (en) | Preparation method of bismuth sodium titanate bismuth laminated piezoelectric ceramic |
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 |