WO2010116975A1 - ニオブ酸アルカリ金属塩粒子の製造方法、およびニオブ酸アルカリ金属塩粒子 - Google Patents
ニオブ酸アルカリ金属塩粒子の製造方法、およびニオブ酸アルカリ金属塩粒子 Download PDFInfo
- Publication number
- WO2010116975A1 WO2010116975A1 PCT/JP2010/056175 JP2010056175W WO2010116975A1 WO 2010116975 A1 WO2010116975 A1 WO 2010116975A1 JP 2010056175 W JP2010056175 W JP 2010056175W WO 2010116975 A1 WO2010116975 A1 WO 2010116975A1
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- WIPO (PCT)
- Prior art keywords
- particles
- longitudinal axis
- niobate
- sodium
- potassium salt
- Prior art date
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- 239000002245 particle Substances 0.000 title claims abstract description 184
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 229910052783 alkali metal Inorganic materials 0.000 title abstract description 17
- 150000001340 alkali metals Chemical class 0.000 title abstract description 17
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims description 50
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 claims description 45
- 239000012670 alkaline solution Substances 0.000 claims description 37
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 36
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 20
- 239000010955 niobium Substances 0.000 claims description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 18
- 229910052758 niobium Inorganic materials 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000004729 solvothermal method Methods 0.000 claims description 14
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910010293 ceramic material Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- -1 niobium halide Chemical class 0.000 claims description 7
- 230000007423 decrease Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 abstract description 11
- 239000007791 liquid phase Substances 0.000 abstract description 4
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 54
- 238000000034 method Methods 0.000 description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 239000000919 ceramic Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000004809 Teflon Substances 0.000 description 9
- 229920006362 Teflon® Polymers 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 150000002822 niobium compounds Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion 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
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- DSYRJFDOOSKABR-UHFFFAOYSA-I niobium(v) bromide Chemical compound [Br-].[Br-].[Br-].[Br-].[Br-].[Nb+5] DSYRJFDOOSKABR-UHFFFAOYSA-I 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 1
- FWIYBTVHGYLSAZ-UHFFFAOYSA-I pentaiodoniobium Chemical compound I[Nb](I)(I)(I)I FWIYBTVHGYLSAZ-UHFFFAOYSA-I 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/02—Oxides
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
- C01G33/006—Compounds containing, besides niobium, two or more other elements, with the exception of oxygen or hydrogen
-
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- 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
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
- H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
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- 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
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/093—Forming inorganic materials
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- 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
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- 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
- H10N30/8542—Alkali metal based oxides, e.g. lithium, sodium or potassium niobates
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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- 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
- C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
- C04B2235/3255—Niobates or tantalates, e.g. silver niobate
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- C—CHEMISTRY; METALLURGY
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- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to a method for producing alkali metal niobate particles and alkali metal niobate particles.
- piezoelectric ceramics In addition to conventional applications such as various sensors and ultrasonic vibrators, piezoelectric ceramics have recently been used for miniaturization of electronic devices such as transformers for liquid crystal backlights for personal computers and head parts for inkjet printers. And greatly contributes to high performance.
- lead-based materials such as PZT are currently mainstream.
- the lead-based material contains a large amount of harmful lead oxide, there is a concern about environmental pollution due to, for example, the outflow of lead oxide at the time of disposal. Therefore, there is a strong demand for the development of a practical lead-free piezoelectric ceramic material that can be substituted for a conventional lead-based material.
- Patent Document 1 proposes a piezoelectric ceramic in which aluminum oxide and iron oxide are added as subcomponents to a solid solution containing lithium sodium niobate as a basic composition.
- Patent Document 2 proposes a composition in which physical properties are improved by adding copper, lithium and tantalum to a piezoelectric ceramic mainly composed of potassium niobate and sodium niobate.
- Non-Patent Document 1 reports a method of synthesizing NaNbO 3 particles by causing NaOH or KOH solution to act on Nb 2 O 5 particles.
- Non-patent document 2 As synthesis of KNbO 3 particles, once synthesized K 4 Nb 6 O 17 particles layered, then method of synthesizing KNbO 3 particles by high temperature heating in a molten salt has also been reported recently (Non-patent document 2 ).
- the particles are aggregated, and it is generally difficult to control the obtained particle size and form to be uniform.
- the particles obtained by the method described in Patent Document 1 are aggregates, and are not suitable as a raw material for molding a piezoelectric element that is becoming finer in recent years. Thus, the problem is that the size and shape of the particles cannot be controlled.
- this is a method suitable for mass production, and is a method for producing alkali metal niobate particles capable of preventing particle aggregation and controlling grain boundaries and particle sizes, and has high uniformity in particle size and shape. Development of fine particles of alkali metal niobate was desired.
- An object of the present invention is to provide a liquid phase production method for producing alkali metal niobate fine particles capable of controlling the size and shape of the alkali metal niobate fine particles.
- the present inventors can prepare sodium niobate / potassium salt particles composed of secondary particles having a uniform size and special shape with good reproducibility by combining sodium and potassium in a specific ratio among alkali metals. As a result, the present invention has been completed.
- the first aspect of the present invention is: Na x K (1-x) NbO 3
- a method for producing sodium niobate / potassium salt particles represented by: (A) mixing a niobium-containing solution and an alkaline solution having a concentration of 0.1 to 30 mol / L to prepare a suspension; (B) allowing the obtained suspension to stand at 80 ° C. to 150 ° C. for 12 to 48 hours; (C) a step of allowing the suspension after standing to undergo a solvothermal reaction at 150 ° C. to 300 ° C.
- the alkaline solution relates to a method for producing sodium niobate / potassium salt particles containing Na + ions and K + ions.
- the molar ratio of Na + ions to K + ions (Na: K) is (1:17) to (17: 1).
- the niobium-containing solution contains niobium oxide or niobium halide, at least one solvent selected from water, ethylene glycol, and polyethylene glycol, and an acid.
- the second aspect of the present invention is: Following formula (1): Na x K (1-x) NbO 3 (1)
- the present invention relates to sodium niobate / potassium salt particles having an aspect ratio of 1 to 5.
- x is in the range of 0.05 ⁇ x ⁇ 0.8.
- the cross section in the direction parallel to the longitudinal axis including the longitudinal axis is a substantially line contrast with the longitudinal axis as the target axis, and the distance from the longitudinal axis to the particle outer contour line is the longitudinal axis. Is a shape that decreases toward the end of the The cross section of the plane perpendicular to the longitudinal axis provides sodium niobate / potassium salt particles having a cross shape.
- the cross section in the direction parallel to the longitudinal axis including the longitudinal axis is a substantially line contrast with the longitudinal axis as the target axis, and the distance from the longitudinal axis to the particle outer contour line is longitudinal. It is a shape that decreases as it goes toward the end of the shaft, Sodium niobate / potassium salt particles having a substantially circular cross section in a plane perpendicular to the longitudinal axis are provided.
- sodium niobate / potassium niobate particles are prepared by the method described above.
- a third aspect of the present invention relates to a piezoelectric ceramic material comprising the sodium niobate / potassium niobate particles.
- secondary particles of sodium niobate / potassium salt can be synthesized in large quantities while controlling the size and form. Moreover, the shape and size of the particles can be freely controlled by adjusting the ratio of sodium and potassium.
- the present invention is an advantageous method in that particles having a size of submicron to several ⁇ m, which is practically suitable as a piezoelectric element, can be synthesized by a method suitable for mass synthesis.
- the ceramic material obtained by pelletizing and firing the niobium-based particles thus obtained is more in comparison with the niobium-based piezoelectric ceramic material prepared by the conventional solid phase method. 1. 1. Low temperature firing is possible. 2. Excellent piezoelectric properties. 3. Densification of ceramic material is easy. There are advantages such as easy slurry preparation when laminating.
- FIG. 2 schematically shows a cross-sectional view (cross-sectional view in the xy plane) of the sodium niobate / potassium niobate particles, which is the first preferred embodiment of the present invention, in a direction parallel to the longitudinal axis.
- FIG. 2 is a schematic representation of a cross-sectional view (cross-sectional view in the xz plane) of the sodium niobate / potassium salt niobate particles according to the first preferred embodiment of the present invention cut perpendicularly to the longitudinal axis.
- FIG. 1 schematically shows a cross-sectional view (cross-sectional view in the xy plane) of the sodium niobate / potassium niobate particles, which is the first preferred embodiment of the present invention, in a direction parallel to the longitudinal axis.
- FIG. 2 is a schematic representation of a cross-sectional view (cross-sectional view in the xz plane) of the sodium niobate
- FIG. 3 schematically shows a cross-sectional view (cross-sectional view in the xy plane) in a direction parallel to the longitudinal axis of the sodium niobate / potassium salt particles of the second preferred embodiment of the present invention.
- FIG. 3 schematically shows a cross-sectional view (cross-sectional view in the xz plane) of a sodium niobate / potassium salt niobate particle, which is a second preferred embodiment of the present invention, cut perpendicularly to the longitudinal axis. It is a SEM photograph of sodium niobate / potassium salt particles obtained when the ratio of Na: K is 6:12.
- FIG. 4 is a SEM photograph of sodium niobate / potassium salt particles obtained when the ratio of Na: K is 5:13.
- 4 is a SEM photograph of Na x K (1-x) NbO 3 particles having an octahedral structure synthesized in Example 4.
- FIG. 4 It is an enlarged photograph of FIG. 4 is an XRD pattern of Na x K (1-x) NbO 3 particles synthesized in Example 4.
- FIG. 4 is a SEM photograph of a cross section of Na x K (1-x) NbO 3 particles synthesized in Example 4.
- FIG. 4 is a SEM photograph of a cross section of Na x K (1-x) NbO 3 particles synthesized in Example 4.
- FIG. 4 is a SEM photograph of a cross section of Na x K (1-x) NbO 3 particles synthesized in Example 4.
- FIG. 4 is an EDS analysis result of a Na x K (1-x) NbO 3 particle cross section synthesized in Example 4.
- FIG. It is a SEM photograph of sodium niobate / potassium salt particles obtained when the ratio of Na: K is 4:14. It is a SEM photograph of sodium niobate / potassium salt particles obtained when the ratio of Na: K is 3:15. It is a SEM photograph of sodium niobate / potassium salt particles obtained when the ratio of Na: K is 2:16. It is a SEM photograph of sodium niobate / potassium salt particles obtained when the ratio of Na: K is 1:17. 2 is an SEM photograph of sodium niobate particles obtained when NaOH is used as an alkaline solution.
- Example 9 It is a SEM photograph of potassium niobate salt particles obtained when KOH is used as an alkaline solution.
- Example 9 it is a SEM photograph of the ceramic prepared from the octahedral Na x K (1-x) NbO 3 particles. It is an enlarged photograph of FIG.
- the first aspect of the present invention is Na x K (1-x) NbO 3
- a method for producing sodium niobate / potassium salt particles represented by: (A) mixing a niobium-containing solution and an alkaline solution having a concentration of 0.1 to 30 mol / L to prepare a suspension; (B) allowing the obtained suspension to stand at 80 ° C. to 150 ° C. for 12 to 48 hours; (C) a step of allowing the suspension after standing to undergo a solvothermal reaction at 150 ° C. to 300 ° C.
- the alkaline solution relates to a method for producing sodium niobate / potassium salt particles containing Na + ions and K + ions.
- Step (a) is a step of preparing a suspension by mixing a niobium-containing solution that is a niobium source and a high-concentration alkaline solution.
- the method for preparing the niobium-containing solution is not particularly limited, but as an example, it can be prepared by dissolving a niobium compound in an acidic liquid solvent.
- the niobium compound is not particularly limited, but is preferably at least one selected from niobium oxide and niobium halide, more preferably niobium oxide or niobium halide.
- the niobium halide include niobium fluoride, niobium chloride, niobium bromide, and niobium iodide, and niobium chloride is preferred from the viewpoint of handleability and reactivity. These may be used alone or in combination of two or more.
- Water Although it does not specifically limit as a solvent contained in the said acidic liquid solvent, Water; Alcohols, such as methyl alcohol and ethyl alcohol; Polyols, such as ethylene glycol (EG), glycerol, and polyethyleneglycol (PEG). Among these, water, ethylene glycol and polyethylene glycol, and a mixture thereof are preferable, and water is particularly preferable because it has a relatively high boiling point and can be applied to a solvothermal method.
- Alcohols such as methyl alcohol and ethyl alcohol
- Polyols such as ethylene glycol (EG), glycerol, and polyethyleneglycol (PEG).
- EG ethylene glycol
- PEG polyethyleneglycol
- organic acids such as inorganic acids, such as hydrochloric acid, a sulfuric acid, and nitric acid, and trifluoroacetic acid, are mentioned.
- hydrochloric acid and nitric acid are preferable because hydrochloric acid is easily removed after the reaction, and hydrochloric acid is particularly preferable.
- the alkaline solution in the present invention contains both Na + ions and K + ions. Although it does not specifically limit as a kind of alkali contained in an alkaline solution, The mixture of KOH and NaOH etc. are mentioned. A mixture of KOH and NaOH is preferred because it is convenient to obtain a highly concentrated alkaline solution necessary to achieve the present invention.
- the concentration of the alkaline solution is less than 0.1 mol / L, the particles do not grow sufficiently, and it is not preferable because particles having a desired size and form cannot be obtained.
- the concentration of the alkaline solution exceeds 30 mol / L, the alkaline solution usually reaches a saturated concentration. Therefore, the upper limit of the concentration of the alkaline solution is practically the alkali saturation concentration, and this upper limit can vary depending on the nature of the alkali. Further, the lower limit of the concentration of the alkaline solution is preferably 1 mol / L, more preferably 2 mol / L.
- concentration sufficient care is required for handling.
- the ratio of Na + ions and K + ions contained in the alkaline solution (Na: K) is preferably (1:17) to (17: 1), more preferably (4.5: 13.5) to ( 6.5: 12.5).
- secondary particles of sodium niobate / potassium salt having a rugby ball-like substantially elliptical sphere or a peculiar shape of a substantially octahedral shape are obtained. (See FIGS. 5-8).
- the niobium-containing solution prepared separately in this way and the alkaline solution are mixed to prepare a suspension.
- the addition method is not particularly limited, and the niobium-containing solution may be added to the alkaline solution, or the alkaline solution may be added to the niobium-containing solution. It is preferable to slowly drop into the alkaline solution over a certain period of time.
- the temperature and pressure at the time of mixing are not particularly limited, and the mixing can usually be performed at normal temperature (15 ° C. to 30 ° C.) and normal pressure (about 1 atm).
- Step (b) is a step of heating the suspension for a long time at a relatively low temperature.
- it is a great feature to take two steps, a process of heating at a relatively low temperature for a long time and a solvothermal reaction process of heating at a high temperature for a short time.
- step (b) is not performed, agglomerates are usually formed and the particle size cannot often be controlled sufficiently.
- step (b) is not carried out, it is often difficult to obtain particles having a substantially elliptical shape or a substantially octahedral shape, which is one feature of the present invention.
- step (b) the suspension is heated to a temperature of 80-150 ° C.
- This temperature is preferably 80 to 120 ° C., more preferably 90 to 110 ° C., and still more preferably the boiling point of the solvent. That is, when water is used as the solvent, it is preferably heated to 100 ° C.
- the step (b) is characterized by being allowed to stand for 12 to 48 hours at the specific temperature. By standing for such a time, the aggregation of the particles can be prevented, and the growth of the particles into a substantially rectangular parallelepiped shape can be promoted. If the standing time is too short, the particle growth does not proceed sufficiently. On the other hand, if it is too long, the effect is saturated and it is not economical. Therefore, it is appropriate to stand for 12 to 48 hours. This time is preferably 15 to 36 hours, more preferably 18 to 30 hours, still more preferably 20 to 26 hours.
- a process (b) is not specifically limited, Usually, it is performed under a normal pressure (about 1 atmosphere (about 0.10 MPa)).
- Step (c) is a step in which the suspension heated at a relatively low temperature in step (b) is subjected to a solvothermal reaction at a higher temperature.
- the solvothermal reaction is a reaction carried out under moderate to high pressure (usually 1 atm to 10,000 atm (0.10 to 1,000 MPa)) and temperature (usually 100 ° C to 1000 ° C), Is particularly used as a solvent, it is referred to as “hydrothermal reaction”. By passing through this step, it is possible to stabilize the particles and control the particle shape.
- the temperature during the solvothermal reaction is 150 ° C. to 300 ° C. Although not particularly limited, it is preferably 150 ° C to 250 ° C.
- the time for performing the solvothermal reaction is usually 1 to 12 hours, preferably 1 to 8 hours, more preferably 2 to 5 hours.
- the pressure for carrying out the solvothermal reaction is not particularly limited, but is usually 0.10 to 4.0 MPa.
- Step (d) is a step of recovering the alkali metal niobate particles from the reaction product of the solvothermal reaction.
- the method for recovering the alkali metal niobate particles is not particularly limited, and desired alkali metal niobate particles can be obtained by ordinary filtration, washing, drying and the like.
- the number of times of washing and the solvent used are not particularly limited, and can be appropriately selected.
- the alkali metal niobate particles of the present invention have the following formula (1): Following formula (1): Na x K (1-x) NbO 3 (1)
- FIG. 1 is a cross-sectional view of a particle of sodium niobate / potassium salt, which is an embodiment of the present invention, cut so as to include the maximum diameter L1.
- an axis including a straight line connecting two points on the outer contour line having the maximum diameter is referred to as a “longitudinal axis”.
- the longitudinal axis in FIG. 1 is the y axis.
- the ratio of the long side to the short side (long side / short side) of the smallest rectangle (usually called circumscribed rectangle) when the particle is surrounded by a rectangle is called the aspect ratio.
- the circumscribed rectangle is represented by a broken line.
- the long side is in a direction parallel to the longitudinal axis (y-axis direction in FIG. 1), and the length of the long side coincides with the maximum diameter L1.
- the short side is oriented in the direction perpendicular to the longitudinal axis (in the x-axis direction in FIG. 1), and the length is indicated as L2 in FIG.
- the short side length means a particle having the maximum length among particle diameters in a direction perpendicular to the longitudinal axis.
- the aspect ratio is represented by L1 / L2.
- the particle length in the longitudinal axis direction is 0.05 to 20 ⁇ m.
- the thickness is preferably 0.5 to 10 ⁇ m, more preferably 1 to 5 ⁇ m. If the particle length in the longitudinal axis direction is within this range, the uniformity of the size and shape is high, which is advantageous when applied to a molded article having a fine shape.
- the aspect ratio of the particles is 1 to 5, preferably 1 to 3, more preferably 1 to 2.
- the aspect ratio is 1 to 1.5.
- the sodium / potassium niobate particles of the present invention usually have a special shape such as a rugby ball-like substantially elliptical sphere or a substantially octahedral shape (see FIGS. 5 and 6).
- x in the formula (1) is preferably in the range of 0.05 ⁇ x ⁇ 0.8, and the range of 0.25 ⁇ x ⁇ 0.36. It is more preferable that
- a preferred embodiment of the present invention relates to sodium / potassium niobate particles having such a special shape.
- FIGS. 1 and 2 and the SEM photograph of FIG. 6 relate to octahedral sodium niobate / potassium niobate particles, which is one of the preferred embodiments of the present invention.
- FIG. 1 schematically shows a cross-sectional view (cross-sectional view in the xy plane) in a direction parallel to the longitudinal axis of the particles.
- FIG. 2 schematically shows a cross-sectional view (cross-sectional view in the xz plane) of the particles cut perpendicular to the longitudinal axis.
- the octahedral sodium niobate / potassium niobate particles have a cross section in a direction parallel to the longitudinal axis including the longitudinal axis (corresponding to the y-axis in FIG. 1). It has a line contrast structure (substantially diamond). Further, in FIG. 1, the distance from the longitudinal axis to the particle outer contour line (L3 in FIG. 1) decreases as it goes toward the end of the longitudinal axis.
- the cross section of the surface perpendicular to the longitudinal axis has a cross shape.
- the particles of this embodiment are a collection of finer particles (so-called primary particles). It is thought that it is an aggregate formed.
- the lattices in FIGS. 1 and 2 are intended for primary particles.
- sodium niobate / potassium niobate particles having a new shape were produced.
- the particles of the present embodiment can be obtained, for example, when the ratio of Na: K is 5:13, but is not particularly limited to this condition.
- the diameter of the primary particles constituting this embodiment is approximately 10 to 500 nm. Since the particles of this embodiment are aggregates of such primary particles, the maximum diameter is 3 to 20 ⁇ m as can be seen from the SEM photograph of FIG.
- the thickness is preferably 3 to 10 ⁇ m, more preferably 3 to 5 ⁇ m. When the particle length in the longitudinal axis direction is within this range, it is advantageous when applied to a molded article having a fine shape.
- the aspect ratio of the particles is 1 to 5, preferably 1 to 3, and more preferably 1 to 2. In the typical particles shown in FIG. 6, the aspect ratio is 1 to 1.5.
- FIG. 3 schematically shows a cross-sectional view (cross-sectional view in the xy plane) in a direction parallel to the longitudinal axis of the particles.
- FIG. 4 schematically shows a cross-sectional view (cross-sectional view in the xz plane) of the particle cut perpendicular to the longitudinal axis.
- L1, L2, and L3 have the same meaning as in FIG.
- the octahedral sodium niobate / potassium niobate particles have a cross section in a direction parallel to the longitudinal axis including the longitudinal axis (corresponding to the y-axis in FIG. 1). It has a line contrast structure (substantially oval).
- the distance from the longitudinal axis to the particle outer contour line (L3 in FIG. 3) decreases as it goes toward the end of the longitudinal axis.
- the cross section of the surface perpendicular to the longitudinal axis is substantially circular. That is, it has a shape filled with primary particles compared to octahedral particles.
- the maximum diameter of the particles of the present embodiment is 0.05 to 20 ⁇ m.
- the thickness is preferably 3 to 10 ⁇ m.
- the aspect ratio of the particles is 1 to 5, preferably 1 to 3, more preferably 1 to 2.
- a typical particle shown in the upper left of FIG. 5 has an aspect ratio of 1 to 1.5.
- the method for preparing the sodium niobate / potassium salt particles is not particularly limited, but the sodium niobate / potassium salt particles are preferably prepared by the above-described production method according to the first aspect of the present invention.
- the above method is an epoch-making method in which the particle size can be controlled only by chemical means regardless of physical means such as pulverization, and is preferable in that the process can be simplified as compared with conventional means.
- pulverization or the like it is generally difficult to suppress the variation in particle size.
- the size of each particle can be controlled. Aggregation can also be prevented. As a result, the particle size of the obtained particles can be controlled to a high degree. Therefore, the production method of the first aspect is preferred as a method for preparing sodium niobate / potassium salt particles.
- a third aspect of the present invention relates to a piezoelectric ceramic material comprising the above sodium / potassium niobate salt.
- the method for producing the piezoelectric ceramic material is not particularly limited, but is usually a composition obtained by kneading dried sodium niobate / potassium salt particles and necessary additives such as an organic binder, a dispersant, a plasticizer and a solvent.
- Known molding methods include press molding and mold molding.
- a piezoelectric element such as a piezoelectric buzzer or a piezoelectric vibrator can be obtained.
- Example 3 Synthesis of Na x K (1-x) NbO 3 particles 2
- a Teflon (registered trademark) container (30 mL volume)
- 6 mL of an aqueous alkaline solution containing NaOH and KOH final NaOH concentration in the aqueous alkaline solution: 12 mol / L, Final KOH concentration: 24 mol / L
- ion-exchanged water was added with stirring so that the total volume became 12 mL.
- the Teflon (registered trademark) container was sealed and left to stand at 100 ° C. for 24 hours.
- Na x K (1-x) NbO 3 particles can be synthesized, and the particle size can be controlled in the range of 0.5 to 30 ⁇ m. Furthermore, it is possible to synthesize Na x K (1-x) NbO 3 particles having a unique shape.
- Example 4 Synthesis of Na x K (1-x) NbO 3 particles 3)
- a Teflon (registered trademark) beaker 185 mL of an aqueous alkaline solution containing NaOH and KOH (final NaOH concentration in the aqueous alkaline solution: 12 mol / L, final KOH concentration: 24 mol / L) was prepared and stirred at room temperature.
- the obtained niobium chloride solution was added to the alkaline solution while stirring at a rate of 15 mL / min. After the addition, the solution was stirred at room temperature for 10 minutes.
- the obtained suspension was transferred to an autoclave with a Teflon (registered trademark) inner cylinder, heated to 100 ° C. over 30 minutes while stirring, and then stirred at 100 ° C. for 24 hours. Then, the temperature was raised to 200 ° C. over 2 hours and 30 minutes, and a hydrothermal reaction was carried out by heating at 200 ° C. with stirring for 3 hours.
- the particles were particles having an octahedral shape and a diffraction pattern that could be attributed to tetragonal KNbO 3 . Furthermore, after cutting the particles using a cross section polisher, the EDS analysis was performed to examine the internal state of the crystal and the internal elemental composition (FIGS. 10 to 12). The stirring operation at the time of heating is effective for making the particle shape uniform.
- Example 1 Example 1 except that the molar ratio of NaOH / KOH was 4:14 (Example 5), 3:15 (Example 6), 2:16 (Example 7), and 1:17 (Example 8), respectively.
- sodium / potassium niobate particles were obtained. SEM photographs of the obtained particles are shown in FIGS.
- Example 1 Sodium niobate particles were obtained in the same manner as in Example 1 except that 6.0 mL of a 12.0 M NaOH aqueous solution was used as the alkaline solution. The obtained particles were fine particles having a substantially rectangular parallelepiped structure (FIG. 17).
- Example 9 (Preparation of Na x K (1-x) NbO 3 ceramics by sintering and evaluation of piezoelectric properties)
- the Na x K (1-x) NbO 3 particles synthesized in Example 4 were formed into pellets, fired at 1025 ° C., and the piezoelectric characteristics of the obtained ceramics were evaluated.
- SEM photographs of the obtained sintered body are shown in FIGS. 19 and 20, and each characteristic value is shown in Table 1.
- FIG. In the table, kp is an electromechanical coupling coefficient, and was calculated from measurement of resonance frequency and anti-resonance frequency with an impedance analyzer. Further, ⁇ 33 T / ⁇ 0 is a relative dielectric constant, and was measured with an impedance analyzer.
- Np is a frequency constant, and was calculated from the measurement of the resonance frequency with an impedance analyzer and the diameter of the element.
- tan ⁇ is a dielectric loss, and was measured with an impedance analyzer.
- d33 is a piezoelectric constant, and was measured with a d33 meter.
- the sodium / potassium niobate particles of the present invention can be suitably used as a piezoelectric material.
- the production method of the present invention is a method for obtaining sodium-potassium niobate particles having a specific shape directly only by chemical means without passing through physical means such as grinding.
- the obtained particles have high uniformity in both size and shape, and the size of the particles is excellent in handleability on the order of micrometers, and can be suitably used as a piezoelectric material.
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Abstract
Description
NaxK(1-x)NbO3 (1)
で表されるニオブ酸ナトリウム・カリウム塩粒子の製造方法であって、
(a)ニオブ含有溶液と、0.1~30mol/Lの濃度を有するアルカリ溶液とを混合し、懸濁液を調製する工程と、
(b)得られた懸濁液を80℃~150℃で12~48時間静置する工程と、
(c)静置後の懸濁液を150℃~300℃で1~12時間ソルボサーマル反応させる工程と、
(d)ソルボサーマル反応後の反応物からナトリウム・カリウム塩粒子を回収する工程と、
を含み、
上記アルカリ溶液はNa+イオン及びK+イオンを含有する
ニオブ酸ナトリウム・カリウム塩粒子の製造方法に関する。
下記式(1):
NaxK(1-x)NbO3 (1)
で表されるニオブ酸ナトリウム・カリウム塩粒子であって、
前記粒子の最大径は0.05~20μmであり、
前記粒子のアスペクト比が1~5であるニオブ酸ナトリウム・カリウム塩粒子に関する。
長手軸と垂直な面の断面は十字形状を有するニオブ酸ナトリウム・カリウム塩粒子を提供する。
長手軸と垂直な面の断面は略円形であるニオブ酸ナトリウム・カリウム塩粒子を提供する。
1.低温焼成が可能である
2.優れた圧電特性を示す
3.セラミック材料の緻密化が容易である
4.積層化する際のスラリー調製が容易である
などの利点を有する。
<ニオブ酸ナトリウム・カリウム塩粒子の製造方法>
上述の通り、本発明の第一の態様は、
NaxK(1-x)NbO3 (1)
で表されるニオブ酸ナトリウム・カリウム塩粒子の製造方法であって、
(a)ニオブ含有溶液と、0.1~30mol/Lの濃度を有するアルカリ溶液とを混合し、懸濁液を調製する工程と、
(b)得られた懸濁液を80℃~150℃で12~48時間静置する工程と、
(c)静置後の懸濁液を150℃~300℃で1~12時間ソルボサーマル反応させる工程と、
(d)ソルボサーマル反応後の反応物からニオブ酸ナトリウム・カリウム塩粒子を回収する工程と、
を含み、
上記アルカリ溶液はNa+イオン及びK+イオンを含有する
ニオブ酸ナトリウム・カリウム塩粒子の製造方法に関する。
工程(a)は、ニオブ源であるニオブ含有溶液と、高濃度アルカリ溶液とを混合し、懸濁液を調製する工程である。
本発明におけるアルカリ溶液は、Na+イオンとK+イオンの両方を含有するものである。アルカリ溶液に含まれるアルカリの種類としては、特に限定されないが、KOHとNaOHの混合物などが挙げられる。KOHとNaOHの混合物は、本願発明を達成するのに必要な高濃度のアルカリ溶液を得るのに好都合な点で好ましい。
[OH-]=1.0×10-1mol/L
[H+][OH-]=1.0×10-14であるから、
[H+]=1.0×10-13
pH=-log[H+]=13
に相当すると考えられる。
工程(b)は、比較的低温で長時間懸濁液を加熱する工程である。本発明においては、比較的低温で長時間加熱する工程と、高温で短時間加熱するソルボサーマル反応工程の二段階を採ることが大きな特徴である。工程(b)を行わない場合には、通常、凝集体が生成し、粒径を充分に制御することができない場合が多い。また工程(b)を行わない場合には、通常、本発明の一つの特徴でもある略楕円球状や、略八面体形状の粒子を得るのは困難な場合が多い。
工程(c)は、工程(b)で比較的低温で加温した懸濁液を、さらに高温にてソルボサーマル反応させる工程である。
工程(d)は、ソルボサーマル反応の反応物からニオブ酸アルカリ金属塩粒子を回収する工程である。
次に本発明の第二の態様である、ニオブ酸アルカリ金属塩粒子について説明する。本発明のニオブ酸アルカリ金属塩粒子は、下記式(1):
下記式(1):
NaxK(1-x)NbO3 (1)
で表されるニオブ酸ナトリウム・カリウム塩粒子であって、
上記粒子の最大径は0.05~20μmであり、
上記粒子のアスペクト比が1~5であることを特徴とする。
まず粒子の外側輪郭線上の任意の2点のうち、その間の距離が最大になるように選んだ時のその2点間の距離が「最大径」である。図1は、本発明の一実施形態であるニオブ酸ナトリウム・カリウム塩の粒子を、最大径L1を含むように切断した断面図である。ここで、最大径をとる外側輪郭線上の2点を結ぶ直線を含む軸を「長手軸」と呼ぶ。図1における長手軸はy軸である。
上述の通り、図1は該粒子の長手軸と平行方向の断面図(xy平面における断面図)を模式的に表したものである。また図2は、該粒子の、長手軸に垂直に切断した断面の図(xz平面における断面図)を模式的に表したものである。
本発明の第三の態様は、上記ニオブ酸ナトリウム・カリウム塩からなる圧電セラミックス材料に関する。
(NaxK(1-x)NbO3粒子の合成1)
塩化ニオブ27.02g(=100mmol)に0.10M HCl水溶液150mLを加え完全に溶解した後、容積200mLのメスフラスコに加え、0.10M HCl水溶液を用いて全量を200mLとすることにより0.50M NbCl5の0.10M HCl水溶液を得た。ついで、総アルカリ濃度が18.0Mの水酸化ナトリウムと水酸化カリウム(NaOH:KOH=6:12(mol/mol))の混合水溶液6.0mLを加えた30mL容のテフロン(登録商標)製容器に上記0.50M NbCl5塩酸水溶液6.0mLを室温で攪拌しながらゆっくり加えた後、得られた白色懸濁液をテフロン(登録商標)容器中、100℃で24時間加熱静置した。ついで、内容物をテフロン(登録商標)内筒製オートクレーブに移し、250℃で3時間静置して加熱経時することにより水熱反応を行った。得られた懸濁液から固体を遠心分離で回収後、水に超音波分散・遠心沈降・乾燥してニオブ酸ナトリウム・カリウム粒子を得た。得られた固体粒子のサイズ・形態を走査型電子顕微鏡(SEM、HITACHI、S-4800)で観察し、X線回折測定(XRD、Rigaku、Ultima-IV、40kV、40mA)により固体粒子の結晶構造を評価した。得られた粒子はラグビーボール状の特異形状を有する粒子であった(図5)。
総アルカリ濃度が18.0Mの混合水溶液の水酸化ナトリウムと水酸化カリウムのモル比を(NaOH:KOH=5:13(mol/mol)とした以外は、実施例1と同様の操作によりニオブ酸ナトリウム・カリウム粒子を得た。得られた粒子は略八面体構造の特異形状を有する粒子であった(図6)。
(NaxK(1-x)NbO3粒子の合成2)
テフロン(登録商標)製容器(30mL容)中の五酸化ニオブ0.40g(=3.0mmol)に、NaOH及びKOHを含有するアルカリ水溶液6mL(該アルカリ水溶液中の最終NaOH濃度:12mol/L、最終KOH濃度:24mol/L)を添加し、全体積が12mLとなるようにイオン交換水を攪拌しながら加えた。ついで、テフロン(登録商標)製容器を密封し、100℃で24時間加熱静置した。ついで、内容物をテフロン(登録商標)内筒製オートクレーブに移し、250℃で3時間静置して加熱経時することにより水熱反応を行った。得られた懸濁液から固体を遠心分離で回収後、水に超音波分散・遠心沈降・乾燥してNaNbO3粒子を得た。得られた粒子の評価は、実施例1に示した方法と同様の手法により行った。この際、初期NaOH濃度を1~17M,KOH濃度を17~1Mとし、総アルカリ濃度を18Mとすることで、NaxK(1-x)NbO3粒子中、xを0.05-0.8の範囲で制御しつつ、NaxK(1-x)NbO3粒子を合成することができ、その粒径を0.5~30μmの範囲で制御できる。さらに、特異な形状からなるNaxK(1-x)NbO3粒子の合成も可能である。
(NaxK(1-x)NbO3粒子の合成3)
テフロン(登録商標)ビーカー中でNaOH及びKOHを含むアルカリ水溶液185mL(該アルカリ水溶液中の最終NaOH濃度:12mol/L、最終KOH濃度:24mol/L)を調製し、室温で攪拌した。一方で、塩化ニオブ25g(=92.5mmol)を0.10M HCl水溶液185mLに加えることにより0.50M NbCl5の0.10M HCl水溶液を得た。得られた塩化ニオブ溶液をアルカリ溶液に15mL/分の速度で攪拌しながら添加し、添加後、室温で10分間攪拌した。得られた懸濁液をテフロン(登録商標)製内筒のオートクレーブに移し、30分かけて100℃に攪拌しながら昇温し、昇温後、100℃で24時間攪拌を続けた。ついで、2時間30分かけて200℃に昇温し、200℃で3時間攪拌しながら加熱することにより水熱反応を行った。加熱後、懸濁液を自然冷却し、得られた懸濁液から固体を遠心分離で回収後、水に超音波分散・遠心沈降による洗浄を6回行った。ついで、洗浄液をアセトンとし、さらに3回遠心洗浄後デシケーター中で乾燥することでニオブ酸ナトリウム・カリウム粒子を得た。得られた固体粒子のサイズ・形態を走査型電子顕微鏡で観察し、X線回折測定により固体粒子の結晶構造を評価した。合成した粒子のSEM写真を図7及び8に、XRD測定結果を図9にそれぞれ示す。粒子は八面体型の特異形状を有する粒子であり、正方晶のKNbO3と帰属できる回折パターンであった。さらに、クロスセクションポリッシャーを用いて粒子を切断後、EDS分析を行うことで結晶内部の状態および内部の元素組成を調べた(図10~12)。なお、加熱時の攪拌操作は粒子形状の均一化に有効である。
NaOH/KOHのモル比をそれぞれ4:14(実施例5)、3:15(実施例6)、2:16(実施例7)、1:17(実施例8)とした以外は実施例1と同様にしてニオブ酸ナトリウム・カリウム粒子を得た。得られた粒子のSEM写真を図13~16に示す。
アルカリ溶液として12.0M NaOH水溶液6.0mLを用いた以外は実施例1と同様の操作により、ニオブ酸ナトリウム粒子を得た。得られた粒子は略直方体構造の微粒子であった(図17)。
アルカリ溶液として12.0M KOH水溶液6.0mLを用いた以外は実施例1と同様の操作により、ニオブ酸カリウム粒子を得た。得られた粒子は略直方体構造の微粒子であった(図18)。
(焼結によるNaxK(1-x)NbO3セラミックスの調製と圧電特性評価)
実施例4で合成したNaxK(1-x)NbO3粒子をペレット成型後、1025℃で焼成し、得られたセラミックの圧電特性を評価した。得られた焼結体のSEM写真を図19および図20に、各特性値を表1に示す。
表中、kpは電気機械結合係数であり、インピーダンスアナライザーにて共振周波数と反共振周波数の測定から算出した。また、ε33 T/ε0は比誘電率であり、インピーダンスアナライザーにて測定した。Npは周波数定数であり、インピーダンスアナライザーにて共振周波数の測定と素子の直径から算出した。tanδは誘電損失であり、インピーダンスアナライザーにて測定した。d33は圧電定数であり、d33メータにて測定した。
L2 粒子の外接長方形の短辺の長さ
L3 長手軸から粒子外側輪郭線までの距離
Claims (9)
- NaxK(1-x)NbO3 (1)
で表されるニオブ酸ナトリウム・カリウム塩粒子の製造方法であって、
(a)ニオブ含有溶液と、0.1~30mol/Lの濃度を有するアルカリ溶液とを混合し、懸濁液を調製する工程と、
(b)得られた懸濁液を80℃~150℃で12~48時間静置する工程と、
(c)静置後の懸濁液を150℃~300℃で1~12時間ソルボサーマル反応させる工程と、
(d)ソルボサーマル反応後の反応物からナトリウム・カリウム塩粒子を回収する工程と、
を含み、
前記アルカリ溶液はNa+イオン及びK+イオンを含有する
ニオブ酸ナトリウム・カリウム塩粒子の製造方法。 - 前記Na+イオンとK+イオンのモル比(Na:K)は(1:17)~(17:1)である
請求項1に記載の製造方法。 - 前記ニオブ含有溶液は、
酸化ニオブ又はハロゲン化ニオブと、
水、エチレングリコール及びポリエチレングリコールから選択される少なくとも一つの溶媒と、
酸と、
を含む請求項1又は2に記載の製造方法。 - 下記式(1):
NaxK(1-x)NbO3 (1)
で表されるニオブ酸ナトリウム・カリウム塩粒子であって、
前記粒子の最大径は0.05~20μmであり、
前記粒子のアスペクト比が1~5であるニオブ酸ナトリウム・カリウム塩粒子。 - 前記xは、0.05≦x≦0.8の範囲である請求項4記載のニオブ酸ナトリウム・カリウム塩粒子。
- 長手軸を含む長手軸と平行な方向の断面は、長手軸を対象軸とした略線対照で、かつ、長手軸から粒子外側輪郭線までの距離が、長手軸の端部方向に向かうにつれて減少する形状であり、
長手軸と垂直な面の断面は十字形状を有する請求項4又は5記載のニオブ酸ナトリウム・カリウム塩粒子。 - 長手軸を含む長手軸と平行な方向の断面は、長手軸を対象軸とした略線対照で、かつ、長手軸から粒子外側輪郭線までの距離が、長手軸の端部方向に向かうにつれて減少する形状であり、
長手軸と垂直な面の断面は略円形である請求項4又は5記載のニオブ酸ナトリウム・カリウム塩粒子。 - 請求項1~3のいずれか一項に記載の製造方法によって調製される
請求項4~7いずれか一項に記載のニオブ酸ナトリウム・カリウム塩粒子。 - 請求項4~8のいずれか一項に記載のニオブ酸ナトリウム・カリウム塩粒子からなる圧電セラミックス材料。
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CN102115168A (zh) * | 2011-03-04 | 2011-07-06 | 浙江大学 | 一种纳米结构Li3NbO4的制备方法 |
JP2012232862A (ja) * | 2011-04-28 | 2012-11-29 | Toyama Prefecture | 異方形状粉末及びその製造方法 |
JP2012246178A (ja) * | 2011-05-27 | 2012-12-13 | Canon Inc | ニオブ酸ナトリウム粉末、ニオブ酸ナトリウム粉末の製造方法、板状粒子、板状粒子の製造方法、配向セラミックスの製造方法 |
US9318689B2 (en) | 2011-05-27 | 2016-04-19 | Canon Kabushiki Kaisha | Sodium niobate powder, method of manufacturing a sodium niobate powder, plate-like particle, method of manufacturing a plate-like particle, and method of manufacturing an oriented ceramics |
CN102502833A (zh) * | 2011-10-27 | 2012-06-20 | 浙江大学 | 一种微纳结构K3Nb7O19六棱片的制备方法 |
CN102583538A (zh) * | 2012-02-28 | 2012-07-18 | 齐齐哈尔大学 | 一种制备铌酸钠钾纳米棒的溶胶-凝胶方法 |
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Also Published As
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US8920924B2 (en) | 2014-12-30 |
EP2418175A1 (en) | 2012-02-15 |
KR20120006019A (ko) | 2012-01-17 |
EP2418175B1 (en) | 2017-02-01 |
US20140103246A1 (en) | 2014-04-17 |
KR101642167B1 (ko) | 2016-07-22 |
JP2010241659A (ja) | 2010-10-28 |
US20120094126A1 (en) | 2012-04-19 |
EP2418175A4 (en) | 2013-10-09 |
JP5578504B2 (ja) | 2014-08-27 |
CN102369161B (zh) | 2014-12-10 |
CN102369161A (zh) | 2012-03-07 |
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