CN1272251C - 钛酸钡基粉末的制备方法 - Google Patents
钛酸钡基粉末的制备方法 Download PDFInfo
- Publication number
- CN1272251C CN1272251C CNB028159187A CN02815918A CN1272251C CN 1272251 C CN1272251 C CN 1272251C CN B028159187 A CNB028159187 A CN B028159187A CN 02815918 A CN02815918 A CN 02815918A CN 1272251 C CN1272251 C CN 1272251C
- Authority
- CN
- China
- Prior art keywords
- barium titanate
- titanate powder
- oxalate
- prepare
- titanyl
- 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.)
- Expired - Fee Related
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 55
- 239000000843 powder Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 45
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 15
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 11
- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 claims description 40
- 229940094800 barium oxalate Drugs 0.000 claims description 40
- 238000001238 wet grinding Methods 0.000 claims description 21
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 11
- 229940045511 barium chloride Drugs 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 150000003868 ammonium compounds Chemical class 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 150000001413 amino acids Chemical class 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 239000004475 Arginine Substances 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- -1 Carboxyl Chemical group 0.000 claims description 3
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 3
- XUYPXLNMDZIRQH-LURJTMIESA-N N-acetyl-L-methionine Chemical compound CSCC[C@@H](C(O)=O)NC(C)=O XUYPXLNMDZIRQH-LURJTMIESA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229930182817 methionine Natural products 0.000 claims description 3
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims 2
- 150000001455 metallic ions Chemical class 0.000 claims 2
- 238000010298 pulverizing process Methods 0.000 abstract description 13
- 229910052788 barium Inorganic materials 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 abstract description 2
- 239000011324 bead Substances 0.000 abstract description 2
- QKKWJYSVXDGOOJ-UHFFFAOYSA-N oxalic acid;oxotitanium Chemical compound [Ti]=O.OC(=O)C(O)=O QKKWJYSVXDGOOJ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 22
- 239000002002 slurry Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 241000370738 Chlorion Species 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000003483 aging Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000009837 dry grinding Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- MTZOKGSUOABQEO-UHFFFAOYSA-L barium(2+);phthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O MTZOKGSUOABQEO-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
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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
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
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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
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
- C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3215—Barium 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
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
- C04B2235/3234—Titanates, not containing zirconia
- C04B2235/3236—Alkaline earth titanates
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, 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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
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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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
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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
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Abstract
本发明涉及一种用于制备钛酸钡基粉末的方法。更具体地说，本发明提供一种用于制备钛酸钡粉末的方法，包括下述步骤：通过经由一个喷嘴向草酸水溶液喷淋氯化钡(BaCl2·2H2O)和四氯化钛(TiCl4)水溶液的混合物，沉淀出钛氧基草酸钡(BaTiO(C2O4)2·4H2O)；在添加了添加剂、例如胺之后，利用一个珠磨机进行湿粉碎；干燥；热解；并进行再粉碎。
Description
发明的领域
本发明涉及一种用于制备钛酸钡基粉末的方法。更具体地说，本发明提供一种用于制备钛酸钡基的方法，包括以下步骤：通过经由一个喷嘴向草酸的水溶液喷淋氯化钡(BaCl2·2H2O)和四氯化钛(TiCl4)的水溶液混合物，沉淀出钛氧基草酸钡(BaTiO(C2O4)·4H2O)；在添加例如胺的添加剂之后，采用一个珠磨机(beads mill)进行湿粉碎；干燥；热解；并再次粉末化。
发明的背景
钛酸钡粉末已经广泛地用于生产多层陶瓷片电容器(MLCC)、正温度系数热敏电阻、电阻器等。已知可以利用碳酸钡(BaCO3)和二氧化钛(TiO2)在高温下的固态反应制造钛酸钡粉末。MLCC(多层陶瓷片电容器)的发展趋势是在越来越小型化，同时保持大容量、在低温、高频下的煅烧、以及容积效率，不仅对于更加精细和更均匀的钛酸钡粉末的要求极大地增加，而且对于纯度和分布的需要也逐步提高。因此，已经开发出多种液态反应方法、例如水热法、共同沉淀(草酸盐)法和烷氧化物法，用以生产满足这些特性的钛酸钡粉末。
在Journal of Research of the National Bureau of Standards，Vol.56(5)，289-291(1956)中，W.S.Clabaugh等人对草酸盐法进行了探讨，通过向草酸中添加包含Ba和Ti离子的混合物溶液，沉淀钛氧基草酸钡(barium titanyl oxalate)，生产钛酸钡。然而，该方法存在一些缺点：(i)难以控制颗粒尺寸和Ba相对于Ti的化学计量摩尔比；(ii)在热解过程中形成颗粒之间的硬质聚集体，因此需要强力粉碎以取出这些硬质聚集体；(iii)由于在强力粉碎过程中大量产生极其精细的颗粒，所以难以分散这些粉末并且在烧结过程中发生反常晶粒长大。因此，按照这种方式生产的钛酸钡粉末不适用于多层陶瓷电容器。
因此，由于在MLCC中存在需要更薄和更多层的介电层的倾向，所以最近人们对水热法给与关注。然而，尽管产品质量很高，但是这种方法也存在缺点，例如由于采用高压釜所以制造成本高且工艺复杂。因此，需要开发更为简便的低价制备钛酸钡粉末的方法，以便在市场中更具竞争力。
本发明的发明人在南韩提出了用于钛酸钡制备的专利申请(韩国专利申请Nos.2000-46125和2001-9066)，这种制备方法表现出可以以缩短的反应时间和钡相对于钛的最佳的化学计量提高生产产量。在上述韩国专利申请中公开的用于制备钛酸钡粉末的方法包括以下步骤：通过经由一个喷嘴向草酸的水溶液高速喷淋氯化钡(BaCl2·2H2O)和四氯化钛(TiCl4)的水溶液混合物、并对其进行陈化、过滤和清洗，制备钛氧基草酸钡(BaTiO(C2O4)·4H2O)；粉碎所获得的钛氧基草酸钡，干燥并热解，以便生产钛酸钡(BaTiO3)粉末；并且对预粉碎的钛酸钡粉末进行再粉碎。在粉碎过程中，可以利用例如采用一个喷雾器和喷射式磨机的干粉碎的方法、或采用一个球磨机、行星式磨机和珠磨机。在需要在研磨步骤中将钛酸钡(BaTiO3)与其它金属添加剂混合的情况下，更优选采用湿粉碎。在湿粉碎装置之中，行星式磨机或球磨机适于实验室规模的生产，而珠磨机适用于工业规模的生产。
然而，当采用珠磨机进行钛氧基草酸钡的湿粉碎时，会导致下述问题：
(1)在沉淀步骤中，存在于溶液中的杂质堵塞钛氧基草酸钡颗粒的内侧。因此，无论怎样清洗，杂质、例如草酸或氯离子也会保留在通过共同沉淀(草酸盐)法制备的钛氧基草酸钡中。由于这种与水混合的钛氧基草酸钡的pH值在3左右，所以可能导致以不锈钢为材料的预混合器的腐蚀。进而，在采用耐酸材料、例如聚氨酯的情况下，难以控制放热。因此，需要采用昂贵的材料、例如钛作为预混合器。在湿粉碎之后，钛氧基草酸钡浆料的pH值变为2，比湿粉碎之前的pH值低。因此，会减小珠磨机(磨室内部)的材料、例如锆和聚氨酯的耐用性。进而，导致干燥机的腐蚀。
(2)在钛氧基草酸钡中存在氯离子在烧结过程中将导致BaCl2液相的形成，在Journal of Inorganic chemistry，vol.9(11)2381～89(1970)中公开了这一点。因此，经过煅烧的钛酸钡更为聚集在一起，并且表现出很差的介电特性。
发明的概述
因此，本发明的一个目的是，通过解决在韩国专利Nos.2000-46125和2001-9066中公开的用于制备钛酸钡的工艺中、与钛氧基草酸钡的湿粉碎有关的问题，提供一种经济地生产钛酸钡粉末的工艺。
具体的，本发明涉及一种用于制备钛酸钡粉末的方法，包括步骤：
通过经由一个喷嘴高速地向草酸水溶液中喷淋氯化钡和四氯化钛水溶液的混合物，陈化，过滤并清洗，以获得钛氧基草酸钡；
在添加了选自氨、胺、铵化合物以及氨基酸的至少一种含氮添加剂之后，利用一个珠磨机对所获得的钛氧基草酸钡进行湿粉碎，干燥并热解，以生产钛酸钡粉末；并且
对所获得的钛酸钡粉末进行再粉碎，其中
所述胺由下面的式(1)表示，
其中，R1表示C1-C5的烷基，且R2和R3单独地表示氢原子或C1-C5的烷基；且
所述铵化合物由下面的式(2)表示，
其中，其中R1、R2、R3和R4单独地表示氢原子或C1-C5的烷基；A表示羟基，其中n＝1；硝酸根，其中n＝1；硫酸根，其中n＝2；磷酸根，其中n＝3；碳酸根，其中n＝2；碳酸氢根，其中n＝1；C1-C10羧基，其中n＝1；或C2-C10二羧基，其中n＝2；且
所述氨基酸是选自精氨酸和赖氨酸的至少一种，
其中，所述含氮添加剂相对于钛氧基草酸钡的使用范围在0.5至20mol％。
附图的简单说明
结合附图，从本发明的下述详细说明中可以更加清楚地理解本发明的上述目的，其中：
图1表示利用本发明方法生产的钛酸钡粉末的SEM图像。
发明的详细说明
本发明提供一种用于制备钛酸钡粉末的方法，包括步骤：
通过经由一个喷嘴向草酸水溶液喷淋氯化钡(BaCl2·2H2O)和四氯化钛(TiCl4)的水溶液混合物，沉淀钛氧基草酸钡(BaTiO(C2O4)2·4H2O)；
在添加了从氨、胺、铵化合物和氨基酸中选出的添加剂之后，利用一个珠磨机进行湿粉碎；
热解以生产钛酸钡粉末；并且
对所获得的钛酸钡粉末进行再粉碎。
从本发明的下述说明可以理解本发明，其中更加详细地描述了用于制备钛酸钡的工艺。
第一步是通过经由一个喷嘴向草酸水溶液高速喷淋氯化钡和四氯化钛的水溶液混合物以沉淀钛氧基草酸钡、陈化、过滤并且用水清洗。通过在水中溶解二水合氯化钡制备氯化钡水溶液，并且优选的氯化钡浓度在从0.2至2.0mol/l的范围内。通过稀释四氯化钛溶液制备四氯化钛水溶液，并且优选的四氯化钛浓度在从0.2至2.0mol/l的范围内。当相互添加氯化钡和四氯化钛水溶液时，钡化合物/钛化合物的摩尔比控制在1至1.5的范围内，更优选在1至1.1的范围内。草酸水溶液的浓度优选在0.2至5.0mol/l的范围内，并且温度保持在20至100℃的范围内，更优选在50至90℃的范围内。
所制备的氯化钡和四氯化钛的混合物，通过喷淋经由一个喷嘴持续1至3小时添加到草酸水溶液中。本发明中采用的喷嘴可以为单流体喷嘴或双流体喷嘴，为了方便起见，优选采用单流体喷嘴。
进行0.5至2小时的陈化，然后用水对粗制钛氧基草酸钡进行清洗，直到清洗的pH值变为中性为止，以便生产相应的钛氧基草酸钡。
第二个步骤是利用一个珠磨机对所获得的钛氧基草酸钡进行湿粉碎并干燥。在湿粉碎中采用的溶剂为去离子水，所用的量为相对于1份重量的钛氧基草酸钡采用1到10份重量的去离子水。在湿粉碎的过程中，加入含氮的添加剂，以防止由于在钛氧基草酸钡中存在氯离子而引起的在粉碎之后混合物的酸化、和粉末介电特性的下降。
含氮添加剂的例子包括氨、胺、铵化合物和氨基酸。特别地，由于粉末的介电特性、例如介电常数和绝缘电阻下降，所以采用无机碱、例如氢氧化钠、碳酸钾和碳酸氢钠去除氯离子并不是优选的。然而，由于不含有金属阳离子，所以本发明中采用的含氮添加剂则是优选的。
在本发明中采用的胺由下面的式(1)表示，
其中，R1、R2和R3单独地表示氢原子或C1-C5烷基。
伯胺、仲胺或叔胺的例子包括甲胺、二甲胺、三甲胺、二乙胺、三乙胺。
本发明中采用的铵化合物由下面的式(2)表示，
其中R1、R2和R3单独地表示氢原子或C1-C5烷基；A表示羟基(n＝1)，硝酸根(n＝1)，硫酸根(n＝2)，磷酸根(n＝3)，碳酸根(n＝2)，碳酸氢根(n＝1)，C1-C10羧基(n＝1)，或C2-C10二羧基(n＝2)。
铵化合物的优选例子包括氢氧化铵、碳酸铵、乙酸铵、磷酸铵、草酸铵、碳酸氢铵和氢氧化三甲铵。氨基酸的例子包括精氨酸和赖氨酸。
在相对于钛氧基草酸钡的0.5至20mol％的范围内使用含氮添加剂。如果低于0.5mol％，则在酸性和浆料中的氯化物含量方面不能令人满意。另一方面，如果超过20mol％，则由于成分钛的损失而造成Ba相对于Ti的非化学当量摩尔比。
进而，二价或四价金属可以与含氮添加剂任意结合并且取代Ba或Ti的位置。二价金属可以取代Ba，四价金属可以取代Ti。二价金属的例子包括Mg、Ca、Sr和Pb，并且四价元素的例子包括Zr、Hf和Sn。这些金属可以以氧化物、碳酸盐、氯化物或硝酸盐的形式使用。例如，将这种替换元素的氧化物、碳酸盐、氯化物或硝酸盐添加到钛氧基草酸钡中，以生产钙钛矿型钛酸钡基粉末、例如Ba(Ti1-zZrz)O3、(Ba1-xCax)(Ti1-zZrz)O3、(Ba1-x-yCaxSry)(Ti1-zZrz)O3等。
对湿粉碎的钛氧基草酸钡进行干燥并热解，以便在存在添加剂的情况下形成钛酸钡。在热解过程中加热的速率优选在0.5至10℃/min的范围内，并且温度保持在700至1200℃。
最后的步骤是对所获得的钛酸钡粉末进行再粉碎。通过采用一个喷雾器或喷射式磨机进行干粉碎、或者采用一个球磨机、行星式磨机或珠磨机进行湿粉碎，可以容易地对钛酸钡粉末进行粉碎。仅当进行湿粉碎时，采用加热炉、干燥器或喷雾干燥器进行干燥。
下述例子用于进一步解释本发明，而不对其范围进行限制。进而，本发明的范围不限于钛酸钡粉末，根据添加剂的种类和添加量还包括潜在的以钛酸钡为基的粉末。
例1
将1200l的1mol/l的TiCl4的水溶液和1320l的1mol/l的BaCl2的水溶液加入到玻璃衬里的4M3的反应器中并进行混合。通过一个例如充圆锥型的单流体喷嘴以21l/min的速度将该混合物喷淋到6M3的反应器中的2520l的1mol/l的草酸水溶液中。以150rpm的速度对草酸溶液进行搅拌，并将其温度保持在90℃。采用一个膜片泵作为喷淋混合物溶液的供应泵。在向草酸喷淋混合物2小时之后，在反应温度下对混合物溶液搅拌1小时并在室温下搅拌1小时，以生产钛氧基草酸钡浆料。利用离心机对钛氧基草酸钡浆料进行过滤，并且用水清洗，直到滤出液的pH达到pH6以上为止。基于Ti离子产率为98％，并且Ba对于Ti的摩尔比为0.999(水含量为24％)。
将0.5kg的29wt.％的氨水(相对于钛氧基草酸钡为10.1mol％)添加到在250kg的去离子水中的50kg的钛氧基草酸钡中。对浆料进行搅拌，并且其pH值在粉碎之前为9.3。然后，采用珠磨机对浆料进行湿粉碎，形成15μm的最大颗粒尺寸。浆料的pH值在粉碎之后为5.1。在于加热炉中以120℃对所获得的钛氧基草酸钡浆料干燥12小时之后，氯离子的含量为200ppm。然后，在一个电炉中，在1200℃下对钛氧基草酸钡浆料进行热解，并进行干粉碎，以生产钛酸钡粉末。图1中表示出草酸钡粉末的SEM图像。
例2-6
除了在湿粉碎过程中改变氨水的量之外，以与例1相同的步骤制备钛酸钡粉末。在表1中汇总出了所获得的浆料的特性。
比较例1
采用与例1相同的步骤制备钛氧基草酸钡，并且Ba/Ti的摩尔比为0.999(水含量为24％)。
将50kg的钛氧基草酸钡和250kg的去离子水置于反应器中并进行搅拌。浆料在粉碎之前的pH值为3.0。然后，利用一个珠磨机将浆料湿粉碎至最大颗粒尺寸为15μm。钛氧基草酸钡浆料在粉碎之后的pH值为2.0。在于加热炉中在120℃下对所获得的钛氧基草酸钡浆料干燥12小时之后，氯离子含量为10000ppm。然后，利用与例1相同的步骤制备钛酸钡粉末。
表1
| 类别 | 氨水的使用量(mol％) | 粉碎前 | 粉碎后 | |||
| pH | Ba/Ti比* | pH | Cl-的含量 | Ba/Ti比* | ||
| 例1 | 10.1 | 9.3 | 0.999 | 5.1 | 200 | 0.999 |
| 例2 | 0.4 | 8.3 | 0.999 | 3.0 | 500 | 0.999 |
| 例3 | 0.5 | 9.0 | 0.999 | 5.0 | 200 | 0.999 |
| 例4 | 20 | 10.0 | 0.999 | 5.2 | 200 | 0.999 |
| 例5 | 21 | 10.2 | 0.999 | 5.4 | 200 | 1.001 |
| 例6 | 25 | 10.2 | 0.999 | 5.4 | 200 | 1.005 |
| 比较例1 | - | 3.0 | 0.999 | 2.0 | 10000 | 0.999 |
| Ba/Ti比*：XRF测量 | ||||||
例7-12
除了在湿粉碎过程中采用不同量的不同添加剂之外，利用与例1相同的步骤制备钛酸钡粉末。在表2中汇总了所获得的浆料的特性。
表2
| 类别 | 添加剂 | 粉碎前 | 粉碎后 | ||||
| 添加剂 | 量(mol％) | pH | Ba/Ti比* | pH | Cl-的含量 | Ba/Ti比* | |
| 例7 | 醋酸铵 | 10 | 6.8 | 0.999 | 5.1 | 200 | 0.999 |
| 例8 | 硝酸铵 | 8 | 5.5 | 0.999 | 4.9 | 200 | 0.999 |
| 例9 | 三乙胺 | 15 | 10.2 | 0.999 | 5.0 | 200 | 0.999 |
| 例10 | 碳酸铵 | 14 | 7.9 | 0.999 | 4.8 | 200 | 0.999 |
| 例11 | 磷酸铵 | 13 | 8.1 | 0.999 | 5.0 | 200 | 0.999 |
| 例12 | 精氨酸 | 12 | 8.0 | 0.999 | 4.8 | 200 | 0.999 |
| Ba/Ti比*：XRF测量 | |||||||
例13
除了在粉碎过程中添加氨水并额外添加CaCO3和ZrO2之外，利用与例1相同的步骤制备钛氧基草酸钡。然后，在1190℃下进行干燥、热解，并进行粉碎，以生产(Ba0.952Ca0.05)(Ti0.84Zr0.16)O3。
所获得的钙钛矿型钛酸钡粉末具有0.52μm的平均颗粒尺寸和4.02m2/g的比表面积。
比较例2
除了在粉碎过程中不添加氨水之外，利用与例13相同的步骤制备(Ba0.952Ca0.05)(Ti0.84Zr0.16)O3。
所获得的钙钛矿型钛酸钡粉末具有0.54μm的平均颗粒尺寸和4.01m2/g的比表面积。
试验例：导电特性的确定
将PVA粘合剂和一些用于Y5V的添加剂加入到在例13和比较例2中制备的各钛酸钡粉末中。在一个氧化铝研体中将各混合物充分混合并干燥。然后，在该研体中将各混合物压碎并筛选，以便获得颗粒。在一个模具中将0.4g的各个颗粒压成Φ10mm的盘状。然后，对一些介电特性进行测试，并且将结果表示在表3中。
表3
| 类别 | 生坯密度(g/cm3) | 烧结密度(g/cm3) | 介电常数 | 介电损耗(％) | 绝缘电阻(1011Ω) | TCC*(％) |
| 例13 | 3.69 | 5.90 | 12100 | 3.72 | 0.44 | -60.3/10.2 |
| 比较例2 | 3.68 | 5.89 | 10000 | 4.57 | 0.01 | -67.2/13.8 |
| *TCC：电容的温度系数 | ||||||
如表3所示，根据本发明的通过在湿粉碎过程中采用添加剂制备的钛酸钡粉末(例13)与利用传统方法制备的钛酸钡粉末(比较例2)相比，具有优异的导电特性(例如，较高的介电性、较高的绝缘电阻、较低的介电损耗)。
如上所述，在采用草酸衍生法制备高质量的钛酸钡粉末的工艺中，通过在湿粉碎过程中对钛氧基草酸钡采用含氮添加剂、例如胺，以防止在粉碎之前和之后、由于氯离子的存在而使浆料酸化且粉末的介电特性下降，本发明提供了一种改进的钛酸钡粉末制造工艺。因此，本发明适用于用作多层陶瓷电容器、PTC热敏电阻、电阻器等的材料。
Claims (8)
1、一种用于制备钛酸钡粉末的方法，包括步骤：
通过经由一个喷嘴高速地向草酸水溶液中喷淋氯化钡和四氯化钛水溶液的混合物，陈化，过滤并清洗，以获得钛氧基草酸钡；
在添加了选自氨、胺、铵化合物以及氨基酸的至少一种含氮添加剂之后，利用一个珠磨机对所获得的钛氧基草酸钡进行湿粉碎，干燥并热解，以生产钛酸钡粉末；并且
对所获得的钛酸钡粉末进行再粉碎，其中
所述胺由下面的式(1)表示，
其中，R1表示C1-C5的烷基，且R2和R3单独地表示氢原子或C1-C5的烷基；且
所述铵化合物由下面的式(2)表示，
其中，其中R1、R2、R3和R4单独地表示氢原子或C1-C5的烷基；A表示羟基，其中n＝1；硝酸根，其中n＝1；硫酸根，其中n ＝2；磷酸根，其中n＝3；碳酸根，其中n＝2；碳酸氢根，其中n＝1；C1-C10羧基，其中n＝1；或C2-C10二羧基，其中n ＝2；且
所述氨基酸是选自精氨酸和赖氨酸的至少一种，
其中，所述含氮添加剂相对于钛氧基草酸钡的使用范围在0.5至20mol％。
2、如权利要求1所述的用于制备钛酸钡粉末的方法，其中R4表示氢原子。
3、如权利要求1所述的用于制备钛酸钡粉末的方法，其中，所述胺是选自甲胺、二甲胺、三甲胺、二乙胺和三乙胺的至少一种。
4、如权利要求1所述的用于制备钛酸钡粉末的方法，其中，所述铵化合物是选自氢氧化铵、碳酸铵、乙酸铵、磷酸铵、草酸铵、碳酸氢铵和氢氧化三甲铵的至少一种。
5、如权利要求1所述的用于制备钛酸钡粉末的方法，其中，二价或四价金属离子与所述含氮添加剂一起使用。
6、如权利要求5所述的用于制备钛酸钡粉末的方法，其中，所述二价金属离子是从Mg、Ca、Sr和Pb组成的组中选出的至少一种。
7、如权利要求5所述的用于制备钛酸钡粉末的方法，其中，所述四价金属离子是从Zr、Hf和Sn组成的组中选出的至少一种。
8、如权利要求5、6和7任何一项所述的用于制备钛酸钡粉末的方法，其中，所述金属离子是所述金属的氧化物、碳酸盐、氯化物或硝酸盐的形式。
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| US8137647B2 (en) * | 2006-12-28 | 2012-03-20 | E. I. Du Pont De Nemours And Company | Processes for producing titanium dioxide |
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| US9375750B2 (en) | 2012-12-21 | 2016-06-28 | Valinge Photocatalytic Ab | Method for coating a building panel and a building panel |
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| JP7438867B2 (ja) | 2019-07-16 | 2024-02-27 | 日本化学工業株式会社 | Ｍｅ元素置換有機酸バリウムチタニル、その製造方法及びチタン系ペロブスカイト型セラミック原料粉末の製造方法 |
| JP7102462B2 (ja) | 2020-06-12 | 2022-07-19 | 日本化学工業株式会社 | シュウ酸バリウムチタニル、その製造方法及びチタン酸バリウムの製造方法 |
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| EP1441985A1 (en) | 2004-08-04 |
| JP2005500239A (ja) | 2005-01-06 |
| JP4060791B2 (ja) | 2008-03-12 |
| WO2003016219A1 (en) | 2003-02-27 |
| CN1541188A (zh) | 2004-10-27 |
| DE60222289T2 (de) | 2008-05-29 |
| DE60222289D1 (de) | 2007-10-18 |
| US20040253172A1 (en) | 2004-12-16 |
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| KR20030015011A (ko) | 2003-02-20 |
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