JP2021017441A - Me element substituted organic acid barium titanyl and method of producing the same, and method of producing titanium-based perovskite-type ceramic material powder - Google Patents
Me element substituted organic acid barium titanyl and method of producing the same, and method of producing titanium-based perovskite-type ceramic material powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 226
- 229910052788 barium Inorganic materials 0.000 title claims abstract description 134
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 123
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000010936 titanium Substances 0.000 title claims description 86
- 229910052719 titanium Inorganic materials 0.000 title claims description 43
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 38
- 238000000034 method Methods 0.000 title abstract description 21
- 229910010293 ceramic material Inorganic materials 0.000 title description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 91
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 64
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- 238000006467 substitution reaction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 110
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 86
- 238000004519 manufacturing process Methods 0.000 claims description 61
- 239000000919 ceramic Substances 0.000 claims description 40
- 238000010304 firing Methods 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 35
- 239000002994 raw material Substances 0.000 claims description 34
- 235000006408 oxalic acid Nutrition 0.000 claims description 27
- 238000004458 analytical method Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 23
- -1 barium titanate organic acid Chemical class 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000013507 mapping Methods 0.000 claims description 19
- 150000001552 barium Chemical class 0.000 claims description 18
- 229910052712 strontium Inorganic materials 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 15
- 150000001553 barium compounds Chemical class 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 150000003609 titanium compounds Chemical class 0.000 claims description 10
- 239000000523 sample Substances 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 7
- 229910001626 barium chloride Inorganic materials 0.000 claims description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000010191 image analysis Methods 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 claims description 2
- 238000005204 segregation Methods 0.000 abstract description 32
- 239000011575 calcium Substances 0.000 description 101
- AWYLBRXYPXRMFS-UHFFFAOYSA-J calcium barium(2+) oxalate Chemical compound [Ca++].[Ba++].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O AWYLBRXYPXRMFS-UHFFFAOYSA-J 0.000 description 35
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 32
- 229960005069 calcium Drugs 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000003756 stirring Methods 0.000 description 18
- 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 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 14
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- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 7
- 229940094800 barium oxalate Drugs 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 description 6
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 6
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- QKKWJYSVXDGOOJ-UHFFFAOYSA-N oxalic acid;oxotitanium Chemical compound [Ti]=O.OC(=O)C(O)=O QKKWJYSVXDGOOJ-UHFFFAOYSA-N 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000007561 laser diffraction method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SRLPPRVVQNACSW-UHFFFAOYSA-L 2-hydroxypropanoate;titanium(2+) Chemical compound [Ti+2].CC(O)C([O-])=O.CC(O)C([O-])=O SRLPPRVVQNACSW-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- FWZUNOYOVVKUNF-UHFFFAOYSA-N allyl acetate Chemical compound CC(=O)OCC=C FWZUNOYOVVKUNF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 229910052758 niobium Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 229910052706 scandium Inorganic materials 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- 238000005245 sintering Methods 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、誘電体、圧電体、オプトエレクトロニクス材、半導体、センサー等の機能性セラミックの原料として有用なバリウム元素の一部を他の元素で置換した有機酸バリウムチタニル及びその製造方法に関するものである。 The present invention relates to barium titanyl organic acid in which a part of barium element useful as a raw material for functional ceramics such as dielectrics, piezoelectric materials, optelectronic materials, semiconductors, and sensors is replaced with another element, and a method for producing the same. is there.
積層セラミックチップコンデンサ（ＭＬＣＣ） の誘電体層は、主原料であるチタン酸バリウムと微量の添加剤とから構成される多成分系の形をとることが一般的である。例えば、カルシウムは添加剤としてよく使用される成分であるが、チタン酸バリウムにおけるバリウムサイトへ置換固溶することで、誘電体の比誘電率の温度特性をなめらかにするディプレッサーとしての効果、あるいは焼結助剤となるガラスの成分として使用されることなどが知られている。 The dielectric layer of a multilayer ceramic chip capacitor (MLCC) generally takes the form of a multi-component system composed of barium titanate, which is a main raw material, and a trace amount of additives. For example, calcium is a component often used as an additive, but it has the effect of a depressor that smoothes the temperature characteristics of the relative permittivity of a dielectric by substituting and solidifying it in barium site in barium titanate. It is known that it is used as a component of glass as a sintering aid.
前記した多成分系の形をとるチタン酸バリウムは、従来から知られている固相法、シュウ酸塩法、水熱合成法、アルコキシド法等を用いて、微量成分を添加することにより得られる。これらのうち、シュウ酸塩法は、湿式合成されたシュウ酸塩前駆体を熱処理し、脱シュウ酸することでチタン酸バリウムを合成する製法である。そして、シュウ酸塩法の最大の特徴は、前駆体結晶におけるバリウムとチタンの組成比（Ｂａ／Ｔｉ）から高品位で化学量論的なチタン酸バリウムが得られることである。 The above-mentioned barium titanate in the form of a multi-component system can be obtained by adding a trace amount of components using a conventionally known solid-phase method, oxalate method, hydrothermal synthesis method, alkoxide method, or the like. .. Of these, the oxalate method is a production method for synthesizing barium titanate by heat-treating a wet-synthesized oxalate precursor and deoxalic acid. The greatest feature of the oxalate method is that high-quality and stoichiometric barium titanate can be obtained from the composition ratio (Ba / Ti) of barium and titanium in the precursor crystal.
シュウ酸塩法には、いくつかのプロセスが報告されているが、工業的には、塩化チタンと塩化バリウムの混合液をシュウ酸水溶液に添加して反応を行う方法が一般的である。このシュウ酸塩法を用いてバリウム元素の一部を他の金属元素で置換したシュウ酸バリウムチタニルを製造する方法が提案されている。 Although several processes have been reported for the oxalate method, industrially, a method of adding a mixed solution of titanium chloride and barium chloride to an oxalic acid aqueous solution to carry out the reaction is common. A method for producing barium titanyl oxalate in which a part of barium element is replaced with another metal element by using this oxalate method has been proposed.
例えば、特許文献１では、塩化チタン、塩化バリウムの混合液に、置換する他のアルカリ土類金属化合物を含有させて、これをシュウ酸水溶液に添加して行う方法が記載されている。しかし、定量的に反応が進みにくいため工業的に有利でない欠点がある。 For example, Patent Document 1 describes a method in which a mixed solution of titanium chloride and barium chloride is contained with another alkaline earth metal compound to be substituted, and this is added to an aqueous oxalic acid solution. However, there is a drawback that it is not industrially advantageous because the reaction does not proceed quantitatively.
そこで、定量的に反応を進めるために、特許文献２では、四塩化チタンとシュウ酸を含有する溶液を、バリウム化合物と、置換する他の元素を含む化合物を含有する溶液に添加して反応を行うと、反応性が向上し、バリウムと置換する他の元素の置換率が高いシュウ酸バリウムチタニルが得られることが記載されている。 Therefore, in order to proceed with the reaction quantitatively, in Patent Document 2, a solution containing titanium tetrachloride and oxalic acid is added to a solution containing a barium compound and a compound containing another element to be substituted to carry out the reaction. It is described that this results in barium titanyl oxalate, which has improved reactivity and a high substitution rate for other elements that replace barium.
また、特許文献３には、シュウ酸とチタンを含む第１の水溶液を、アンモニアとカルシウム、バリウム及びストロンチウムから選ばれる少なくとも１種とを含む第２の水溶液に滴下、混合することにより、バリウム、カルシウムといったアルカリ土類金属及びチタンの分散性が良好で、均一性に優れたセラミックス原料微粉末が得られることが記載されている。 Further, in Patent Document 3, a first aqueous solution containing oxalic acid and titanium is added dropwise and mixed with a second aqueous solution containing ammonia and at least one selected from calcium, barium and strontium to obtain barium. It is described that fine powders of ceramic raw materials having good dispersibility of alkaline earth metals such as calcium and titanium and excellent uniformity can be obtained.
しかし、引用文献２に記載の方法では、バリウムサイトにカルシウムなどの他の元素を高い確率で置換させることができるが、反応性が高過ぎるため、シュウ酸バリウムチタニル全体に均一に置換元素を分布させることが困難となる問題があった。 However, in the method described in Cited Document 2, barium sites can be substituted with other elements such as calcium with a high probability, but since the reactivity is too high, the substituted elements are uniformly distributed throughout barium titanyl oxalate. There was a problem that it was difficult to make it.
また、引用文献３の実施例によると、仕込み組成に応じた組成の生成物が得られることが記載されているが、均一性に関する評価はなく、また、アンモニアを用いてｐＨ調整を行うこともあり、工業的に有利な方法であるとはいえない。 Further, according to the examples of Cited Document 3, it is described that a product having a composition corresponding to the charged composition can be obtained, but there is no evaluation regarding uniformity, and pH adjustment may be performed using ammonia. Yes, it is not an industrially advantageous method.
従って、本発明の目的は、Ｂａサイトの一部が他の元素（Ｍｅ元素）で置換されている有機酸バリウムチタニル及びチタン酸バリウムであって、置換元素が偏析せずに、有機酸バリウムチタニル粉末全体又はチタン酸バリウム粉末全体に、均一に分布しているＭｅ元素置換有機酸バリウムチタニル粉末及びチタン酸バリウム粉末を提供すること、及び該有機酸バリウムチタニル又は該チタン酸バリウム粉末を工業的に有利に製造する方法を提供することにある。 Therefore, an object of the present invention is barium titanyl organic acid and barium titanate in which a part of Basite is substituted with another element (Me element), and barium titanyl organic acid without segregation of the substituted element. To provide a uniformly distributed Me element-substituted barium titanyl organic acid powder and barium titanate powder throughout the powder or barium titanate powder, and to industrially produce the barium titanyl organic acid or the barium titanate powder. The purpose is to provide a method for producing in an advantageous manner.
本発明者らは、上記実情に鑑み鋭意研究を重ねた結果、有機酸バリウムチタニルのＴｉに対するＢａ及びＭｅ元素の合計のモル比を１より少し小さい範囲の０．９８０〜０．９９９とし、且つ、Ｂａに対するＭｅ元素のモル比の範囲を０．００１〜０．２００とすることにより、偏析が少ない有機酸バリウムチタニル粉末が得られることを見出し、本発明を完成させるに至った。 As a result of diligent research in view of the above circumstances, the present inventors set the total molar ratio of Ba and Me elements to Ti of barium titanyl organic acid to 0.980 to 0.999 in a range slightly smaller than 1. By setting the molar ratio of the Me element to Ba to 0.001 to 0.200, it was found that a barium titanyl organic acid powder with less segregation can be obtained, and the present invention has been completed.
すなわち、本発明（１）は、Ｂａサイトの一部がＭｅ元素（Ｍｅは、Ｃａ、Ｓｒ及びＭｇから選ばれる少なくとも１種を示す。）に置換されているＭｅ元素置換有機酸バリウムチタニルであり、
Ｔｉに対するＢａとＭｅ元素の合計のモル比（（Ｂａ＋Ｍｅ）／Ｔｉ）が０．９８０以上０．９９９未満であり、Ｂａに対するＭｅ元素のモル比（Ｍｅ／Ｂａ）が０．００１以上０．２５０以下であること、
を特徴とするＭｅ元素置換有機酸バリウムチタニル粉末を提供するものである。
That is, the present invention (1) is a Me element-substituted barium titanyl organic acid in which a part of the Ba site is replaced with a Me element (Me indicates at least one selected from Ca, Sr and Mg). ,
The total molar ratio of Ba and Me element to Ti ((Ba + Me) / Ti) is 0.980 or more and less than 0.999, and the molar ratio of Me element to Ba (Me / Ba) is 0.001 or more and 0.250. Must be
The present invention provides a barium titanyl powder of a Me element-substituted organic acid characterized by the above.
また、本発明（２）は、電子プローブマイクロアナライザ（ＥＰＭＡ）分析において、前記Ｍｅ元素置換有機酸バリウムチタニル粉末を焼成して得られるＭｅ元素置換チタン酸バリウム粉末の粒子に、前記Ｍｅ元素が均一に分布していることを特徴とする（１）のＭｅ元素置換有機酸バリウムチタニル粉末を提供するものである。 Further, in the present invention (2), in electron probe microanalyzer (EPMA) analysis, the Me element is uniform on the particles of the Me element-substituted barium titanate powder obtained by firing the Me element-substituted barium titanate organic acid powder. It provides the barium titanyl powder of the Me element-substituted organic acid of (1), which is characterized by being distributed in.
また、本発明（３）は、電子プローブマイクロアナライザ（ＥＰＭＡ）分析を用いて、前記Ｍｅ元素置換有機酸バリウムチタニル粉末を焼成して得られるＭｅ元素置換チタン酸バリウムの圧粉体の表面上を、一辺が２０５μｍの正方形の範囲となるように０．８μｍ間隔で縦横２５６点のマッピング分析して得られる画像解析において、ＣａのＣＶ値（標準偏差／平均値）が０．４以下であることを特徴とする（１）のＭｅ元素置換有機酸バリウムチタニル粉末を提供するものである。 Further, in the present invention (3), the Me element-substituted barium titanate powder obtained by firing the Me element-substituted barium titanate powder using electron probe microanalyzer (EPMA) analysis is applied on the surface of the green compact of Me element-substituted barium titanate. The CV value (standard deviation / average value) of Ca is 0.4 or less in the image analysis obtained by mapping analysis of 256 points in the vertical and horizontal directions at 0.8 μm intervals so that one side is in the range of a square of 205 μm. (1) Me element-substituted barium titanate organic acid powder according to (1) is provided.
また、本発明（４）は、バリウム化合物、Ｍｅ元素化合物及びチタン化合物を水に混合して得られる水溶液（Ａ液）を、有機酸水溶液（Ｂ液）に添加することにより、Ｍｅ元素置換有機酸バリウムチタニルを得るＭｅ元素置換有機酸バリウムチタニル粉末の製造方法であり、
該Ａ液中、原子換算で、Ｂａに対するＭｅ元素のモル比（Ｍｅ／Ｂａ）が０．０２０以上５．０００以下であり、Ｔｉに対するＢａのモル比（Ｂａ／Ｔｉ）が０．３００以上１．２００以下であり、且つ、Ａ液とＢ液の混合温度が１０〜５０℃であること、
を特徴とするＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を提供するものである。
Further, in the present invention (4), a Me element-substituted organic substance is added by adding an aqueous solution (solution A) obtained by mixing a barium compound, a Me element compound and a titanium compound with water to an organic acid aqueous solution (solution B). It is a method for producing a Me element-substituted organic acid barium titanyl powder for obtaining barium titanyl acid.
In the liquid A, the molar ratio of Me element to Ba (Me / Ba) is 0.020 or more and 5.000 or less, and the molar ratio of Ba to Ti (Ba / Ti) is 0.300 or more and 1 .200 or less, and the mixing temperature of solution A and solution B is 10 to 50 ° C.
The present invention provides a method for producing a barium titanyl powder containing a Me element-substituted organic acid.
また、本発明（５）は、前記バリウム化合物が、塩化バリウム、炭酸バリウム及び水酸化バリウムからなる群から選ばれる少なくとも１種であることを特徴とする（４）のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を提供するものである。 Further, the present invention (5) is characterized in that the barium compound is at least one selected from the group consisting of barium chloride, barium carbonate and barium hydroxide, and the Me element-substituted organic acid barium titanyl according to (4). It provides a method for producing a powder.
また、本発明（６）は、前記Ｍｅ元素化合物が、Ｍｅ元素の塩化物、Ｍｅ元素の炭酸塩及びＭｅ元素の水酸化物からなる群から選ばれる少なくとも１種であることを特徴とする（４）又は（５）のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を提供するものである。 Further, the present invention (6) is characterized in that the Me element compound is at least one selected from the group consisting of Me element chloride, Me element carbonate and Me element hydroxide (6). It provides the method for producing the barium titanyl powder of Me element-substituted organic acid according to 4) or (5).
また、本発明（７）は、前記チタン化合物が、四塩化チタン及び乳酸チタンから選ばれる少なくとも１種であることを特徴とする（４）〜（６）いずれかのＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を提供するものである。 Further, the present invention (7) is characterized in that the titanium compound is at least one selected from titanium tetrachloride and titanium lactate lactate, which is any Me element-substituted organic acid barium titanyl (4) to (6). It provides a method for producing a powder.
また、本発明（８）は、前記有機酸がシュウ酸、クエン酸、マロン酸及びコハク酸からなる群から選ばれる少なくとも１種であることを特徴とする（４）〜（７）いずれかのＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を提供するものである。 Further, the present invention (8) is characterized in that the organic acid is at least one selected from the group consisting of oxalic acid, citric acid, malonic acid and succinic acid (4) to (7). The present invention provides a method for producing a barium titanyl powder of a Me element-substituted organic acid.
また、本発明（９）は、（１）〜（３）いずれかのＭｅ元素置換有機酸バリウムチタニル粉末を焼成することにより、Ｍｅ元素置換チタン酸バリウムを得ることを特徴とする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を提供するものである。 Further, the present invention (9) is a titanium-based perovskite type, characterized in that a Me element-substituted barium titanate powder is obtained by firing any of the Me element-substituted organic acid barium titanyl powders (1) to (3). It provides a method for producing a ceramic raw material powder.
また、本発明（１０）は、（４）〜（８）いずれかのＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を行い得られるＭｅ元素置換有機酸バリウムチタニル粉末を焼成することにより、Ｍｅ元素置換チタン酸バリウム粉末を得ることを特徴とする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を提供するものである。 Further, in the present invention (10), the Me element by firing the barium titanyl powder substituted organic acid obtained by carrying out the method for producing the barium titanyl powder substituted organic acid according to any one of (4) to (8). The present invention provides a method for producing a titanium-based perovskite-type ceramic raw material powder, which comprises obtaining a substituted barium titanate powder.
本発明によれば、Ｂａサイトの一部が他の元素（Ｍｅ元素）で置換されている有機酸バリウムチタニル及びチタン酸バリウムであって、置換元素が偏析せずに、有機酸バリウムチタニル粉末全体又はチタン酸バリウム粉末全体に、均一に分布しているＭｅ元素置換有機酸バリウムチタニル粉末及びチタン酸バリウム粉末を提供すること、及び該有機酸バリウムチタニル又は該チタン酸バリウム粉末を工業的に有利に製造する方法を提供することができる。 According to the present invention, barium titanyl organic acid and barium titanate in which a part of Basite is substituted with another element (Me element), and the entire barium titanyl organic acid powder is powdered without segregation of the substitution elements. Alternatively, providing a uniformly distributed Me element-substituted barium titanyl organic acid powder and barium titanate powder throughout the barium titanate powder, and industrially advantageous barium titanyl organic acid or the barium titanate powder. A method of manufacturing can be provided.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末は、Ｂａサイトの一部がＭｅ元素（Ｍｅは、Ｃａ、Ｓｒ及びＭｇから選ばれる少なくとも１種を示す。）に置換されているＭｅ元素置換有機酸バリウムチタニルであり、
Ｔｉに対するＢａとＭｅ元素の合計のモル比（（Ｂａ＋Ｍｅ）／Ｔｉ）が０．９８０以上０．９９９未満であり、Ｂａに対するＭｅ元素のモル比（Ｍｅ／Ｂａ）が０．００１以上０．２５０以下であること、
を特徴とするＭｅ元素置換有機酸バリウムチタニル粉末である。
The Me element-substituted organic acid barium titanyl powder of the present invention is a Me element-substituted organic acid in which a part of Basite is replaced with a Me element (Me indicates at least one selected from Ca, Sr and Mg). Barium titanil,
The total molar ratio of Ba and Me element to Ti ((Ba + Me) / Ti) is 0.980 or more and less than 0.999, and the molar ratio of Me element to Ba (Me / Ba) is 0.001 or more and 0.250. Must be
It is a barium titanyl powder of Me element-substituted organic acid characterized by.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末は、粉末状であり、Ｂａサイトの一部がＭｅ元素で置換された有機酸バリウムチタニルの粒子の集合物である。 The Me element-substituted barium titanyl organic acid powder of the present invention is in the form of a powder and is an aggregate of particles of barium titanyl organic acid in which a part of Basite is substituted with Me element.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末において、有機酸バリウムチタニルのＢａサイトの一部を置換しているＭｅ元素は、Ｃａ、Ｓｒ及びＭｇから選ばれる少なくとも１種の元素であり、好ましくはＣａ、Ｓｒであり、特に好ましくはＣａである。Ｍｅは、１種であっても、２種以上であってもよい。 In the Me element-substituted barium titanyl organic acid powder of the present invention, the Me element substituting a part of the Ba site of barium titanyl organic acid is at least one element selected from Ca, Sr and Mg, and is preferable. Ca and Sr, particularly preferably Ca. Me may be one kind or two or more kinds.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末中、有機酸は、シュウ酸、クエン酸、マロン酸及びコハク酸からなる群から選ばれる少なくとも１種であり、好ましくはシュウ酸、クエン酸であり、特に好ましくはシュウ酸である。 In the Me element-substituted organic acid barium titanyl powder of the present invention, the organic acid is at least one selected from the group consisting of oxalic acid, citric acid, malonic acid and succinic acid, preferably oxalic acid and citric acid. Particularly preferred is oxalic acid.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末中のＴｉに対するＢａとＭｅ元素の合計のモル比（（Ｂａ＋Ｍｅ）／Ｔｉ）は、０．９８０以上０．９９９未満であり、好ましくは０．９８３以上０．９９８以下、特に好ましくは０．９８５以上０．９９７以下である。（Ｂａ＋Ｍｅ）／Ｔｉが上記範囲にあることにより、Ｍｅ元素が粉末全体に均一に分布しており、Ｍｅ元素の偏析が少ない、Ｍｅ元素置換有機酸バリウムチタニル粉末が得られ、且つ、焼成により、Ｍｅ元素が粉末全体に均一に分布しており、Ｍｅ元素の偏析が少ない、Ｍｅ元素置換チタン酸バリウム粉末が得られる。一方、（Ｂａ＋Ｍｅ）／Ｔｉが上記範囲未満だと、所望の特性を有するＭｅ元素置換チタン酸バリウムが得られ難く、また、上記範囲を超えると、Ｍｅ元素の偏析が起こり易くなる。 The total molar ratio of Ba and Me element to Ti in the Me element-substituted organic acid barium titanyl powder of the present invention ((Ba + Me) / Ti) is 0.980 or more and less than 0.999, preferably 0.983 or more. It is 0.998 or less, particularly preferably 0.985 or more and 0.997 or less. When (Ba + Me) / Ti is in the above range, the Me element is uniformly distributed throughout the powder, and the Me element-substituted barium titanate organic acid powder having less segregation of the Me element can be obtained, and by firing, A barium titanate powder substituted with Me element is obtained in which the Me element is uniformly distributed throughout the powder and the segregation of the Me element is small. On the other hand, if (Ba + Me) / Ti is less than the above range, it is difficult to obtain barium titanate substituted with Me element having desired characteristics, and if it exceeds the above range, segregation of Me element is likely to occur.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末中のＢａに対するＭｅ元素のモル比（Ｍｅ／Ｂａ）が０．００１以上０．２５０以下であり、好ましくは０．００５以上０．１５０以下である。Ｍｅ／Ｂａが上記範囲にあることにより、Ｍｅ元素が粉末全体に均一に分布しており、Ｍｅ元素の偏析の少ない、Ｍｅ元素置換有機酸バリウムチタニルが得られ、且つ、焼成により、Ｍｅ元素が粒子全体に均一に分布しており、Ｍｅ元素の偏析の少ない、Ｍｅ元素置換チタン酸バリウムが得られる。一方、Ｍｅ／Ｂａが上記範囲未満だと、所望の特性を有するＭｅ元素置換チタン酸バリウムが得られ難く、また、上記範囲を超えると、Ｍｅ元素の偏析が起こり易くなる。 The molar ratio (Me / Ba) of the Me element to Ba in the barium titanyl powder of the Me element substituted organic acid of the present invention is 0.001 or more and 0.250 or less, preferably 0.005 or more and 0.150 or less. When Me / Ba is in the above range, the Me element is uniformly distributed throughout the powder, and the Me element-substituted barium titanate organic acid having less segregation of the Me element can be obtained, and the Me element can be obtained by firing. Barium titanate substituted with Me element, which is uniformly distributed over the entire particle and has less segregation of Me element, can be obtained. On the other hand, if Me / Ba is less than the above range, it is difficult to obtain barium titanate substituted with Me element having desired characteristics, and if it exceeds the above range, segregation of Me element is likely to occur.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末のうち、有機酸がシュウ酸であるものとしては、例えば、下記一般式（１）：
（Ｂａ１−ｐＭｅｐ）ｑＴｉＯ（Ｃ２Ｏ４）２・ｎＨ２Ｏ （１）
（式中、Ｍｅは、Ｃａ、Ｓｒ及びＭｇから選ばれる少なくとも１種の元素を表し、ｐが、０．００１≦ｐ≦０．２００であり、ｑが、０．９８０≦ｑ＜０．９９９であり、ｎは、１〜８の整数である。）
で表されるＭｅ元素置換シュウ酸バリウムチタニル粉末が挙げられる。
Among the Me element-substituted organic acid barium titanyl powders of the present invention, examples of the powder in which the organic acid is oxalic acid include the following general formula (1):
(Ba 1-p Me p ) q TiO (C 2 O 4 ) 2. nH 2 O (1)
(In the formula, Me represents at least one element selected from Ca, Sr and Mg, p is 0.001 ≦ p ≦ 0.200, and q is 0.980 ≦ q <0.999. And n is an integer of 1-8.)
Examples thereof include barium titanyl oxalate powder substituted with Me element represented by.
一般式（１）中、Ｍｅは、Ｃａ、Ｓｒ及びＭｇから選ばれる少なくとも１種の元素であり、好ましくはＣａ、Ｓｒであり、特に好ましくはＣａである。Ｍｅは、１種であっても、２種以上であってもよい。つまり、一般式（１）で表されるＭｅ元素置換シュウ酸バリウムチタニル粉末は、Ｂａサイトの一部が、Ｃａ、Ｓｒ及びＭｇから選ばれる１種又は２種以上で置換されている。 In the general formula (1), Me is at least one element selected from Ca, Sr and Mg, preferably Ca and Sr, and particularly preferably Ca. Me may be one kind or two or more kinds. That is, in the Me element-substituted barium titanyl oxalate powder represented by the general formula (1), a part of the Ba site is replaced with one or more selected from Ca, Sr and Mg.
一般式（１）中、ｑの値は、原子換算のＴｉに対するＢａとＭｅ元素の合計のモル比（（Ｂａ＋Ｍｅ）／Ｔｉ）に相当する。ｑは、０．９８０以上０．９９９未満であり、好ましくは０．９８３以上０．９９８以下、特に好ましくは０．９８５以上０．９９７以下である。ｑが上記範囲にあることにより、Ｍｅ元素が粉末全体に均一に分布しており、Ｍｅ元素の偏析が少ない、Ｍｅ元素置換シュウ酸バリウムチタニル粉末が得られ、且つ、焼成により、Ｍｅ元素が粉末全体に均一に分布しており、Ｍｅ元素の偏析が少ない、Ｍｅ元素置換チタン酸バリウム粉末が得られる。一方、ｑが上記範囲未満だと、所望の特性を有するＭｅ元素置換チタン酸バリウムが得られ難く、また、上記範囲を超えると、Ｍｅ元素の偏析が起こり易くなる。 In the general formula (1), the value of q corresponds to the total molar ratio of Ba and Me elements to Ti in terms of atoms ((Ba + Me) / Ti). q is 0.980 or more and less than 0.999, preferably 0.983 or more and 0.998 or less, and particularly preferably 0.985 or more and 0.997 or less. When q is in the above range, the Me element is uniformly distributed throughout the powder, a Me element-substituted barium titanate oxalate powder having less segregation of the Me element can be obtained, and the Me element is powdered by firing. A Me element-substituted barium titanate powder that is uniformly distributed throughout and has little segregation of Me elements can be obtained. On the other hand, if q is less than the above range, it is difficult to obtain barium titanate substituted with Me element having desired characteristics, and if it exceeds the above range, segregation of Me element is likely to occur.
一般式（１）中、ｐは、原子換算のＢａに対するＭｅ元素のモル比（Ｍｅ／Ｂａ）に相当する。ｐは、０．００１以上０．２００以下であり、好ましくは０．００５以上０．１５０以下である。ｐが上記範囲にあることにより、Ｍｅ元素が粉末全体に均一に分布しており、Ｍｅ元素の偏析の少ない、Ｍｅ元素置換シュウ酸バリウムチタニルが得られ、且つ、焼成により、Ｍｅ元素が粒子全体に均一に分布しており、Ｍｅ元素の偏析の少ない、Ｍｅ元素置換チタン酸バリウムが得られる。一方、ｐが上記範囲未満だと、所望の特性を有するＭｅ元素置換チタン酸バリウムが得られ難く、また、上記範囲を超えると、Ｍｅ元素の偏析が起こり易くなる。 In the general formula (1), p corresponds to the molar ratio (Me / Ba) of the Me element to the atomically converted Ba. p is 0.001 or more and 0.200 or less, preferably 0.005 or more and 0.150 or less. When p is in the above range, the Me element is uniformly distributed throughout the powder, and the Me element-substituted barium titanate oxalate having less segregation of the Me element can be obtained, and the Me element is contained in the entire particle by firing. Me element-substituted barium titanate can be obtained, which is uniformly distributed in the above and has less segregation of Me element. On the other hand, if p is less than the above range, it is difficult to obtain barium titanate substituted with Me element having desired characteristics, and if it exceeds the above range, segregation of Me element is likely to occur.
一般式（１）中、ｎは、１〜８の整数である。ｎは、３〜７の整数が好ましい。 In the general formula (1), n is an integer of 1 to 8. n is preferably an integer of 3 to 7.
なお、一般式（１）で表されるＭｅ元素置換シュウ酸バリウムチタニル中のＴｉ、Ｂａ、Ｍｅの各原子のモル比については、蛍光Ｘ線分析装置（株式会社リガク製、ＺＳＸ１００ｅ）の測定値に基づいて算出することができる。また、一般式（１）で表されるＭｅ元素置換シュウ酸バリウムチタニル中のＴｉ、Ｂａ、Ｍｅの各原子のモル比については、Ｍｅ元素置換シュウ酸バリウムチタニルを焼成して得られるＭｅ元素置換チタン酸バリウムを、蛍光Ｘ線分析装置（株式会社リガク製、ＺＳＸ１００ｅ）で測定して得られた値に基づいて算出することもできる。 The molar ratio of each atom of Ti, Ba, and Me in the Me element-substituted barium titanyl oxalate represented by the general formula (1) is a measured value of a fluorescent X-ray analyzer (ZSX100e, manufactured by Rigaku Co., Ltd.). Can be calculated based on. Further, regarding the molar ratio of each atom of Ti, Ba, and Me in the Me element-substituted barium titanate oxalate represented by the general formula (1), the Me element substitution obtained by firing the Me element-substituted barium titanate oxalate. Barium titanate can also be calculated based on the value obtained by measuring with a fluorescent X-ray analyzer (ZSX100e, manufactured by Rigaku Co., Ltd.).
本発明のＭｅ元素置換有機酸バリウムチタニル粉末の平均粒子径は、特に制限されないが、好ましくは０．１〜３００μｍ、特に好ましくは０．５〜２００μｍである。なお、本発明において、Ｍｅ元素置換有機酸バリウムチタニルの平均粒子径は、レーザ回折・散乱法により求められる粒度分布における体積積算５０％の粒子径（Ｄ５０）を指す。 The average particle size of the barium titanyl powder of Me element-substituted organic acid of the present invention is not particularly limited, but is preferably 0.1 to 300 μm, and particularly preferably 0.5 to 200 μm. In the present invention, the average particle size of the Me element-substituted barium titanyl organic acid refers to the particle size (D50) of 50% volume integration in the particle size distribution obtained by the laser diffraction / scattering method.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末を６００〜１２００℃、好ましくは６５０〜１１００℃で焼成して得られる焼成物は、チタン系ペロブスカイト型複合酸化物であり、Ｂａサイトの一部がＭｅ元素で置換されたチタン酸バリウムである。つまり、本発明のＭｅ元素置換有機酸バリウムチタニル粉末の焼成物は、下記一般式（２）：
（Ｂａ１−ｘＭｅｘ）ｙＴｉＯ３ （２）
で表されるＭｅ元素置換チタン酸バリウム粉末である。一般式（２）中、Ｍｅは、Ｃａ、Ｓｒ及びＭｇから選ばれる少なくとも１種である。ｘは、０．００１≦ｘ≦０．２００であり、好ましくは０．０１０≦ｘ≦０．１５０である。また、ｙは、０．９８０≦ｙ＜０．９９９であり、好ましくは０．９８３≦ｙ≦０．９９８、特に好ましくは０．９８５≦ｙ≦０．９９７である。
The calcined product obtained by calcining the barium titanyl powder of the Me element-substituted organic acid of the present invention at 600 to 1200 ° C., preferably 650 to 1100 ° C. is a titanium-based perovskite-type composite oxide, and a part of Basite is Me. Barium titanate substituted with elements. That is, the calcined product of the barium titanyl powder of the Me element-substituted organic acid of the present invention has the following general formula (2):
(Ba 1-x Me x ) y TiO 3 (2)
It is a Me element-substituted barium titanate powder represented by. In the general formula (2), Me is at least one selected from Ca, Sr and Mg. x is 0.001 ≦ x ≦ 0.200, preferably 0.010 ≦ x ≦ 0.150. Further, y is 0.980 ≦ y <0.999, preferably 0.983 ≦ y ≦ 0.998, and particularly preferably 0.985 ≦ y ≦ 0.997.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末を、６００〜１２００℃、好ましくは６５０〜１１００℃で焼成することにより得られるＭｅ元素置換チタン酸バリウム粉末では、各粒子において、Ｍｅ元素が粒子に均一に分布している。なお、本発明において、Ｍｅ元素置換チタン酸バリウムの粒子に、Ｍｅ元素が均一に分布していることは、電子プローブマイクロアナライザ（ＥＰＭＡ）分析を用いて、Ｍｅ元素置換チタン酸バリウムの圧粉体の表面上を、一辺が２０５μｍの正方形の範囲となるように０．８μｍ間隔で縦横２５６点のマッピング分析して得られる画像解析において、ＣａのＣＶ値（標準偏差／平均値）を算出し、この値が０．４以下であることを差す。 In the Me element-substituted barium titanate powder obtained by firing the Me element-substituted barium titanate organic acid powder of the present invention at 600 to 1200 ° C., preferably 650 to 1100 ° C., the Me element is uniform in each particle. It is distributed in. In the present invention, the fact that the Me element is uniformly distributed in the particles of the Me element-substituted barium titanate is determined by using electron probe microanalyzer (EPMA) analysis to determine that the powder of the Me element-substituted barium titanate is used. The CV value (standard deviation / average value) of Ca was calculated in the image analysis obtained by mapping analysis of 256 points in the vertical and horizontal directions at 0.8 μm intervals so that the side of the surface would be a square area of 205 μm. It means that this value is 0.4 or less.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法は、バリウム化合物、Ｍｅ元素化合物（Ｍｅは、Ｃａ、Ｓｒ及びＭｇから選ばれる少なくとも１種を示す。）及びチタン化合物を水に混合して得られる水溶液（Ａ液）を、有機酸水溶液（Ｂ液）に添加することにより、Ｍｅ元素置換有機酸バリウムチタニルを得るＭｅ元素置換有機酸バリウムチタニル粉末の製造方法であり、
該Ａ液中、原子換算で、Ｂａに対するＭｅ元素のモル比（Ｍｅ／Ｂａ）が０．０２０以上５．０００以下であり、原子換算のＴｉに対するＢａのモル比（Ｂａ／Ｔｉ）が０．３００以上１．２００以下であり、且つ、Ａ液のＢ液への添加速度が２．０ｍｌ／分以上であること、
を特徴とするＭｅ元素置換有機酸バリウムチタニル粉末の製造方法である。
In the method for producing barium titanyl powder of Me element-substituted organic acid of the present invention, a barium compound, a Me element compound (Me indicates at least one selected from Ca, Sr and Mg) and a titanium compound are mixed with water. A method for producing a Me element-substituted barium titanyl organic acid powder, which obtains a Me element-substituted barium titanyl organic acid by adding the obtained aqueous solution (solution A) to an organic acid aqueous solution (solution B).
In the liquid A, the molar ratio (Me / Ba) of the Me element to Ba is 0.020 or more and 5.000 or less in terms of atoms, and the molar ratio of Ba to Ti in terms of atoms (Ba / Ti) is 0. 300 or more and 1.200 or less, and the rate of addition of solution A to solution B is 2.0 ml / min or more.
It is a method for producing barium titanyl powder of Me element-substituted organic acid, which is characterized by the above.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法は、先ず、反応容器に反応に用いるＢ液の全量を入れておき、次いで、反応容器にＡ液を供給して、Ａ液をＢ液に添加することにより、Ｍｅ元素で置換された有機酸バリウムチタニルの生成反応を行うＭｅ元素置換有機酸バリウムチタニルの製造方法である。 In the method for producing barium titanyl powder of Me element-substituted organic acid of the present invention, first, the entire amount of solution B used for the reaction is placed in the reaction vessel, then solution A is supplied to the reaction vessel, and solution A is used as solution B. This is a method for producing barium titanyl organic acid substituted with Me element, which reacts to produce barium titanyl organic acid substituted with Me element by adding to.
本発明のＭｅ元素置換有機酸バリウムチタニルの製造方法に係るＡ液は、バリウム化合物、Ｍｅ元素化合物及びチタン化合物を水に混合して得られる水溶液である。 The solution A according to the method for producing barium titanyl having a Me element-substituted organic acid of the present invention is an aqueous solution obtained by mixing a barium compound, a Me element compound and a titanium compound with water.
本発明のＭｅ元素置換有機酸バリウムチタニルの製造方法に係るバリウム化合物としては、特に制限されず、塩化バリウム、炭酸バリウム、水酸化バリウム、酢酸バリウム、硝酸バリウム等が挙げられる。バリウム化合物は、１種であっても、２種以上の併用であってもよい。バリウム化合物としては、塩化バリウム、炭酸バリウム及び水酸化バリウムからなる群から選ばれる１種又は２種以上が好ましい。 The barium compound according to the method for producing the Me element-substituted organic acid barium titanyl of the present invention is not particularly limited, and examples thereof include barium chloride, barium carbonate, barium hydroxide, barium acetate, and barium nitrate. The barium compound may be one kind or a combination of two or more kinds. As the barium compound, one or more selected from the group consisting of barium chloride, barium carbonate and barium hydroxide is preferable.
本発明のＭｅ元素置換有機酸バリウムチタニルの製造方法に係るＭｅ元素化合物としては、特に制限されず、Ｃａ、Ｓｒ及びＭｇからなる群から選択される１種又は２種以上の元素を含む塩化物、水酸化物、炭酸塩、酢酸塩、硝酸塩等が挙げられる。Ｍｅ元素化合物は、１種であっても、２種以上の併用であってもよい。Ｍｅ元素化合物としては、Ｍｅ元素の塩化物、Ｍｅ元素の炭酸塩及びＭｅ元素の水酸化物からなる群から選ばれる１種又は２種以上が好ましい。 The Me element compound according to the method for producing the Me element-substituted organic acid barium titanyl of the present invention is not particularly limited, and is a chloride containing one or more elements selected from the group consisting of Ca, Sr and Mg. , Hydroxides, carbonates, acetates, nitrates and the like. The Me element compound may be one kind or a combination of two or more kinds. As the Me element compound, one or more selected from the group consisting of Me element chloride, Me element carbonate and Me element hydroxide is preferable.
本発明のＭｅ元素置換有機酸バリウムチタニルの製造方法に係るチタン化合物としては、特に制限されず、四塩化チタン、乳酸チタン等が挙げられる。チタン化合物は、１種であっても、２種以上の併用であってもよい。チタン化合物としては、四塩化チタンが好ましい。 The titanium compound according to the method for producing the Me element-substituted organic acid barium titanyl of the present invention is not particularly limited, and examples thereof include titanium tetrachloride and titanium lactate. The titanium compound may be one kind or a combination of two or more kinds. As the titanium compound, titanium tetrachloride is preferable.
本発明のＭｅ元素置換有機酸バリウムチタニルの製造方法に係る有機酸としては、シュウ酸、クエン酸、マロン酸及びコハク酸等が挙げられる。有機酸は、１種であっても、２種以上の併用であってもよい。有機酸としては、シュウ酸が好ましい。 Examples of the organic acid according to the method for producing the Me element-substituted organic acid barium titanyl of the present invention include oxalic acid, citric acid, malonic acid and succinic acid. The organic acid may be one kind or a combination of two or more kinds. As the organic acid, oxalic acid is preferable.
そして、本発明においては、バリウム化合物として塩化バリウムを用い、Ｍｅ元素化合物としてＭｅ元素の塩化物を用い、チタン化合物として四塩化チタンを用い、有機酸としてシュウ酸を用いることが、反応性が高くなり、且つ、安定した品質のものが、高収率で得られる点で好ましい。 In the present invention, it is highly reactive that barium chloride is used as the barium compound, Me element chloride is used as the Me element compound, titanium tetrachloride is used as the titanium compound, and oxalic acid is used as the organic acid. It is preferable that the compound has a stable quality and can be obtained in a high yield.
Ａ液中、原子換算のＢａに対するＭｅ元素のモル比（Ｍｅ／Ｂａ）は、０．０２０以上５．０００以下、好ましくは０．０５０以上４．０００以下である。Ａ液中の原子換算のＢａに対するＭｅ元素のモル比（Ｍｅ／Ｂａ）が、上記範囲にあることにより、Ｍｅ元素が粉末全体に均一に分布しており、Ｍｅ元素の偏析が少ないＭｅ元素置換有機酸バリウムチタニル粉末が得られ、焼成により、Ｍｅ元素が粉末全体に均一に分布しており、Ｍｅ元素の偏析が少ないＭｅ元素置換チタン酸バリウム粉末が得られる。一方、Ａ液中の原子換算のＴｉに対するＢａのモル比（Ｂａ／Ｔｉ）が上記範囲未満だと、Ｍｅ元素の置換が進み難く、また、上記範囲を超えると、Ｍｅ元素の偏析が起こり易くなる。 The molar ratio (Me / Ba) of the Me element to the atomically converted Ba in the liquid A is 0.020 or more and 5.000 or less, preferably 0.050 or more and 4.000 or less. Since the molar ratio (Me / Ba) of the Me element to the atomic equivalent Ba in the liquid A is within the above range, the Me element is uniformly distributed throughout the powder, and the Me element substitution with less segregation of the Me element. An organic barium titanyl powder is obtained, and by firing, a Me element-substituted barium titanate powder in which the Me element is uniformly distributed throughout the powder and the segregation of the Me element is small can be obtained. On the other hand, if the molar ratio of Ba to the atomic equivalent Ti in the liquid A (Ba / Ti) is less than the above range, the substitution of the Me element is difficult to proceed, and if it exceeds the above range, segregation of the Me element is likely to occur. Become.
Ａ液中、原子換算のＴｉに対するＢａのモル比（Ｂａ／Ｔｉ）は、０．３００以上１．２００以下、好ましくは０．３５０以上１．１５０以下である。Ａ液中の原子換算のＴｉに対するＢａのモル比（Ｂａ／Ｔｉ）が、上記範囲にあることにより、Ｍｅ元素が粒子全体に均一に分布しており、Ｍｅ元素の偏析が少ないＭｅ元素置換有機酸バリウムチタニルが得られ、焼成により、Ｍｅ元素が粒子全体に均一に分布しており、Ｍｅ元素の偏析が少ないＭｅ元素置換チタン酸バリウムが得られる。一方、Ａ液中の原子換算のＴｉに対するＢａのモル比（Ｂａ／Ｔｉ）が、上記範囲未満だと、Ｍｅ元素の置換が進み難く、また、上記範囲を超えると、Ｍｅ元素の偏析が起こり易くなる。 In the liquid A, the molar ratio (Ba / Ti) of Ba to Ti in terms of atoms is 0.300 or more and 1.200 or less, preferably 0.350 or more and 1.150 or less. Since the molar ratio of Ba to Ti in liquid A (Ba / Ti) is in the above range, Me elements are uniformly distributed throughout the particles, and Me element-substituted organics with little segregation of Me elements. Barium titanate acid is obtained, and by firing, Me element is uniformly distributed throughout the particles, and Me element-substituted barium titanate with less segregation of Me element is obtained. On the other hand, if the molar ratio of Ba to the atomic equivalent Ti in the liquid A (Ba / Ti) is less than the above range, the substitution of the Me element is difficult to proceed, and if it exceeds the above range, segregation of the Me element occurs. It will be easier.
Ａ液中のＢａ濃度は、特に制限されないが、原子換算で、好ましくは０．０５〜１．００ｍｏｌ／Ｌ、特に好ましくは０．１０〜０．９０ｍｏｌ／Ｌである。 The Ba concentration in the liquid A is not particularly limited, but is preferably 0.05 to 1.00 mol / L, particularly preferably 0.10 to 0.90 mol / L in terms of atoms.
Ａ液中のＭｅ元素濃度は、特に制限されないが、原子換算で、好ましくは０．００２〜６．５０ｍｏｌ／Ｌ、特に好ましくは０．１０〜６．００ｍｏｌ／Ｌである。 The concentration of the Me element in the liquid A is not particularly limited, but is preferably 0.002 to 6.50 mol / L, particularly preferably 0.10 to 6.00 mol / L in terms of atoms.
Ａ液中のＴｉ濃度は、特に制限されないが、原子換算で、好ましくは０．０５〜１．３５ｍｏｌ／Ｌ、特に好ましくは０．１０〜１．３０ｍｏｌ／Ｌである。 The Ti concentration in the liquid A is not particularly limited, but is preferably 0.05 to 1.35 mol / L, particularly preferably 0.10 to 1.30 mol / L in terms of atoms.
本発明のＭｅ元素置換有機酸バリウムチタニルの製造方法に係るＢ液は、有機酸を水に溶解して得られる有機酸水溶液である。 The liquid B according to the method for producing barium titanyl, which is a Me element-substituted organic acid of the present invention, is an aqueous organic acid solution obtained by dissolving an organic acid in water.
Ｂ液中の有機酸イオンのモル数に対するＡ液中の原子換算のＢａ、Ｍｅ元素及びＴｉの合計モル数の比は０．８００以上１．４００以下、好ましくは０．８５０以上１．３００以下、特に好ましくは０．９００以上１．２５０以下である。Ｂ液中の有機酸イオンのモル数に対するＡ液中の原子換算のＢａ、Ｍｅ元素及びＴｉの合計モル数の比が、上記範囲にあることにより、Ｍｅ元素が粒子全体に均一に分布しており、Ｍｅ元素の偏析の少ない、Ｍｅ元素置換有機酸バリウムチタニルが得られる。 The ratio of the total number of moles of Ba, Me element and Ti in terms of atoms in solution A to the number of moles of organic acid ions in solution B is 0.800 or more and 1.400 or less, preferably 0.850 or more and 1.300 or less. , Especially preferably 0.900 or more and 1.250 or less. When the ratio of the total number of moles of the atomic equivalent Ba, Me element and Ti in the liquid A to the number of moles of the organic acid ion in the liquid B is within the above range, the Me element is uniformly distributed over the entire particle. Therefore, barium titanyl, a Me element-substituted organic acid, with less segregation of the Me element can be obtained.
Ｂ液中の有機酸イオンの濃度は、特に制限されないが、好ましくは０．１０〜５．００ｍｏｌ／Ｌ、特に好ましくは０．５０〜３．００ｍｏｌ／Ｌである。 The concentration of the organic acid ion in the liquid B is not particularly limited, but is preferably 0.10 to 5.00 mol / L, and particularly preferably 0.50 to 3.00 mol / L.
本発明のＭｅ元素置換有機酸バリウムチタニルの製造方法では、先ず、反応容器にＢ液の全量を入れておき、次いで、反応容器にＡ液を供給して、Ｂ液にＡ液を添加することにより、反応容器内で、Ｍｅ元素置換有機酸バリウムチタニルの生成反応を行う。 In the method for producing barium titanyl Me element-substituted organic acid of the present invention, first, the entire amount of solution B is placed in the reaction vessel, then solution A is supplied to the reaction vessel, and solution A is added to solution B. In the reaction vessel, a reaction for producing barium titanyl, which is a Me element-substituted organic acid, is carried out.
Ｂ液にＡ液を添加するときのＡ液の添加速度は、実施する規模にもよるが、例えば０．５Ｌスケールの実験室レベルでは、２．０ｍｌ／分以上、特に３．０ｍｌ／分以上であることが好ましい。前記添加速度でＢ液にＡ液を添加することで、Ｍｅ元素が粒子全体に均一に分布しており、Ｍｅ元素の偏析の少ない、Ｍｅ元素置換有機酸バリウムチタニルが得られる。なお、上記添加速度を満たしていれば上限は特に制限されない。 The rate of addition of solution A when adding solution A to solution B depends on the scale of implementation, but for example, at the laboratory level of 0.5 L scale, 2.0 ml / min or more, especially 3.0 ml / min or more. Is preferable. By adding the solution A to the solution B at the addition rate, the Me element is uniformly distributed throughout the particles, and barium titanyl, which is a Me element-substituted organic acid, can be obtained with little segregation of the Me element. The upper limit is not particularly limited as long as the above addition rate is satisfied.
Ｂ液にＡ液を添加するときの混合温度、すなわち、反応容器にＡ液を添加するときのＡ液及び反応容器内の反応液（又はＢ液）の温度は、通常１０〜５０℃、好ましくは１５〜４５℃である。前記混合温度でＢ液にＡ液を添加することで、Ｍｅ元素が粒子全体に均一に分布しており、Ｍｅ元素の偏析の少ない、Ｍｅ元素置換有機酸バリウムチタニルが得られる。 The mixing temperature when the solution A is added to the solution B, that is, the temperature of the solution A and the reaction solution (or the solution B) in the reaction vessel when the solution A is added to the reaction vessel is usually 10 to 50 ° C., preferably. Is 15-45 ° C. By adding the solution A to the solution B at the mixing temperature, the Me element is uniformly distributed throughout the particles, and barium titanyl, which is a Me element-substituted organic acid, can be obtained with little segregation of the Me element.
Ｂ液にＡ液の全量を添加した後、直ちに、反応液を冷却することにより、あるいは、ろ過等で反応液を除去することにより、反応を終了させてもよいし、あるいは、Ｂ液にＡ液の全量を添加した後、反応液を所定の温度で一定時間維持する熟成を行ってもよい。熟成を行う場合、熟成温度は、好ましくは１０℃以上、特に好ましくは２０〜８０℃であり、熟成時間は、好ましくは０．１時間以上、特に好ましくは０．２時間以上である。 Immediately after adding the entire amount of solution A to solution B, the reaction may be terminated by cooling the reaction solution or by removing the reaction solution by filtration or the like, or solution A may be added to solution B. After adding the entire amount of the liquid, the reaction liquid may be aged at a predetermined temperature for a certain period of time. When aging is performed, the aging temperature is preferably 10 ° C. or higher, particularly preferably 20 to 80 ° C., and the aging time is preferably 0.1 hour or longer, particularly preferably 0.2 hour or longer.
Ｂ液にＡ液を添加しているときは、反応液（又はＢ液）を撹拌しながらＢ液へのＡ液の添加を行うことが好ましい。また、Ｂ液にＡ液の全量を添加した後、熟成を行う場合、反応液を撹拌しながら熟成を行うことが好ましい。撹拌速度は、特に制限されないが、Ｂ液へのＡ液の添加開始からＡ液の全量添加終了まで、熟成を行う場合は、熟成の終了までの間、生成するＭｅ元素置換有機酸バリウムチタニルを含む反応液が、常に流動する状態となる撹拌速度であればよい。 When the solution A is added to the solution B, it is preferable to add the solution A to the solution B while stirring the reaction solution (or the solution B). Further, when aging is carried out after adding the entire amount of the solution A to the solution B, it is preferable to carry out the aging while stirring the reaction solution. The stirring speed is not particularly limited, but the Me element-substituted barium titanyl organic acid produced is used from the start of addition of solution A to solution B to the end of addition of the entire amount of solution A, and in the case of aging, until the end of aging. The stirring speed may be such that the reaction solution contained is always in a flowing state.
Ｂ液へＡ液を全量添加した後、熟成を行う場合は、熟成終了後、常法により反応液の固液分離を行い、次いで、固形分を水洗する。水洗方法としては、特に制限されないが、リパルプ等で洗浄を行うことが、洗浄効率が高い点で好ましい。洗浄後、固形分を乾燥し、必要に応じて、粉砕して、Ｍｅ元素置換有機酸バリウムチタニル、すなわち、Ｂａサイトの一部がＭｅ元素で置換されている有機酸バリウムチタニルを得る。 When aging is performed after adding the entire amount of solution A to solution B, the reaction solution is solid-liquid separated by a conventional method after the aging is completed, and then the solid content is washed with water. The washing method is not particularly limited, but washing with repulp or the like is preferable in terms of high washing efficiency. After washing, the solid content is dried and, if necessary, pulverized to obtain barium titanyl organic acid substituted with Me element, that is, barium titanyl organic acid in which a part of Basite is substituted with Me element.
このようにして、本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を行い得られるＭｅ元素置換有機酸バリウムチタニル粉末は、Ｂａサイトの一部がＭｅ元素で置換されている有機酸バリウムチタニルであり、Ｔｉに対するＢａとＭｅ元素の合計のモル比（（Ｂａ＋Ｍｅ）／Ｔｉ）が０．９８０以上０．９９９未満であり、Ｂａに対するＭｅ元素のモル比（Ｍｅ／Ｂａ）が０．００１以上０．２５０以下である。 In this way, the Me element-substituted barium titanyl organic acid powder obtained by performing the method for producing the barium titanyl powder of Me element-substituted organic acid of the present invention has barium titanyl organic acid in which a part of Basite is substituted with Me element. The total molar ratio of Ba and Me element to Ti ((Ba + Me) / Ti) is 0.980 or more and less than 0.999, and the molar ratio of Me element to Ba (Me / Ba) is 0.001 or more. It is 0.250 or less.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を行い得られるＭｅ元素置換有機酸バリウムチタニルにおいて、Ｍｅ元素は、Ｃａ、Ｓｒ及びＭｇから選ばれる少なくとも１種の元素を表し、好ましくはＣａ、Ｓｒであり、特に好ましくはＣａであり、Ｔｉに対するＢａとＭｅ元素の合計のモル比（（Ｂａ＋Ｍｅ）／Ｔｉ）は、０．９８０以上０．９９９未満、好ましくは０．９８３以上０．９９８以下、特に好ましくは０．９８５以上０．９９７以下であり、Ｂａに対するＭｅ元素のモル比（Ｍｅ／Ｂａ）は、０．００１以上０．２５０以下であり、好ましくは０．００５以上０．１５０以下である。 In the Me element-substituted barium titanyl organic acid obtained by carrying out the method for producing barium titanyl powder of Me element-substituted organic acid of the present invention, the Me element represents at least one element selected from Ca, Sr and Mg, and is preferably Ca. , Sr, particularly preferably Ca, and the total molar ratio of Ba and Me elements to Ti ((Ba + Me) / Ti) is 0.980 or more and less than 0.999, preferably 0.983 or more and 0.998. Hereinafter, particularly preferably, it is 0.985 or more and 0.997 or less, and the molar ratio (Me / Ba) of the Me element to Ba is 0.001 or more and 0.250 or less, preferably 0.005 or more and 0.150. It is as follows.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を行い得られるＭｅ元素置換有機酸バリウムチタニル粉末の平均粒径は、特に制限されないが、好ましくは０．１〜３００μｍ、特に好ましくは０．５〜２００μｍである。 The average particle size of the Me element-substituted barium titanyl organic acid powder obtained by the method for producing the barium titanyl powder of Me element-substituted organic acid of the present invention is not particularly limited, but is preferably 0.1 to 300 μm, particularly preferably 0. It is 5 to 200 μm.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法では、Ｍｅ元素が粉末全体に均一に分布しており、Ｍｅ元素の偏析が少ないＭｅ元素置換有機酸バリウムチタニル粉末が得られる。なお、Ｍｅ元素がＭｅ元素置換有機酸バリウムチタニル粉末全体に均一に分布しており、Ｍｅ元素の偏析が少ないことは、本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を行い得られるＭｅ元素置換有機酸バリウムチタニル粉末を、６００〜１２００℃で焼成し、得られるＭｅ元素置換チタン酸バリウムを、ＥＰＭＡでマッピング分析を行うことにより、確認される。 In the method for producing barium titanyl powder of Me element-substituted organic acid of the present invention, barium titanyl powder substituted organic acid with Me element is obtained in which the Me element is uniformly distributed throughout the powder and the segregation of the Me element is small. The fact that the Me element is uniformly distributed throughout the barium titanyl powder of the Me element-substituted organic acid and the segregation of the Me element is small means that the Me element-substituted barium titanyl organic acid powder of the present invention can be produced. The element-substituted barium titanyl organic acid powder is calcined at 600 to 1200 ° C., and the obtained barium element-substituted barium titanate is confirmed by mapping analysis with EPMA.
また、本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を行い得られるＭｅ元素置換有機酸バリウムチタニル粉末を、６００〜１２００℃、好ましくは６５０〜１１００℃で焼成することにより得られるＭｅ元素置換チタン酸バリウムでは、粒子表面にＭｅ元素が均一に分布している。また、本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を行い得られるＭｅ元素置換有機酸バリウムチタニル粉末では、粒子の深さ方向に、Ｍｅ元素が均一に分布している。 Further, the Me element obtained by firing the Me element-substituted barium titanyl organic acid powder obtained by the method for producing the barium titanyl powder of the Me element-substituted organic acid of the present invention at 600 to 1200 ° C., preferably 650 to 1100 ° C. In the substituted barium titanate, the Me element is uniformly distributed on the particle surface. Further, in the Me element-substituted barium titanyl organic acid powder obtained by the method for producing the barium titanyl powder of Me element-substituted organic acid of the present invention, the Me element is uniformly distributed in the depth direction of the particles.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末、及び本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を行い得られるＭｅ元素置換有機酸バリウムチタニル粉末を焼成して得られるＭｅ元素置換チタン酸バリウム粉末は、誘電体セラミック材料のチタン系ペロブスカイト型セラミック原料粉末として好適に用いられる。つまり、本発明のＭｅ元素置換有機酸バリウムチタニル粉末、又は本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を行い得られるＭｅ元素置換有機酸バリウムチタニル粉末を、６００〜１２００℃、好ましくは６５０〜１１００℃で焼成することにより、チタン系ペロブスカイト型セラミック原料粉末を得ることができる。 The Me element-substituted organic acid barium titanyl powder of the present invention and the Me element-substituted organic acid barium titanyl powder obtained by the method for producing the Me element-substituted organic acid barium titanyl powder of the present invention are fired to obtain Me element-substituted titanium acid. Barium powder is preferably used as a titanium-based perovskite-type ceramic raw material powder as a dielectric ceramic material. That is, the Me element-substituted barium titanyl organic acid powder of the present invention or the barium titanyl powder of Me element-substituted organic acid obtained by the method for producing the barium titanyl powder of Me element-substituted organic acid of the present invention is preferably 600 to 1200 ° C. By firing at 650 to 1100 ° C., a titanium-based perovskite type ceramic raw material powder can be obtained.
本発明のＭｅ元素置換有機酸バリウムチタニル粉末、及び本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を行い得られるＭｅ元素置換有機酸バリウムチタニル粉末を焼成して得られるＭｅ元素置換チタン酸バリウム粉末は、下記一般式（２）：
（Ｂａ１−ｘＭｅｘ）ｙＴｉＯ３ （２）
で表されるＭｅ元素置換チタン酸バリウム粉末である。一般式（２）中、Ｍｅは、Ｃａ、Ｓｒ及びＭｇから選ばれる少なくとも１種である。ｘは、０．００１≦ｘ≦０．２００であり、好ましくは０．００５≦ｘ≦０．１５０である。また、ｙは、０．９８０≦ｙ＜０．９９９であり、好ましくは０．９８３≦ｙ≦０．９９８、特に好ましくは０．９８５≦ｙ≦０．９９７である。
The Me element-substituted organic acid barium titanyl powder of the present invention and the Me element-substituted organic acid barium titanyl powder of the present invention can be produced by firing the Me element-substituted organic acid barium titanic powder. The barium powder has the following general formula (2):
(Ba 1-x Me x ) y TiO 3 (2)
It is a Me element-substituted barium titanate powder represented by. In the general formula (2), Me is at least one selected from Ca, Sr and Mg. x is 0.001 ≦ x ≦ 0.200, preferably 0.005 ≦ x ≦ 0.150. Further, y is 0.980 ≦ y <0.999, preferably 0.983 ≦ y ≦ 0.998, and particularly preferably 0.985 ≦ y ≦ 0.997.
上記焼成を行う前に、必要により、微細で且つ低温域で焼成を行っても結晶性の高いチタン系ペロブスカイト型セラミック原料粉末が得られるように、Ｍｅ元素置換有機酸バリウムチタニルの平均粒径が、好ましくは４μｍ以下、特に好ましくは０．０２〜０．５μｍとなるように、ボールミル、ビーズミル等で、Ｍｅ元素置換有機酸バリウムチタニル粉末の湿式粉砕処理を行ってもよい。この場合、湿式粉砕処理で用いる溶媒としては、Ｍｅ元素置換有機酸バリウムチタニルに対して不活性であるものが用いられ、例えば、水、メタノール、エタノール、プロパノール、ブタノール、トルエン、キシレン、アセトン、塩化メチレン、酢酸エチル、ジメチルホルムアミド及びジエチルエーテル等が挙げられる。この中、湿式粉砕処理用の溶媒としては、メタノール、エタノール、プロパノール、ブタノール、トルエン、キシレン、アセトン、塩化メチレン、酢酸エチル、ジメチルホルムアミド及びジエチルエーテル等の有機溶媒で且つＢａ元素、Ｔｉ元素及びＭｅ元素の溶出が少ないものが、結晶性の高いチタン系ペロブスカイト型セラミック原料粉末を得ることができる点で好ましい。 Before the above firing, if necessary, the average particle size of the Me element-substituted organic acid ballium titanyl is adjusted so that a titanium-based perovskite-type ceramic raw material powder having high crystallinity can be obtained even if the firing is performed in a fine and low temperature range. The wet pulverization treatment of the Me element-substituted organic acid barium titanyl powder may be carried out with a ball mill, a bead mill or the like so as to be preferably 4 μm or less, particularly preferably 0.02 to 0.5 μm. In this case, as the solvent used in the wet pulverization treatment, a solvent inactive with respect to barium titanyl, which is a Me element-substituted organic acid, is used. For example, water, methanol, ethanol, propanol, butanol, toluene, xylene, acetone, and chloride are used. Examples thereof include methylene, ethyl acetate, dimethylformamide and diethyl ether. Among these, the solvent for the wet pulverization treatment is an organic solvent such as methanol, ethanol, propanol, butanol, toluene, xylene, acetone, methylene chloride, ethyl acetate, dimethylformamide and diethyl ether, and Ba element, Ti element and Me. A solvent with less elution of elements is preferable because a titanium-based perovskite-type ceramic raw material powder having high crystallinity can be obtained.
本発明の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は、本発明のＭｅ元素置換有機酸バリウムチタニル粉末、又は本発明のＭｅ元素置換有機酸バリウムチタニル粉末の製造方法を行い得られるＭｅ元素置換有機酸バリウムチタニル粉末を焼成することにより、Ｍｅ元素置換チタン酸バリウムを得ることを特徴とする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である。 The method for producing the titanium-based perovskite type ceramic raw material powder of the present invention is the method for producing the Me element-substituted organic acid barium titanyl powder of the present invention or the Me element-substituted organic acid barium titanyl powder of the present invention. A method for producing a titanium-based perovskite-type ceramic raw material powder, which comprises obtaining barium titanate substituted with Me element by firing barium titanyl acid powder.
Ｍｅ元素置換有機酸バリウムチタニル粉末に含まれる有機酸由来の有機物は、材料の誘電体特性を損なうとともに、セラミック化のための熱工程における挙動の不安定要因となるため好ましくない。従って、本発明の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で、Ｍｅ元素置換有機酸バリウムチタニル粉末を焼成することにより、Ｍｅ元素含有有機酸バリウムチタニルを熱分解して、目的とするチタン系ペロブスカイト型セラミック原料粉末であるＭｅ元素置換チタン酸バリウムを得ると共に、有機酸由来の有機物を除去する。 The organic acid-derived organic substance contained in the barium titanyl powder of Me element-substituted organic acid is not preferable because it impairs the dielectric properties of the material and causes unstable behavior in the thermal process for ceramicization. Therefore, in the method for producing a titanium-based perovskite-type ceramic raw material powder of the present invention, the Me element-containing barium titanate organic acid is thermally decomposed by firing the barium titanyl powder containing Me element, and the target titanium-based perovskite is obtained. The Me element-substituted barium titanate, which is a mold ceramic raw material powder, is obtained, and organic substances derived from organic acids are removed.
本発明の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において、焼成する際の焼成温度は、６００〜１２００℃ 、好ましくは６５０〜１１００℃である。焼成温度が、上記範囲未満だと、単一相のチタン系ペロブスカイト型セラミック粉末が得られ難く、また、上記範囲を超えると、粒径のバラツキが大きくなる。本発明の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において、焼成する際の焼成時間は、好ましくは０．２〜３０時間、特に好ましくは０．５〜２０時間である。本発明の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において、焼成する際の焼成の雰囲気は、特に制限されず、大気雰囲気下又は不活性ガス雰囲気下の何れであってもよい。 In the method for producing a titanium-based perovskite-type ceramic raw material powder of the present invention, the firing temperature at the time of firing is 600 to 1200 ° C., preferably 650 to 1100 ° C. If the firing temperature is less than the above range, it is difficult to obtain a single-phase titanium-based perovskite-type ceramic powder, and if it exceeds the above range, the particle size varies widely. In the method for producing a titanium-based perovskite-type ceramic raw material powder of the present invention, the firing time at the time of firing is preferably 0.2 to 30 hours, particularly preferably 0.5 to 20 hours. In the method for producing a titanium-based perovskite-type ceramic raw material powder of the present invention, the firing atmosphere at the time of firing is not particularly limited, and may be either an air atmosphere or an inert gas atmosphere.
本発明の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では、焼成を１回だけ行ってもよいし、必要に応じて、２回以上繰り返し行ってもよい。焼成を繰り返す場合、粉体特性を均一にするために、１度焼成したものを粉砕した後に、次の焼成を行ってもよい。 In the method for producing a titanium-based perovskite-type ceramic raw material powder of the present invention, firing may be performed only once, or may be repeated twice or more if necessary. When the firing is repeated, in order to make the powder characteristics uniform, the one fired once may be crushed and then the next firing may be performed.
本発明の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では、焼成後、適宜冷却し、必要に応じて粉砕することにより、チタン系ペロブスカイト型複合酸化物であり、チタン系ペロブスカイト型セラミック原料粉末として好適な、Ｍｅ元素置換チタン酸バリウム粉末を得る。なお、必要に応じて行われる粉砕は、焼成して得られるＭｅ元素置換チタン酸バリウム粉末がもろく結合したブロック状のものである場合等に、適宜行うものであり、Ｍｅ元素置換チタン酸バリウム粉末の粒子自体は、特定の平均粒径、ＢＥＴ比表面積を有するものである。すなわち、本発明の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を行い得られるＭｅ元素置換チタン酸バリウム粉末は、走査型電子顕微鏡（ＳＥＭ）により求められる平均粒径が、０．０１〜４μｍ、好ましくは０．０２〜０．５μｍであり、ＢＥＴ比表面積が、０．２５〜１００ｍ２／ｇ、好ましくは２〜５０ｍ２／ｇであり、組成のバラツキが少ないものである。なお、本発明において、Ｍｅ元素置換チタン酸バリウム粉末の平均粒子径については、走査型電子顕微鏡（ＳＥＭ）写真により、任意に２００個の粒子を測定し、その平均値を平均粒子径とした。 In the method for producing a titanium-based perovskite-type ceramic raw material powder of the present invention, it is a titanium-based perovskite-type composite oxide by appropriately cooling after firing and pulverizing if necessary, and is suitable as a titanium-based perovskite-type ceramic raw material powder. A Me element-substituted barium titanate powder is obtained. It should be noted that the pulverization performed as necessary is appropriately performed when the Me element-substituted barium titanate powder obtained by firing is in the form of a brittlely bonded block, and the Me element-substituted barium titanate powder is appropriately performed. The particles themselves have a specific average particle size and BET specific surface area. That is, the Me element-substituted barium titanate powder obtained by the method for producing the titanium-based perovskite-type ceramic raw material powder of the present invention has an average particle size of 0.01 to 4 μm, preferably 0.01 to 4 μm, as determined by a scanning electron microscope (SEM). Is 0.02 to 0.5 μm, and the BET specific surface area is 0.25 to 100 m 2 / g, preferably 2 to 50 m 2 / g, and there is little variation in composition. In the present invention, with respect to the average particle size of the Me element-substituted barium titanate powder, 200 particles were arbitrarily measured by a scanning electron microscope (SEM) photograph, and the average value was taken as the average particle size.
なお、本発明の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を行い得られるチタン系ペロブスカイト型セラミック原料粉末には、必要により、誘電特性や温度特性を調製する目的で、副成分元素含有化合物を、該チタン系ペロブスカイト型セラミック原料粉末に添加し含有させることができる。用いることができる副成分元素含有化合物としては、例えば、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕの希土類元素、Ｌｉ、Ｂｉ、Ｚｎ、Ｍｎ、Ａｌ、Ｓｉ、Ｃｏ、Ｎｉ、Ｃｒ、Ｆｅ、Ｔｉ、Ｖ、Ｎｂ、Ｍｏ、Ｗ及びＳｎからなる群より選ばれる少なくとも１種の元素を含む化合物が挙げられる。 The titanium-based perovskite-type ceramic raw material powder obtained by the method for producing the titanium-based perovskite-type ceramic raw material powder of the present invention contains, if necessary, a subcomponent element-containing compound for the purpose of adjusting dielectric properties and temperature characteristics. It can be added to and contained in the titanium-based perovskite type ceramic raw material powder. Examples of the subcomponent element-containing compound that can be used include rare earth elements such as Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. , Li, Bi, Zn, Mn, Al, Si, Co, Ni, Cr, Fe, Ti, V, Nb, Mo, W and Sn. Examples thereof include compounds containing at least one element selected from the group.
副成分元素含有化合物は、無機物又は有機物のいずれであってもよく、例えば、上記元素を含む酸化物、水酸化物、塩化物、硝酸塩、シュウ酸塩、カルボン酸塩及びアルコキシド等が挙げられる。なお、副成分元素含有化合物がＳｉ元素を含有する化合物である場合は、上記酸化物等に加えて、シリカゾルや珪酸ナトリウム等も用いることができる。上記副成分元素含有化合物は、１種又は２種以上適宜組み合わせて用いられ、その添加量や添加化合物の組み合わせは目的に応じて、適宜選択される。 The subcomponent element-containing compound may be either an inorganic substance or an organic substance, and examples thereof include oxides, hydroxides, chlorides, nitrates, oxalates, carboxylates and alkoxides containing the above elements. When the subcomponent element-containing compound is a compound containing a Si element, silica sol, sodium silicate, or the like can be used in addition to the above oxides and the like. The above-mentioned subcomponent element-containing compounds are used in an appropriate combination of one type or two or more types, and the amount of the added amount and the combination of the added compounds are appropriately selected according to the purpose.
チタン系ペロブスカイト型セラミック原料粉末に、副成分元素を含有させる方法は、例えば、本発明の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を行い得られるチタン系ペロブスカイト型セラミック原料粉末と副成分元素含有化合物を均一混合後、焼成を行う方法、あるいは、本発明の有機酸バリウムチタニル粉末又は本発明の有機酸バリウムチタニル粉末の製造方法を行い得られる本発明の有機酸バリウムチタニル粉末と副成分元素含有化合物を均一混合後、焼成する方法が挙げられる。 The method for incorporating the subcomponent element into the titanium-based perovskite-type ceramic raw material powder is, for example, the titanium-based perovskite-type ceramic raw material powder and the sub-component element-containing compound obtained by performing the method for producing the titanium-based perovskite-type ceramic raw material powder of the present invention. The organic acid barium titanyl powder of the present invention and the auxiliary component element-containing compound obtained by the method of uniformly mixing and then firing, or the method for producing the organic acid barium titanyl powder of the present invention or the organic acid barium titanyl powder of the present invention. Can be mentioned as a method of uniformly mixing and then firing.
本発明の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を行い得られるチタン系ペロブスカイト型セラミック原料粉末を、例えば、副成分元素を含め、従来公知の添加剤、有機系バインダ、可塑剤、分散剤等の配合剤と共に、適当な溶媒中に混合分散させてスラリー化し、シート成形を行うことにより、積層セラミックコンデンサの製造に用いられるセラミックシートを得ることができる。 The titanium-based perovskite-type ceramic raw material powder obtained by the method for producing the titanium-based perovskite-type ceramic raw material powder of the present invention can be obtained from, for example, conventionally known additives, organic binders, plasticizers, dispersants, etc., including subcomponent elements. A ceramic sheet used for manufacturing a multilayer ceramic capacitor can be obtained by mixing and dispersing the mixture in an appropriate solvent to form a slurry and forming a sheet.
セラミックシートから積層セラミックコンデンサを作製するには、まず、セラミックシートの一面に内部電極形成用導電ペーストを印刷し、乾燥後、複数枚のセラミックシートを積層し、厚み方向に圧着することにより積層体とする。次に、この積層体を加熱処理して脱バインダ処理を行い、焼成して焼成体を得る。さらに、燒結体にＮｉペースト、Ａｇペースト、ニッケル合金ペースト、銅ペースト、銅合金ペースト等を塗布して焼き付ければ、積層セラミックコンデンサを得ることができる。 To manufacture a laminated ceramic capacitor from a ceramic sheet, first, a conductive paste for forming an internal electrode is printed on one surface of the ceramic sheet, dried, and then a plurality of ceramic sheets are laminated and pressure-bonded in the thickness direction to form a laminated body. And. Next, this laminated body is heat-treated to perform a binder removal treatment, and then fired to obtain a fired body. Further, a multilayer ceramic capacitor can be obtained by applying Ni paste, Ag paste, nickel alloy paste, copper paste, copper alloy paste or the like to the fired body and baking it.
また、例えば、本発明の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を行い得られるチタン系ペロブスカイト型セラミック原料粉末を、エポキシ樹脂、ポリエステル樹脂、ポリイミド樹脂等の樹脂に配合して、樹脂シート、樹脂フィルム、接着剤等とすると、プリント配線板や多層プリント配線板等の材料として好適に用いることができ、また、内部電極と誘電体層との収縮差を抑制するための共材、電極セラミック回路基板、ガラスセラミックス回路基板、回路周辺材料及び無機ＥＬ用等の誘電体材料としても用いることができる。 Further, for example, a titanium-based perovskite-type ceramic raw material powder obtained by performing the method for producing a titanium-based perovskite-type ceramic raw material powder of the present invention is blended with a resin such as an epoxy resin, a polyester resin, or a polyimide resin to form a resin sheet or a resin. When used as a film, an adhesive, etc., it can be suitably used as a material for a printed wiring board, a multilayer printed wiring board, etc., and a co-material or an electrode ceramic circuit for suppressing a shrinkage difference between an internal electrode and a dielectric layer. It can also be used as a substrate, a glass-ceramic circuit board, a circuit peripheral material, and a dielectric material for inorganic EL and the like.
また、本発明の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を行い得られるチタン系ペロブスカイト型セラミック原料粉末を、排ガス除去、化学合成等の反応時に使用される触媒や、帯電防止、クリーニング効果を付与する印刷トナーの表面改質材としても、好適に用いることができる。 Further, the titanium-based perovskite-type ceramic raw material powder obtained by the method for producing the titanium-based perovskite-type ceramic raw material powder of the present invention is provided with a catalyst used in reactions such as exhaust gas removal and chemical synthesis, and antistatic and cleaning effects. It can also be suitably used as a surface modifier for printing toner.
以下、本発明を実施例により詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
実施例においては、以下の方法による特性を測定した。
（１）Ｂａ原子、Ｃａ原子及びＴｉ原子のモル比
各原子のモル比を、蛍光Ｘ線分析装置（株式会社リガク製、ＺＳＸ１００ｅ）の測定値に基づいて算出した。
（２）Ｍｅ元素置換シュウ酸バリウムチタニル粉末の平均粒子径
マイクロトラックベル社製のＭＴ３０００を用いて、レーザ回折・散乱法により、粒度分布を測定し、該粒度分布における体積積算５０％の粒子径（Ｄ５０）を平均粒子径とした。
（３）Ｍｅ元素置換チタン酸バリウムの平均粒子径
日立ハイテクノロジーズ社製のＳ４８００を用いて、走査型電子顕微鏡（ＳＥＭ）写真により、任意に２００個の粒子を測定し、その平均値を平均粒子径とした。
（４）ＥＰＭＡによるＣａ原子マッピング分析
電子プローブマイクロアナライザ（ＥＰＭＡ）（日本電子株式会社製、ＪＸＡ８５００Ｆ）を用いて、Ｃａ原子をマッピング分析した。
（５）Ｍｅ元素置換シュウ酸バリウムチタニル粉末のＸ線回折分析
株式会社リガク社製のＵｌｔｉｍａＩＶを用いて、Ｘ線回折分析を行った。
In the examples, the characteristics were measured by the following methods.
(1) Mole ratio of Ba atom, Ca atom and Ti atom The molar ratio of each atom was calculated based on the measured value of a fluorescent X-ray analyzer (ZSX100e, manufactured by Rigaku Co., Ltd.).
(2) Average particle size of barium titanyl oxalate powder substituted with Me element Using MT3000 manufactured by Microtrac Bell, the particle size distribution was measured by laser diffraction / scattering method, and the particle size of 50% of the volume integration in the particle size distribution was measured. (D50) was defined as the average particle size.
(3) Average particle size of Me element-substituted barium titanate Using S4800 manufactured by Hitachi High-Technologies Corporation, 200 particles are arbitrarily measured by scanning electron microscope (SEM) photography, and the average value is the average particle. The diameter was set.
(4) Ca atom mapping analysis by EPMA Ca atoms were mapped and analyzed using an electron probe microanalyzer (EPMA) (JXA8500F, manufactured by JEOL Ltd.).
(5) X-ray diffraction analysis of Me element-substituted barium titanyl oxalate powder X-ray diffraction analysis was performed using Ultima IV manufactured by Rigaku Co., Ltd.
（実施例１）
塩化バリウム２水塩５０．０ｇ、塩化カルシウム２水塩１０．０ｇ及び四塩化チタン１２０．０ｇを純水５００ｍｌに溶解して、混合水溶液を調製し、これをＡ液とした。なお、Ａ液中の各元素のモル比を表１に示す。
次いで、シュウ酸７０．０ｇを３０℃の温水５００ｍｌに溶解して、シュウ酸水溶液を調製し、これをＢ液とした。
次いで、Ｂ液（滴下開始後は反応液）を３０℃に保持しながら、撹拌下に１２０分かけてＡ液を４．２ｍｌ／分の速度で添加し、更に３０℃で６０分間撹拌下に熟成した。冷却後、ろ過してシュウ酸バリウムカルシウムチタニル粉末を回収した。
次いで、回収したシュウ酸バリウムカルシウムチタニル粉末を、蒸留水でリパルプして洗浄した。次いで、８０℃で乾燥してシュウ酸バリウムカルシウムチタニル粉末を得た。得られたシュウ酸バリウムカルシウムチタニル粉末の物性値は、表１の通りであった。また、得られたシュウ酸バリウムカルシウムチタニル粉末を８００℃で焼成し、得られたチタン酸バリウムカルシウム粉末を電子プローブマイクロアナライザ（ＥＰＭＡ）（日本電子株式会社製、ＪＸＡ８５００Ｆ）を用いて、Ｃａ原子をマッピング分析した。その結果を図１に示す。図１の結果から、得られたチタン酸バリウムカルシウム粉末では、Ｃａ原子の偏析は見られず、均一にＣａが分散していることが分かった。また、得られたチタン酸バリウムカルシウム粉末の元素分析を行った結果、Ｃａ／Ｂａが０．０２０で、（Ｂａ＋Ｃａ）／Ｔｉが０．９９４であった。
なお、得られたチタン酸バリウムカルシウム粉末の元素分析結果及びＡ液をＢ液に添加して得られたシュウ酸バリウムカルシウムチタニルのＸ線回折分析から、本実施例１で得られたシュウ酸バリウムカルシウムチタニルは、（Ｂａ０．０８０Ｃａ０．０２０）０．９９４ＴｉＯ（Ｃ２Ｏ４）２・４Ｈ２Ｏであると認められた。Ｘ線回折分析の結果を図２に示す。
(Example 1)
A mixed aqueous solution was prepared by dissolving 50.0 g of barium chloride dihydrate, 10.0 g of calcium chloride dihydrate and 120.0 g of titanium tetrachloride in 500 ml of pure water, and this was used as solution A. Table 1 shows the molar ratio of each element in the liquid A.
Next, 70.0 g of oxalic acid was dissolved in 500 ml of warm water at 30 ° C. to prepare an oxalic acid aqueous solution, which was used as solution B.
Next, while maintaining the solution B (reaction solution after the start of dropping) at 30 ° C., the solution A was added at a rate of 4.2 ml / min over 120 minutes under stirring, and further under stirring at 30 ° C. for 60 minutes. Aged. After cooling, it was filtered to recover barium calcium oxalate titanyl powder.
Then, the recovered barium calcium oxalate titanyl powder was repulped with distilled water and washed. Then, it was dried at 80 degreeC to obtain barium calcium oxalate titanyl powder. The physical characteristic values of the obtained barium oxalate calcium titanyl powder are as shown in Table 1. Further, the obtained barium calcium oxalate titanyl powder was fired at 800 ° C., and the obtained barium titanate calcium powder was subjected to Ca atom using an electron probe microanalyzer (EPMA) (JXA8500F, manufactured by JEOL Ltd.). Mapping analysis was performed. The result is shown in FIG. From the results shown in FIG. 1, it was found that in the obtained barium titanate calcium powder, segregation of Ca atoms was not observed, and Ca was uniformly dispersed. Moreover, as a result of elemental analysis of the obtained barium titanate calcium powder, Ca / Ba was 0.020 and (Ba + Ca) / Ti was 0.994.
The barium oxalate obtained in Example 1 was obtained from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium oxalate titanyl obtained by adding the solution A to the solution B. calcium titanyl was observed to be (Ba 0.080 Ca 0.020) 0.994 TiO (C 2 O 4) 2 · 4H 2 O. The result of the X-ray diffraction analysis is shown in FIG.
（実施例２）
塩化バリウム２水塩４０．０ｇ、塩化カルシウム２水塩２０．０ｇ及び四塩化チタン１２０．０ｇを純水５００ｍｌに溶解して、混合水溶液を調製し、これをＡ液とした。なお、Ａ液中の各元素のモル比を表１に示す。
次いで、シュウ酸７０．０ｇを３０℃の温水５００ｍｌに溶解して、シュウ酸水溶液を調製し、これをＢ液とした。
次いで、Ｂ液（滴下開始後は反応液）を３０℃に保持しながら、撹拌下に１２０分かけてＡ液を４．２ｍｌ／分の速度で添加し、更に３０℃で６０分間撹拌下に熟成した。
以後の操作は実施例１と同じ方法で行なった。得られたシュウ酸バリウムカルシウムチタニル粉末の物性値は、表１の通りであった。また、得られたシュウ酸バリウムカルシウムチタニル粉末を焼成し、得られたチタン酸バリウムカルシウム粉末をＥＰＭＡを用いて、Ｃａ原子のマッピング分析を行った。その結果を図３に示す。図３の結果から、得られたチタン酸バリウムカルシウム粉末では、Ｃａ原子の偏析は見られず、均一にＣａが分散していることが分かった。また、得られたチタン酸バリウムカルシウム粉末の元素分析を行った結果、Ｃａ／Ｂａが０．０５で、（Ｂａ＋Ｃａ）／Ｔｉが０．９９８であった。
なお、得られたチタン酸バリウムカルシウム粉末の元素分析結果及びＡ液をＢ液に添加して得られたシュウ酸バリウムカルシウムチタニルのＸ線回折分析から、本実施例２で得られたシュウ酸バリウムカルシウムチタニルは、（Ｂａ０．０８Ｃａ０．０５）０．９９８ＴｉＯ（Ｃ２Ｏ４）２・４Ｈ２Ｏであると認められた。Ｘ線回折分析の結果を図２に示す。
(Example 2)
A mixed aqueous solution was prepared by dissolving 40.0 g of barium chloride dihydrate, 20.0 g of calcium chloride dihydrate and 120.0 g of titanium tetrachloride in 500 ml of pure water, and this was used as solution A. Table 1 shows the molar ratio of each element in the liquid A.
Next, 70.0 g of oxalic acid was dissolved in 500 ml of warm water at 30 ° C. to prepare an oxalic acid aqueous solution, which was used as solution B.
Next, while maintaining the solution B (reaction solution after the start of dropping) at 30 ° C., the solution A was added at a rate of 4.2 ml / min over 120 minutes under stirring, and further under stirring at 30 ° C. for 60 minutes. Aged.
Subsequent operations were performed in the same manner as in Example 1. The physical characteristic values of the obtained barium oxalate calcium titanyl powder are as shown in Table 1. Moreover, the obtained barium calcium oxalate titanyl powder was calcined, and the obtained barium titanate calcium powder was subjected to Ca atom mapping analysis using EPMA. The result is shown in FIG. From the results shown in FIG. 3, it was found that in the obtained barium titanate calcium powder, segregation of Ca atoms was not observed, and Ca was uniformly dispersed. Moreover, as a result of elemental analysis of the obtained barium titanate calcium powder, Ca / Ba was 0.05 and (Ba + Ca) / Ti was 0.998.
The barium oxalate obtained in Example 2 was obtained from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium oxalate titanyl obtained by adding the solution A to the solution B. calcium titanyl was observed to be (Ba 0.08 Ca 0.05) 0.998 TiO (C 2 O 4) 2 · 4H 2 O. The result of the X-ray diffraction analysis is shown in FIG.
（実施例３）
塩化バリウム２水塩４０．０ｇ、塩化カルシウム２水塩７．５ｇ及び四塩化チタン１２０．０ｇを純水５００ｍｌに溶解して、混合水溶液を調製し、これをＡ液とした。なお、Ａ液中の各元素のモル比を表１に示す。
次いで、シュウ酸７０．０ｇを３０℃の温水５００ｍｌに溶解して、シュウ酸水溶液を調製し、これをＢ液とした。
次いで、Ｂ液（滴下開始後は反応液）を３０℃に保持しながら、撹拌下に１２０分かけてＡ液を４．２ｍｌ／分の速度で添加し、更に３０℃で６０分間撹拌下に熟成した。
以後の操作は実施例１と同じ方法で行なった。得られたシュウ酸バリウムカルシウムチタニル粉末の物性値は、表１の通りであった。また、得られたシュウ酸バリウムカルシウムチタニル粉末を焼成し、得られたチタン酸バリウムカルシウム粉末をＥＰＭＡを用いて、Ｃａ原子のマッピング分析を行った。その結果を図４に示す。図４の結果から、得られたチタン酸バリウムカルシウム粉末では、Ｃａ原子の偏析は見られず、均一にＣａが分散していることが分かった。また、得られたチタン酸バリウムカルシウム粉末の元素分析を行った結果、Ｃａ／Ｂａが０．０２で、（Ｂａ＋Ｃａ）／Ｔｉが０．９９１であった。
なお、得られたチタン酸バリウムカルシウム粉末の元素分析結果及びＡ液をＢ液に添加して得られたシュウ酸バリウムカルシウムチタニルのＸ線回折分析から、本実施例３で得られたシュウ酸バリウムカルシウムチタニルは、（Ｂａ０．０８Ｃａ０．０２）０．９９１ＴｉＯ（Ｃ２Ｏ４）２・４Ｈ２Ｏであると認められた。Ｘ線回折分析の結果を図２に示す。
(Example 3)
A mixed aqueous solution was prepared by dissolving 40.0 g of barium chloride dihydrate, 7.5 g of calcium chloride dihydrate and 120.0 g of titanium tetrachloride in 500 ml of pure water, and this was used as solution A. Table 1 shows the molar ratio of each element in the liquid A.
Next, 70.0 g of oxalic acid was dissolved in 500 ml of warm water at 30 ° C. to prepare an oxalic acid aqueous solution, which was used as solution B.
Next, while maintaining the solution B (reaction solution after the start of dropping) at 30 ° C., the solution A was added at a rate of 4.2 ml / min over 120 minutes under stirring, and further under stirring at 30 ° C. for 60 minutes. Aged.
Subsequent operations were performed in the same manner as in Example 1. The physical characteristic values of the obtained barium oxalate calcium titanyl powder are as shown in Table 1. Moreover, the obtained barium calcium oxalate titanyl powder was calcined, and the obtained barium titanate calcium powder was subjected to Ca atom mapping analysis using EPMA. The result is shown in FIG. From the results of FIG. 4, it was found that in the obtained barium titanate calcium powder, segregation of Ca atoms was not observed, and Ca was uniformly dispersed. Moreover, as a result of elemental analysis of the obtained barium titanate calcium powder, Ca / Ba was 0.02 and (Ba + Ca) / Ti was 0.991.
The barium oxalate obtained in Example 3 was obtained from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium oxalate titanyl obtained by adding the solution A to the solution B. calcium titanyl was observed to be (Ba 0.08 Ca 0.02) 0.991 TiO (C 2 O 4) 2 · 4H 2 O. The result of the X-ray diffraction analysis is shown in FIG.
（実施例４）
炭酸バリウム５２．０ｇ、炭酸カルシウム４．７ｇ及び四塩化チタン１２０．０ｇを純水４２０ｍｌに溶解して、混合水溶液を調製し、これをＡ液とした。なお、Ａ液中の各元素のモル比を表１に示す。
次いで、シュウ酸７０．０ｇを３０℃の温水４２０ｍｌに溶解して、シュウ酸水溶液を調製し、これをＢ液とした。
次いで、Ｂ液（滴下開始後は反応液）を３０℃に保持しながら、撹拌下に１２０分かけてＡ液を３．５ｍｌ／分の速度で添加し、更に３０℃で６０分間撹拌下に熟成した。冷却後、ろ過してシュウ酸バリウムカルシウムチタニル粉末を回収した。
次いで、回収したシュウ酸バリウムカルシウムチタニル粉末を、蒸留水でリパルプして洗浄した。次いで、８０℃で乾燥してシュウ酸バリウムカルシウムチタニル粉末を得た。得られたシュウ酸バリウムカルシウムチタニル粉末の物性値は、表１の通りであった。また、得られたシュウ酸バリウムカルシウムチタニル粉末を８００℃で焼成し、得られたチタン酸バリウムカルシウム粉末を電子プローブマイクロアナライザ（ＥＰＭＡ）（日本電子株式会社製、ＪＸＡ８５００Ｆ）を用いて、Ｃａ原子をマッピング分析した。その結果を図５に示す。図５の結果から、得られたチタン酸バリウムカルシウム粉末では、Ｃａ原子の偏析は見られず、均一にＣａが分散していることが分かった。また、得られたチタン酸バリウムカルシウム粉末の元素分析を行った結果、Ｃａ／Ｂａが０．０２６で、（Ｂａ＋Ｃａ）／Ｔｉが０．９９８であった。
なお、得られたチタン酸バリウムカルシウム粉末の元素分析結果及びＡ液をＢ液に添加して得られたシュウ酸バリウムカルシウムチタニルのＸ線回折分析から、本実施例４で得られたシュウ酸バリウムカルシウムチタニルは、（Ｂａ０．０８Ｃａ０．０３）０．９９８ＴｉＯ（Ｃ２Ｏ４）２・４Ｈ２Ｏであると認められた。Ｘ線回折分析の結果を図２に示す。
(Example 4)
52.0 g of barium carbonate, 4.7 g of calcium carbonate and 120.0 g of titanium tetrachloride were dissolved in 420 ml of pure water to prepare a mixed aqueous solution, which was used as solution A. Table 1 shows the molar ratio of each element in the liquid A.
Next, 70.0 g of oxalic acid was dissolved in 420 ml of warm water at 30 ° C. to prepare an oxalic acid aqueous solution, which was used as solution B.
Next, while maintaining the solution B (reaction solution after the start of dropping) at 30 ° C., the solution A was added at a rate of 3.5 ml / min over 120 minutes under stirring, and further under stirring at 30 ° C. for 60 minutes. Aged. After cooling, it was filtered to recover barium calcium oxalate titanyl powder.
Then, the recovered barium calcium oxalate titanyl powder was repulped with distilled water and washed. Then, it was dried at 80 degreeC to obtain barium calcium oxalate titanyl powder. The physical characteristic values of the obtained barium oxalate calcium titanyl powder are as shown in Table 1. Further, the obtained barium calcium oxalate titanyl powder was fired at 800 ° C., and the obtained barium titanate calcium powder was subjected to Ca atom using an electron probe microanalyzer (EPMA) (JXA8500F, manufactured by JEOL Ltd.). Mapping analysis was performed. The result is shown in FIG. From the results shown in FIG. 5, it was found that in the obtained barium titanate calcium powder, segregation of Ca atoms was not observed, and Ca was uniformly dispersed. Moreover, as a result of elemental analysis of the obtained barium titanate calcium powder, Ca / Ba was 0.026 and (Ba + Ca) / Ti was 0.998.
The barium oxalate obtained in Example 4 was obtained from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium oxalate titanyl obtained by adding the solution A to the solution B. calcium titanyl was observed to be (Ba 0.08 Ca 0.03) 0.998 TiO (C 2 O 4) 2 · 4H 2 O. The result of the X-ray diffraction analysis is shown in FIG.
（実施例５）
塩化バリウム２水塩３６０．０ｇ、塩化カルシウム２水塩７２．０ｇ及び四塩化チタン８６４．０ｇを純水３６００ｍｌに溶解して、混合水溶液を調製し、これをＡ液とした。なお、Ａ液中の各元素のモル比を表１に示す。
次いで、シュウ酸５０４．０ｇを３０℃の温水３６００ｍｌに溶解して、シュウ酸水溶液を調製し、これをＢ液とした。
次いで、Ｂ液（滴下開始後は反応液）を３０℃に保持しながら、撹拌下に１２０分かけてＡ液を３０ｍｌ／分の速度で添加し、更に３０℃で６０分間撹拌下に熟成した。冷却後、ろ過してシュウ酸バリウムカルシウムチタニル粉末を回収した。
次いで、回収したシュウ酸バリウムカルシウムチタニル粉末を、蒸留水でリパルプして洗浄した。次いで、８０℃で乾燥してシュウ酸バリウムカルシウムチタニル粉末を得た。得られたシュウ酸バリウムカルシウムチタニル粉末の物性値は、表１の通りであった。また、得られたシュウ酸バリウムカルシウムチタニル粉末を８００℃で焼成し、得られたチタン酸バリウムカルシウム粉末を電子プローブマイクロアナライザ（ＥＰＭＡ）（日本電子株式会社製、ＪＸＡ８５００Ｆ）を用いて、Ｃａ原子をマッピング分析した。その結果を図６に示す。図６の結果から、得られたチタン酸バリウムカルシウム粉末では、Ｃａ原子の偏析は見られず、均一にＣａが分散していることが分かった。また、得られたチタン酸バリウムカルシウム粉末の元素分析を行った結果、Ｃａ／Ｂａが０．０２５で、（Ｂａ＋Ｃａ）／Ｔｉが０．９９４であった。
なお、得られたチタン酸バリウムカルシウム粉末の元素分析結果及びＡ液をＢ液に添加して得られたシュウ酸バリウムカルシウムチタニルのＸ線回折分析から、本実施例５で得られたシュウ酸バリウムカルシウムチタニルは、（Ｂａ０．０８Ｃａ０．０２）０．９９４ＴｉＯ（Ｃ２Ｏ４）２・４Ｈ２Ｏであると認められた。Ｘ線回折分析の結果を図２に示す。
(Example 5)
360.0 g of barium chloride dihydrate, 72.0 g of calcium chloride dihydrate and 864.0 g of titanium tetrachloride were dissolved in 3600 ml of pure water to prepare a mixed aqueous solution, which was used as solution A. Table 1 shows the molar ratio of each element in the liquid A.
Next, 504.0 g of oxalic acid was dissolved in 3600 ml of warm water at 30 ° C. to prepare an aqueous oxalic acid solution, which was used as solution B.
Next, while maintaining the solution B (reaction solution after the start of dropping) at 30 ° C., the solution A was added at a rate of 30 ml / min over 120 minutes under stirring, and further aged at 30 ° C. for 60 minutes under stirring. .. After cooling, it was filtered to recover barium calcium oxalate titanyl powder.
Then, the recovered barium calcium oxalate titanyl powder was repulped with distilled water and washed. Then, it was dried at 80 degreeC to obtain barium calcium oxalate titanyl powder. The physical characteristic values of the obtained barium oxalate calcium titanyl powder are as shown in Table 1. Further, the obtained barium calcium oxalate titanyl powder was fired at 800 ° C., and the obtained barium titanate calcium powder was subjected to Ca atom using an electron probe microanalyzer (EPMA) (JXA8500F, manufactured by JEOL Ltd.). Mapping analysis was performed. The result is shown in FIG. From the results of FIG. 6, it was found that in the obtained barium titanate calcium powder, segregation of Ca atoms was not observed, and Ca was uniformly dispersed. Moreover, as a result of elemental analysis of the obtained barium titanate calcium powder, Ca / Ba was 0.025 and (Ba + Ca) / Ti was 0.994.
The barium oxalate obtained in Example 5 was obtained from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium oxalate titanyl obtained by adding the solution A to the solution B. calcium titanyl was observed to be (Ba 0.08 Ca 0.02) 0.994 TiO (C 2 O 4) 2 · 4H 2 O. The result of the X-ray diffraction analysis is shown in FIG.
（比較例１）
塩化バリウム２水塩１５０．０ｇ、塩化カルシウム２水塩１０．０ｇ及び四塩化チタン１２０．０ｇを純水５００ｍｌに溶解し、混合水溶液を調製し、これをＡ液とした。なお、Ａ液中の各元素のモル比を表１に示す。
次に、シュウ酸７０．０ｇを３０℃の温水５００ｍｌに溶解しシュウ酸水溶液を調製し、これをＢ液とした。
次いで、Ｂ液を３０℃に保持しながら、撹拌下に１２０分かけてＡ液を４．２ｍｌ／分の速度で添加し、更に３０℃で６０分間撹拌下に熟成した。冷却後、ろ過してシュウ酸バリウムカルシウムチタニル粉末を回収した。
以後の操作は実施例１と同じ方法で行なった。得られたシュウ酸バリウムカルシウムチタニル粉末の物性値は表１の通りであった。また、得られたシュウ酸バリウムカルシウムチタニル粉末を焼成し、得られたチタン酸バリウムカルシウム粉末をＥＰＭＡを用いて、Ｃａ原子のマッピング分析を行った。その結果を図７に示す。図７の結果から、得られたチタン酸バリウムカルシウム粉末では、Ｃａ原子が偏析していることが分かった。また、得られたチタン酸バリウムカルシウム粉末の元素分析を行った結果、Ｃａ／Ｂａが０．０２０で、（Ｂａ+Ｃａ）／Ｔｉが１．０００であった。
なお、得られたチタン酸バリウムカルシウム粉末の元素分析結果及びＡ液をＢ液に添加して得られたシュウ酸バリウムカルシウムチタニルのＸ線回折分析から、本比較例１で得られたシュウ酸バリウムカルシウムチタニルは、（Ｂａ０．０８０Ｃａ０．０２０）１．０００ＴｉＯ（Ｃ２Ｏ４）２・４Ｈ２Ｏであると認められた。
(Comparative Example 1)
150.0 g of barium chloride dihydrate, 10.0 g of calcium chloride dihydrate and 120.0 g of titanium tetrachloride were dissolved in 500 ml of pure water to prepare a mixed aqueous solution, which was used as solution A. Table 1 shows the molar ratio of each element in the liquid A.
Next, 70.0 g of oxalic acid was dissolved in 500 ml of warm water at 30 ° C. to prepare an oxalic acid aqueous solution, which was used as solution B.
Then, while maintaining the solution B at 30 ° C., the solution A was added at a rate of 4.2 ml / min over 120 minutes under stirring, and further aged at 30 ° C. for 60 minutes under stirring. After cooling, it was filtered to recover barium calcium oxalate titanyl powder.
Subsequent operations were performed in the same manner as in Example 1. The physical characteristic values of the obtained barium oxalate calcium titanyl powder are as shown in Table 1. Moreover, the obtained barium calcium oxalate titanyl powder was calcined, and the obtained barium titanate calcium powder was subjected to Ca atom mapping analysis using EPMA. The result is shown in FIG. From the results shown in FIG. 7, it was found that Ca atoms were segregated in the obtained barium titanate calcium powder. Moreover, as a result of elemental analysis of the obtained barium calcium titanate powder, Ca / Ba was 0.020 and (Ba + Ca) / Ti was 1.000.
The barium oxalate obtained in Comparative Example 1 was obtained from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium oxalate titanyl obtained by adding the solution A to the solution B. calcium titanyl was observed to be (Ba 0.080 Ca 0.020) 1.000 TiO (C 2 O 4) 2 · 4H 2 O.
（比較例２）
塩化バリウム２水塩２７．０ｇ、塩化カルシウム２水塩５．４ｇ及び四塩化チタン６４．１ｇを純水１８０ｍｌに溶解し、混合水溶液を調製し、これをＡ液とした。なお、Ａ液中の各元素のモル比を表１に示す。
次に、シュウ酸３２．５ｇを５５℃の温水１４０ｍｌに溶解しシュウ酸水溶液を調製し、これをＢ液とした。
次いで、Ｂ液を５５℃に保持しながら、撹拌下に１２０分かけてＡ液を１．５ｍｌ／分の速度で添加し、更に５５℃で６０分間撹拌下に熟成した。冷却後、ろ過してシュウ酸バリウムカルシウムチタニル粉末を回収した。
以後の操作は実施例１と同じ方法で行なった。得られたシュウ酸バリウムカルシウムチタニル粉末の物性値は表１の通りであった。また、得られたシュウ酸バリウムカルシウムチタニル粉末を焼成し、得られたチタン酸バリウムカルシウム粉末をＥＰＭＡを用いて、Ｃａ原子のマッピング分析を行った。その結果を図８に示す。図８の結果から、得られたチタン酸バリウムカルシウム粉末では、Ｃａ原子が偏析していることが分かった。また、得られたチタン酸バリウムカルシウム粉末の元素分析を行った結果、Ｃａ／Ｂａが０．０２０で、（Ｂａ＋Ｃａ）／Ｔｉが０．９９９であった。
なお、得られたチタン酸バリウムカルシウム粉末の元素分析結果及びＡ液をＢ液に添加して得られたシュウ酸バリウムカルシウムチタニルのＸ線回折分析から、本比較例２で得られたシュウ酸バリウムカルシウムチタニルは、（Ｂａ０．０８０Ｃａ０．０２０）０．９９９ＴｉＯ（Ｃ２Ｏ４）２・４Ｈ２Ｏであると認められた。
(Comparative Example 2)
27.0 g of barium chloride dihydrate, 5.4 g of calcium chloride dihydrate and 64.1 g of titanium tetrachloride were dissolved in 180 ml of pure water to prepare a mixed aqueous solution, which was used as solution A. Table 1 shows the molar ratio of each element in the liquid A.
Next, 32.5 g of oxalic acid was dissolved in 140 ml of warm water at 55 ° C. to prepare an oxalic acid aqueous solution, which was used as solution B.
Then, while maintaining the solution B at 55 ° C., the solution A was added at a rate of 1.5 ml / min over 120 minutes under stirring, and further aged at 55 ° C. for 60 minutes under stirring. After cooling, it was filtered to recover barium calcium oxalate titanyl powder.
Subsequent operations were performed in the same manner as in Example 1. The physical characteristic values of the obtained barium oxalate calcium titanyl powder are as shown in Table 1. Moreover, the obtained barium calcium oxalate titanyl powder was calcined, and the obtained barium titanate calcium powder was subjected to Ca atom mapping analysis using EPMA. The result is shown in FIG. From the results shown in FIG. 8, it was found that Ca atoms were segregated in the obtained barium titanate calcium powder. Moreover, as a result of elemental analysis of the obtained barium titanate calcium powder, Ca / Ba was 0.020 and (Ba + Ca) / Ti was 0.999.
The barium oxalate obtained in Comparative Example 2 was obtained from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium oxalate titanyl obtained by adding the solution A to the solution B. calcium titanyl was observed to be (Ba 0.080 Ca 0.020) 0.999 TiO (C 2 O 4) 2 · 4H 2 O.
表１及び図１〜８の結果から、実施例のシュウ酸バリウムカルシウムチタニルから得られたチタン酸バリウムカルシウムは、比較例のシュウ酸バリウムカルシウムチタニルから得られたチタン酸バリウムカルシウムと比べて、カルシウム原子が偏析せず、均一に分布していることが判った。 From the results of Table 1 and FIGS. 1 to 8, the barium calcium titanate obtained from the barium calcium oxalate titanyl of the example is calcium as compared with the barium calcium titanate obtained from the barium calcium oxalate titanyl of the comparative example. It was found that the atoms were not segregated and were uniformly distributed.
Claims (10)
Ｔｉに対するＢａとＭｅ元素の合計のモル比（（Ｂａ＋Ｍｅ）／Ｔｉ）が０．９８０以上０．９９９未満であり、Ｂａに対するＭｅ元素のモル比（Ｍｅ／Ｂａ）が０．００１以上０．２５０以下であること、
を特徴とするＭｅ元素置換有機酸バリウムチタニル粉末。 A Me element-substituted barium titanyl organic acid in which a part of the Ba site is substituted with a Me element (Me indicates at least one selected from Ca, Sr and Mg).
The total molar ratio of Ba and Me element to Ti ((Ba + Me) / Ti) is 0.980 or more and less than 0.999, and the molar ratio of Me element to Ba (Me / Ba) is 0.001 or more and 0.250. Must be
Me element-substituted organic acid barium titanyl powder.
該Ａ液中、原子換算で、Ｂａに対するＭｅ元素のモル比（Ｍｅ／Ｂａ）が０．０２０以上５．０００以下であり、Ｔｉに対するＢａのモル比（Ｂａ／Ｔｉ）が０．３００以上１．２００以下であり、且つ、Ａ液とＢ液の混合温度が１０〜５０℃であること、
を特徴とするＭｅ元素置換有機酸バリウムチタニル粉末の製造方法。 An aqueous solution (solution A) obtained by mixing a barium compound, a Me element compound (Me indicates at least one selected from Ca, Sr and Mg) and a titanium compound in water is used as an organic acid aqueous solution (solution B). It is a method for producing a barium titanyl powder of a Me element-substituted organic acid by adding it to the barium titanyl powder of a Me element-substituted organic acid.
In the liquid A, the molar ratio of Me element to Ba (Me / Ba) is 0.020 or more and 5.000 or less, and the molar ratio of Ba to Ti (Ba / Ti) is 0.300 or more and 1 .200 or less, and the mixing temperature of solution A and solution B is 10 to 50 ° C.
A method for producing barium titanyl powder, which is a Me element-substituted organic acid.
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| PCT/JP2020/027199 WO2021010368A1 (en) | 2019-07-16 | 2020-07-13 | Me ELEMENT-SUBSTITUTED ORGANIC ACID TITANYL BARIUM, METHOD FOR PRODUCING SAME, AND METHOD FOR PRODUCING TITANIUM-BASED PEROVSKITE-TYPE CERAMIC RAW MATERIAL POWDER |
| CN202080051268.1A CN114127013B (en) | 2019-07-16 | 2020-07-13 | Me element-substituted organic acid barium titanyl oxide, process for producing the same, and process for producing titanium perovskite ceramic raw material powder |
| KR1020227001056A KR20220035115A (en) | 2019-07-16 | 2020-07-13 | Me element substituted organic acid barium titanyl, method for producing same, and method for producing titanium-based perovskite-type ceramic raw material powder |
| TW109123753A TW202108548A (en) | 2019-07-16 | 2020-07-14 | Barium titanate organic acid powder substituted by Me element, its manufacturing method and manufacturing method of titanium-based perovskite-type ceramic raw material powder wherein the substitute elements do not segregate and are uniform distributed |
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