JP7438867B2 - Me element-substituted organic acid barium titanyl, method for producing the same, and method for producing titanium-based perovskite ceramic raw material powder - Google Patents
Me element-substituted organic acid barium titanyl, method for producing the same, and method for producing titanium-based perovskite ceramic raw material powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims description 216
- 229910052788 barium Inorganic materials 0.000 title claims description 146
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims description 131
- 150000007524 organic acids Chemical class 0.000 title claims description 130
- 239000010936 titanium Substances 0.000 title claims description 85
- 238000004519 manufacturing process Methods 0.000 title claims description 59
- 239000000919 ceramic Substances 0.000 title claims description 43
- 229910052719 titanium Inorganic materials 0.000 title claims description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 38
- 239000002994 raw material Substances 0.000 title claims description 36
- 239000007788 liquid Substances 0.000 claims description 88
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 83
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical class [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 46
- 229910002113 barium titanate Inorganic materials 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 35
- 238000010304 firing Methods 0.000 claims description 33
- 229910052791 calcium Inorganic materials 0.000 claims description 31
- 235000006408 oxalic acid Nutrition 0.000 claims description 26
- 238000004458 analytical method Methods 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 20
- 238000013507 mapping Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 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
- 229910052712 strontium Inorganic materials 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
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 150000001553 barium compounds Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000523 sample Substances 0.000 claims description 9
- 150000003609 titanium compounds Chemical class 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-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 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
- 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
- 150000001552 barium Chemical class 0.000 claims description 2
- 239000011575 calcium Substances 0.000 description 78
- 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 40
- 239000000243 solution Substances 0.000 description 40
- QKKWJYSVXDGOOJ-UHFFFAOYSA-N oxalic acid;oxotitanium Chemical compound [Ti]=O.OC(=O)C(O)=O QKKWJYSVXDGOOJ-UHFFFAOYSA-N 0.000 description 35
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 description 32
- 238000005204 segregation Methods 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 22
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 238000000921 elemental analysis Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- -1 barium titanyl oxalate Chemical class 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 229960005069 calcium Drugs 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 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
- 239000000463 material Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 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
- 238000001816 cooling Methods 0.000 description 6
- 230000005070 ripening Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 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
- 239000000654 additive Substances 0.000 description 4
- 235000005985 organic acids Nutrition 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
- 239000002253 acid 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
- 230000009257 reactivity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000000996 additive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000004703 alkoxides Chemical class 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
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 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
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000007561 laser diffraction method Methods 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
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- IAGCDJZAYOZMCS-UHFFFAOYSA-N 2-hydroxypropanoic acid;titanium Chemical compound [Ti].CC(O)C(O)=O IAGCDJZAYOZMCS-UHFFFAOYSA-N 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 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
- 229910021529 ammonia 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
- 230000015572 biosynthetic process Effects 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
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 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
- 229910010293 ceramic material Inorganic materials 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
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 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
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 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
- 239000006104 solid solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000001238 wet grinding Methods 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)
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 an organic acid barium titanyl in which a part of the barium element is replaced with other elements, which is useful as a raw material for functional ceramics such as dielectrics, piezoelectrics, optoelectronic materials, semiconductors, and sensors, and a method for producing the same. be.
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) is generally in the form of a multicomponent system consisting of barium titanate, the main raw material, and trace amounts of additives. For example, calcium is a component often used as an additive, and by substituting solid solution into the barium site in barium titanate, it has the effect as a depressor that smooths the temperature characteristics of the relative permittivity of the dielectric, or It is known to be 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。 Barium titanate, which takes the form of the multicomponent system described above, can be obtained by adding trace components using conventionally known solid phase methods, oxalate methods, hydrothermal synthesis methods, alkoxide methods, etc. . Among these, the oxalate method is a manufacturing method in which barium titanate is synthesized by heat-treating a wet-synthesized oxalate precursor and deoxalating it. The most important feature of the oxalate method is that high-grade and stoichiometric barium titanate can be obtained from the composition ratio of barium and titanium (Ba/Ti) 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。 Several processes have been reported for the oxalate method, but industrially the most common method is to add a mixture of titanium chloride and barium chloride to an aqueous oxalic acid solution to carry out the reaction. A method has been proposed for producing barium titanyl oxalate in which part of the barium element is replaced with another metal element using this oxalate method.
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 contains another alkaline earth metal compound to be substituted, and this is added to an aqueous oxalic acid solution. However, it has the disadvantage 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, and the reaction is carried out. It is described that when carried out, barium titanyl oxalate can be obtained with improved reactivity and a high substitution rate of other elements replacing 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, barium, barium, It is described that ceramic raw material fine powder with excellent uniformity and good dispersibility of alkaline earth metals such as calcium and titanium 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, although the method described in Cited Document 2 allows barium sites to be substituted with other elements such as calcium with a high probability, the reactivity is too high, so the substituted elements are distributed uniformly throughout the barium titanyl oxalate. There was a problem that it was difficult to do so.
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。 Furthermore, according to the example in Cited Document 3, it is stated that a product with a composition according to the charging composition can be obtained, but there is no evaluation regarding uniformity, and it is also possible to adjust the pH using ammonia. However, it cannot be said that it is 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 to provide organic acid barium titanyl and barium titanate in which a part of the Ba site is substituted with another element (Me element), in which the substituted element does not segregate and the organic acid barium titanyl Providing a Me element-substituted organic acid barium titanyl powder and barium titanate powder uniformly distributed throughout the powder or barium titanate powder, and industrially producing the organic acid barium titanyl or the barium titanate powder. An object of the present invention is to provide an advantageous manufacturing method.
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 extensive research in view of the above circumstances, the present inventors set the molar ratio of the sum of Ba and Me elements to Ti in the organic acid barium titanyl to a range of 0.980 to 0.999, which is slightly smaller than 1, and It was discovered that an organic acid barium titanyl powder with less segregation can be obtained by setting the molar ratio of Me element to Ba to 0.001 to 0.200, and the present invention was completed based on this finding.
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 organic acid barium titanyl in which a part of the Ba site is replaced with Me element (Me represents at least one selected from Ca, Sr, and Mg). ,
The molar ratio of the sum of Ba and Me elements 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. be less than or equal to
The present invention provides a Me element-substituted organic acid barium titanyl powder characterized by the following.
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。 In addition, in the present invention (2), in electron probe microanalyzer (EPMA) analysis, the Me element is uniformly distributed in the particles of the Me element-substituted barium titanate powder obtained by firing the Me element-substituted organic acid barium titanyl powder. The present invention provides the Me element-substituted organic acid barium titanyl powder according to (1), which is characterized in that the Me element is distributed in the following manner.
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。 In addition, the present invention (3) uses electron probe microanalyzer (EPMA) analysis to detect the surface of the Me element-substituted barium titanate compact obtained by firing the Me element-substituted organic acid barium titanyl powder. , The CV value (standard deviation/average value) of Ca shall be 0.4 or less in image analysis obtained by mapping analysis of 256 vertical and horizontal points at 0.8 μm intervals to form a square range of 205 μm on a side. The present invention provides the Me element-substituted organic acid barium titanyl powder of (1), which is characterized by the following.
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。
In addition, in the present invention (4), a Me element-substituted organic A method for producing Me element-substituted organic acid barium titanyl powder to obtain barium titanyl acid,
In the liquid A, the molar ratio of the 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 liquid A and liquid B is 10 to 50°C,
The present invention provides a method for producing Me element-substituted organic acid barium titanyl powder, which is characterized by the following.
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. A method for producing powder is provided.
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 ( The present invention provides a method for producing Me element-substituted organic acid barium titanyl powder 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。 In addition, the present invention (7) is characterized in that the titanium compound is at least one selected from titanium tetrachloride and titanium lactic acid. A method for producing powder is provided.
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. A method for producing Me element-substituted organic acid barium titanyl powder is provided.
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。 In addition, the present invention (9) provides a titanium-based perovskite type characterized in that Me element-substituted barium titanate is obtained by firing the Me element-substituted barium titanyl powder of any one of (1) to (3). The present invention provides a method for producing 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。 In addition, the present invention (10) provides Me element-substituted organic acid barium titanyl powder obtained by performing any of the methods (4) to (8) for producing Me element-substituted organic acid barium titanyl powder. The present invention provides a method for producing a titanium-based perovskite ceramic raw material powder, which is characterized in that a substituted barium titanate powder is obtained.
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, organic acid barium titanyl and barium titanate in which a part of the Ba site is substituted with another element (Me element), the substituted element is not segregated, and the organic acid barium titanyl powder is whole. Alternatively, it is possible to provide a Me element-substituted organic acid barium titanyl powder and a barium titanate powder that are uniformly distributed throughout the barium titanate powder, and to make the organic acid barium titanyl or the barium titanate powder industrially advantageous. A manufacturing method 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 the Ba site is substituted with Me element (Me represents at least one selected from Ca, Sr, and Mg). barium titanyl,
The molar ratio of the sum of Ba and Me elements 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. be less than or equal to
This is a Me element-substituted organic acid barium titanyl powder 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 organic acid barium titanyl powder of the present invention is in powder form and is an aggregate of particles of organic acid barium titanyl in which a part of the Ba site is substituted with the 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 organic acid barium titanyl powder of the present invention, the Me element substituting a part of the Ba site of the organic acid barium titanyl is at least one element selected from Ca, Sr, and Mg, and is preferably Ca and Sr, particularly preferably Ca. Me may be one type or two or more types.
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 molar ratio of the sum of Ba and Me elements 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. By having (Ba+Me)/Ti within the above range, a Me element-substituted organic acid barium titanyl powder can be obtained in which the Me element is uniformly distributed throughout the powder and there is little segregation of the Me element, and upon firing, A Me element-substituted barium titanate powder is obtained in which the Me element is uniformly distributed throughout the powder and there is little segregation of the Me element. On the other hand, if (Ba+Me)/Ti is less than the above range, it will be difficult to obtain Me element-substituted barium titanate having desired properties, and if it exceeds the above range, segregation of the Me element will likely 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 Me element-substituted organic acid barium titanyl powder of the present invention is 0.001 or more and 0.250 or less, preferably 0.005 or more and 0.150 or less. By having Me/Ba within the above range, Me element is uniformly distributed throughout the powder, and Me element-substituted organic acid barium titanyl with less segregation of Me element can be obtained. Barium titanate substituted with Me element can be obtained, which is uniformly distributed throughout the particles and has less segregation of Me element. On the other hand, if Me/Ba is less than the above range, it will be difficult to obtain Me element-substituted barium titanate having desired properties, and if it exceeds the above range, segregation of the Me element will likely 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, those in which the organic acid is oxalic acid include, for example, 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 from 1 to 8.)
Me element-substituted barium titanyl oxalate powder 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 general formula (1), Me is at least one element selected from Ca, Sr and Mg, preferably Ca and Sr, particularly preferably Ca. Me may be one type or two or more types. That is, in the Me element-substituted barium titanyl oxalate powder represented by the general formula (1), a part of the Ba site is substituted 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 molar ratio of the sum 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, particularly preferably 0.985 or more and 0.997 or less. By setting q within the above range, a Me element-substituted barium titanyl oxalate powder can be obtained in which the Me element is uniformly distributed throughout the powder, and the segregation of the Me element is small. A Me element-substituted barium titanate powder is obtained which is uniformly distributed throughout and has little segregation of the Me element. On the other hand, if q is less than the above range, it will be difficult to obtain Me element-substituted barium titanate having desired properties, and if it exceeds the above range, segregation of the Me element will likely 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 of the Me element to Ba (Me/Ba) in terms of atoms. p is 0.001 or more and 0.200 or less, preferably 0.005 or more and 0.150 or less. By having p in the above range, Me element is uniformly distributed throughout the powder, and Me element-substituted barium titanyl oxalate with less segregation of Me element can be obtained. Barium titanate substituted with Me element can be obtained, in which the Me element is uniformly distributed and the Me element is less segregated. On the other hand, if p is less than the above range, it will be difficult to obtain Me element-substituted barium titanate having desired properties, and if it exceeds the above range, segregation of the Me element will likely 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 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 Ti, Ba, and Me atoms in the Me element-substituted barium titanyl oxalate represented by general formula (1) is based on the measured value using a fluorescent X-ray analyzer (manufactured by Rigaku Co., Ltd., ZSX100e). It can be calculated based on In addition, regarding the molar ratio of Ti, Ba, and Me atoms in the Me element-substituted barium titanyl oxalate represented by general formula (1), the Me element-substituted barium titanyl oxalate obtained by firing the Me element-substituted barium titanyl oxalate is It can also be calculated based on the value obtained by measuring barium titanate with a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, ZSX100e).
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 diameter of the Me element-substituted organic acid barium titanyl powder of the present invention is not particularly limited, but is preferably 0.1 to 300 μm, particularly preferably 0.5 to 200 μm. In the present invention, the average particle diameter of the Me element-substituted organic acid barium titanyl refers to the particle diameter at 50% volume integration (D50) in the particle size distribution determined by 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 fired product obtained by firing the Me element-substituted organic acid barium titanyl powder of the present invention at 600 to 1200°C, preferably 650 to 1100°C is a titanium-based perovskite-type composite oxide, in which a part of the Ba site is Me Barium titanate substituted with elements. That is, the fired product of the Me element-substituted organic acid barium titanyl powder of the present invention has the following general formula (2):
(Ba 1-x Me x ) y TiO 3 (2)
This is Me element-substituted barium titanate powder represented by: In 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. Moreover, y is 0.980≦y<0.999, preferably 0.983≦y≦0.998, 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 organic acid barium titanyl powder of the present invention at 600 to 1200°C, preferably 650 to 1100°C, the Me element is uniformly distributed in each particle. It is distributed in In addition, in the present invention, the fact that Me element is uniformly distributed in the particles of Me element-substituted barium titanate has been confirmed using electron probe microanalyzer (EPMA) analysis. In image analysis obtained by mapping analysis of 256 vertical and horizontal points at 0.8 μm intervals on the surface of a square with a side of 205 μm, the CV value (standard deviation / average value) of Ca was calculated, 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。
The method for producing Me element-substituted organic acid barium titanyl powder of the present invention includes mixing a barium compound, a Me element compound (Me represents at least one selected from Ca, Sr, and Mg), and a titanium compound in water. A method for producing Me element-substituted organic acid barium titanyl powder, in which Me element-substituted organic acid barium titanyl is obtained by adding the obtained aqueous solution (Liquid A) to an organic acid aqueous solution (Liquid B),
In the liquid A, the molar ratio of Me to Ba (Me/Ba) is 0.020 to 5.000 in terms of atoms, and the molar ratio of Ba to Ti (Ba/Ti) in terms of atoms is 0.020 to 5.000. 300 or more and 1.200 or less, and the addition rate of liquid A to liquid B is 2.0 ml/min or more;
This is a method for producing Me element-substituted organic acid barium titanyl powder, characterized by:
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 Me element-substituted organic acid barium titanyl powder of the present invention, first, the entire amount of liquid B used for the reaction is placed in a reaction vessel, and then liquid A is supplied to the reaction vessel, and liquid A is replaced with liquid B. This is a method for producing barium titanyl, an organic acid substituted with Me element, in which a reaction is performed to produce barium titanyl organic acid substituted with Me element.
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。 Solution A according to the method for producing barium titanyl 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 in 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 barium titanyl Me element-substituted organic acid of the present invention is not particularly limited, and examples thereof include barium chloride, barium carbonate, barium hydroxide, barium acetate, barium nitrate, and the like. The barium compound may be used alone or in combination of two or more. The barium compound is preferably one or more selected from the group consisting of barium chloride, barium carbonate, and barium hydroxide.
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 Me element-substituted organic acid barium titanyl of the present invention is not particularly limited, and 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 used alone or in combination of two or more types. The Me element compound is preferably one or more selected from the group consisting of Me element chloride, Me element carbonate, and Me element hydroxide.
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 barium titanyl Me element-substituted organic acid of the present invention is not particularly limited, and includes titanium tetrachloride, titanium lactate, and the like. The titanium compound may be used alone or in combination of two or more. As the titanium compound, titanium tetrachloride is preferred.
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 acids used in the method for producing Me element-substituted organic acid barium titanyl of the present invention include oxalic acid, citric acid, malonic acid, and succinic acid. The organic acids may be used alone or in combination of two or more. As the organic acid, oxalic acid is preferred.
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, 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 because of high reactivity. It is preferable to use one with stable quality and 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。 In liquid A, the molar ratio of Me element to Ba (Me/Ba) in terms of atoms is 0.020 or more and 5.000 or less, preferably 0.050 or more and 4.000 or less. Since the molar ratio of Me element to Ba (Me/Ba) in atomic terms in liquid A is within the above range, Me element is uniformly distributed throughout the powder, resulting in Me element substitution with less segregation of Me element. An organic acid 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 less segregation of the Me element is obtained. On the other hand, if the molar ratio of Ba to Ti (Ba/Ti) in terms of atoms in liquid A is less than the above range, substitution of Me elements will be difficult to proceed, and if it exceeds the above range, segregation of Me elements will likely 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 liquid A, the molar ratio of Ba to Ti (Ba/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 (Ba/Ti) in terms of atoms in liquid A is within the above range, the Me element is uniformly distributed throughout the particles, and the Me element substituted organic material has less segregation of the Me element. Barium titanyl acid is obtained, and by calcination, Me element-substituted barium titanate in which the Me element is uniformly distributed throughout the particles and less segregation of the Me element is obtained. On the other hand, if the molar ratio of Ba to Ti (Ba/Ti) in terms of atoms in liquid A is less than the above range, substitution of Me elements will be difficult to proceed, and if it exceeds the above range, segregation of Me elements will occur. It becomes 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 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 Me element concentration in 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 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 B solution according to the method for producing Me element-substituted organic acid barium titanyl of the present invention is an organic acid aqueous 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 elements, and Ti in terms of atoms in liquid A to the number of moles of organic acid ions in liquid B is 0.800 or more and 1.400 or less, preferably 0.850 or more and 1.300 or less. , particularly preferably from 0.900 to 1.250. When the ratio of the total number of moles of Ba, Me elements, and Ti in terms of atoms in liquid A to the number of moles of organic acid ions in liquid B is within the above range, the Me element is uniformly distributed throughout the particles. As a result, Me element-substituted organic acid barium titanyl with less segregation of 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 organic acid ions in liquid B is not particularly limited, but is preferably 0.10 to 5.00 mol/L, 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 liquid B is placed in a reaction vessel, then liquid A is supplied to the reaction vessel, and liquid A is added to liquid B. In this manner, a reaction for producing Me element-substituted organic acid barium titanyl is carried out in the reaction vessel.
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 liquid A when adding liquid A to liquid B depends on the scale of implementation, but for example, at a 0.5L scale laboratory level, the rate of addition of liquid A is 2.0 ml/min or more, especially 3.0 ml/min or more. It is preferable that By adding liquid A to liquid B at the above-mentioned addition rate, Me element-substituted organic acid barium titanyl can be obtained in which Me element is uniformly distributed throughout the particles and there is little segregation of Me element. Note that 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 adding liquid A to liquid B, that is, the temperature of liquid A and the reaction liquid (or liquid B) in the reaction vessel when adding liquid A to the reaction vessel, is usually 10 to 50°C, preferably is 15-45°C. By adding liquid A to liquid B at the above-mentioned mixing temperature, Me element-substituted organic acid barium titanyl can be obtained, in which Me element is uniformly distributed throughout the particles and there is little segregation of 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。 After adding the entire amount of Solution A to Solution B, the reaction may be terminated by immediately cooling the reaction solution, or by removing the reaction solution by filtration, or by adding A to Solution B. After the entire amount of the liquid is added, the reaction liquid may be aged at a predetermined temperature for a certain period of time. In the case of ripening, the ripening temperature is preferably 10°C or higher, particularly preferably 20 to 80°C, and the ripening time is preferably 0.1 hour or more, particularly preferably 0.2 hour or more.
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 adding liquid A to liquid B, it is preferable to add liquid A to liquid B while stirring the reaction liquid (or liquid B). Further, when ripening is performed after adding the entire amount of liquid A to liquid B, it is preferable to carry out the ripening while stirring the reaction liquid. The stirring speed is not particularly limited, but when ripening is performed, from the start of addition of liquid A to liquid B until the end of the addition of the entire amount of liquid A, the Me element-substituted organic acid barium titanyl produced is Any stirring speed may be used as long as the reaction liquid contained therein is constantly in a fluid 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, after completion of aging, solid-liquid separation of the reaction solution is performed by a conventional method, and then the solid content is washed with water. The water washing method is not particularly limited, but washing with repulp or the like is preferred in terms of high washing efficiency. After washing, the solid content is dried and, if necessary, pulverized to obtain Me element-substituted organic acid barium titanyl, that is, organic acid barium titanyl in which a part of the Ba site 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 organic acid barium titanyl powder obtained by carrying out the method for producing the Me element-substituted organic acid barium titanyl powder of the present invention is an organic acid barium titanyl powder in which a part of the Ba site is substituted with the Me element. and the molar ratio of the total of Ba and Me elements 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 organic acid barium titanyl obtained by the method for producing Me element-substituted organic acid barium titanyl powder of the present invention, the Me element represents at least one element selected from Ca, Sr, and Mg, and 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 less than 0.998. The following is particularly preferably 0.985 or more and 0.997 or less, and the molar ratio of Me element to Ba (Me/Ba) is 0.001 or more and 0.250 or less, preferably 0.005 or more and 0.150 or less. 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 organic acid barium titanyl powder obtained by carrying out the method for producing the Me element-substituted organic acid barium titanyl powder of the present invention is not particularly limited, but is preferably 0.1 to 300 μm, particularly preferably 0.1 to 300 μm. 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 Me element-substituted organic acid barium titanyl powder of the present invention, Me element is uniformly distributed throughout the powder, and Me element-substituted organic acid barium titanyl powder with less segregation of Me element can be obtained. Note that the Me element is uniformly distributed throughout the Me element-substituted organic acid barium titanyl powder, and the segregation of the Me element is small. It is confirmed by calcining the element-substituted organic acid barium titanyl powder at 600 to 1200° C. and mapping the obtained Me element-substituted barium titanate using 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 organic acid barium titanyl powder obtained by carrying out the method for producing the Me element-substituted organic acid barium titanyl powder of the present invention at 600 to 1200°C, preferably 650 to 1100°C. In substituted barium titanate, Me element is uniformly distributed on the particle surface. Further, in the Me element-substituted organic acid barium titanyl powder obtained by the method for producing Me element-substituted organic acid barium titanyl powder 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。 Me element-substituted organic acid barium titanyl powder of the present invention and Me element-substituted titanic acid obtained by firing the Me element-substituted organic acid barium titanyl powder obtained by carrying out the method for producing the Me element-substituted organic acid barium titanyl powder of the present invention. Barium powder is suitably used as a titanium-based perovskite ceramic raw material powder for dielectric ceramic materials. That is, the Me element-substituted organic acid barium titanyl powder of the present invention or the Me element-substituted organic acid barium titanyl powder obtained by carrying out the method for producing the Me element-substituted organic acid barium titanyl powder of the present invention is heated to a temperature of 600 to 1200°C, preferably By firing at 650 to 1100°C, a titanium-based perovskite 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。
Me element-substituted organic acid barium titanyl powder of the present invention and Me element-substituted titanic acid obtained by firing the Me element-substituted organic acid barium titanyl powder obtained by carrying out the method for producing the Me element-substituted organic acid barium titanyl powder of the present invention. Barium powder has the following general formula (2):
(Ba 1-x Me x ) y TiO 3 (2)
This is Me element-substituted barium titanate powder represented by: In 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. Moreover, y is 0.980≦y<0.999, preferably 0.983≦y≦0.998, 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 performing the above firing, if necessary, the average particle size of the Me element-substituted organic acid barium titanyl is adjusted so that a fine titanium-based perovskite ceramic raw material powder with high crystallinity can be obtained even if fired at a low temperature. The Me element-substituted organic acid barium titanyl powder may be wet-pulverized using a ball mill, bead mill, etc. so that the particle size is preferably 4 μm or less, particularly preferably 0.02 to 0.5 μm. In this case, the solvent used in the wet pulverization treatment is one that is inert to Me element-substituted organic acid barium titanyl, such as water, methanol, ethanol, propanol, butanol, toluene, xylene, acetone, chloride, etc. Examples include methylene, ethyl acetate, dimethylformamide and diethyl ether. Among these, organic solvents such as methanol, ethanol, propanol, butanol, toluene, xylene, acetone, methylene chloride, ethyl acetate, dimethylformamide, and diethyl ether are used as solvents for wet grinding, and Ba elements, Ti elements, and Me It is preferable to use a material with a small amount of element elution, since it is possible to obtain a titanium-based perovskite-type ceramic raw material powder with high crystallinity.
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 includes the Me element-substituted organic acid barium titanyl powder of the present invention, or the Me element-substituted organic acid barium titanyl powder obtained by carrying out the method of producing the Me element-substituted organic acid barium titanyl powder of the present invention. This is a method for producing a titanium-based perovskite ceramic raw material powder, which is characterized by obtaining Me element-substituted barium titanate 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。 Organic substances derived from organic acids contained in the Me element-substituted organic acid barium titanyl powder are not preferable because they impair the dielectric properties of the material and cause instability in the behavior in the thermal process for ceramic formation. Therefore, in the method for producing a titanium-based perovskite-type ceramic raw material powder of the present invention, by firing the Me element-substituted organic acid barium titanyl powder, the Me element-containing organic acid barium titanyl is thermally decomposed and the desired titanium-based perovskite is produced. While obtaining Me element-substituted barium titanate, which is a type ceramic raw material powder, 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 ceramic raw material powder of the present invention, the firing temperature during 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 ceramic powder, and if it exceeds the above range, the variation in particle size will increase. In the method for producing a titanium-based perovskite ceramic raw material powder of the present invention, the firing time during firing is preferably 0.2 to 30 hours, particularly preferably 0.5 to 20 hours. In the method for producing a titanium-based perovskite ceramic raw material powder of the present invention, the firing atmosphere during 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 ceramic raw material powder of the present invention, firing may be performed only once, or may be repeated two or more times as necessary. In the case of repeating firing, in order to make the powder properties uniform, the powder that has been fired once may be pulverized 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, after firing, the titanium-based perovskite-type ceramic raw material powder is appropriately cooled and optionally pulverized to obtain a titanium-based perovskite-type composite oxide, which is suitable as a titanium-based perovskite-type ceramic raw material powder. A Me element-substituted barium titanate powder is obtained. Note that the pulverization, which is performed as necessary, is carried out appropriately when the Me element-substituted barium titanate powder obtained by firing is in the form of a brittle, bonded block. 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 a titanium-based perovskite ceramic raw material powder of the present invention has an average particle diameter 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, 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, the average particle diameter of the Me element-substituted barium titanate powder was determined by arbitrarily measuring 200 particles using a scanning electron microscope (SEM) photograph, and the average value was taken as the average particle diameter.
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。 Incidentally, the titanium-based perovskite-type ceramic raw material powder obtained by carrying out the method for producing a titanium-based perovskite-type ceramic raw material powder of the present invention may optionally contain 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 ceramic raw material powder. Examples of the subcomponent element-containing compounds 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.
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 subsidiary component element-containing compound may be either inorganic or organic, and includes, for example, oxides, hydroxides, chlorides, nitrates, oxalates, carboxylates, and alkoxides containing the above elements. In addition, when the subcomponent element-containing compound is a compound containing Si element, silica sol, sodium silicate, etc. can also be used in addition to the above-mentioned oxides. The above-mentioned subcomponent element-containing compounds may be used alone or in an appropriate combination of two or more, and the amount added and the combination of additive compounds are appropriately selected depending on 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。 A method for incorporating a subcomponent element into a titanium-based perovskite-type ceramic raw material powder includes, for example, a titanium-based perovskite-type ceramic raw material powder obtained by carrying out the method for producing a titanium-based perovskite-type ceramic raw material powder of the present invention and a compound containing a subcomponent element. The organic acid barium titanyl powder of the present invention and the subcomponent element-containing compound obtained by performing a method of uniformly mixing and then firing, or a method of producing the organic acid barium titanyl powder of the present invention or the organic acid barium titanyl powder of the present invention. One example is 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 titanium-based perovskite-type ceramic raw material powder of the present invention may be used, for example, with conventionally known additives, organic binders, plasticizers, dispersants, etc., including subcomponent elements. A ceramic sheet used in the production of a multilayer ceramic capacitor can be obtained by mixing and dispersing the mixture in an appropriate solvent to form a slurry, and forming the slurry into 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 make a multilayer ceramic capacitor from ceramic sheets, first, conductive paste for forming internal electrodes is printed on one side of the ceramic sheet, and after drying, multiple ceramic sheets are laminated and pressed in the thickness direction to form a laminate. shall be. Next, this laminate is heat-treated to remove the binder, and then fired to obtain a fired body. Further, by applying Ni paste, Ag paste, nickel alloy paste, copper paste, copper alloy paste, etc. to the sintered body and baking it, a multilayer ceramic capacitor can be obtained.
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。 For example, the titanium-based perovskite-type ceramic raw material powder obtained by the method for producing titanium-based perovskite-type ceramic raw material powder of the present invention may be blended with a resin such as an epoxy resin, a polyester resin, or a polyimide resin to produce a resin sheet. When used as a film, adhesive, etc., it can be suitably used as a material for printed wiring boards, multilayer printed wiring boards, etc. It can also be used as a co-material for suppressing the shrinkage difference between internal electrodes and dielectric layers, and for electrode ceramic circuits. It can also be used as a dielectric material for substrates, glass ceramic circuit boards, circuit peripheral materials, inorganic EL, etc.
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。 In addition, the titanium-based perovskite-type ceramic raw material powder obtained by the method of manufacturing the titanium-based perovskite-type ceramic raw material powder of the present invention can be used as a catalyst used in reactions such as exhaust gas removal and chemical synthesis, and can be given antistatic and cleaning effects. It can also be suitably used as a surface modification material 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。 EXAMPLES Hereinafter, the present invention will be explained 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, characteristics were measured by the following method.
(1) Molar ratio of Ba, Ca, and Ti atoms The molar ratio of each atom was calculated based on the measured values of a fluorescent X-ray analyzer (manufactured by Rigaku Co., Ltd., ZSX100e).
(2) Average particle size of Me element-substituted barium titanyl oxalate powder Particle size distribution was measured by laser diffraction/scattering method using MT3000 manufactured by Micro Track Bell Co., Ltd., and the particle size at 50% of the volume integration in the particle size distribution (D50) was defined as the average particle diameter.
(3) Average particle diameter of Me element-substituted barium titanate Measure 200 particles arbitrarily using a scanning electron microscope (SEM) photograph using S4800 manufactured by Hitachi High-Technologies, and calculate the average value as the average particle size. The diameter was taken as the diameter.
(4) Ca atom mapping analysis using EPMA Mapping analysis of Ca atoms was performed using an electron probe microanalyzer (EPMA) (manufactured by JEOL Ltd., JXA8500F).
(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)
50.0 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 designated as liquid A. Note that Table 1 shows the molar ratio of each element in Liquid A.
Next, 70.0 g of oxalic acid was dissolved in 500 ml of 30° C. warm water to prepare an oxalic acid aqueous solution, which was used as Solution B.
Next, while maintaining the B solution (the reaction solution after starting the dropwise addition) at 30°C, the A solution was added at a rate of 4.2 ml/min over 120 minutes with stirring, and the mixture was further stirred at 30°C for 60 minutes. Aged. After cooling, it was filtered to recover barium calcium titanyl oxalate powder.
Next, the recovered barium calcium titanyl oxalate powder was repulped and washed with distilled water. Then, it was dried at 80°C to obtain barium calcium titanyl oxalate powder. The physical properties of the obtained barium calcium titanyl oxalate powder were as shown in Table 1. In addition, the obtained barium calcium titanate powder was calcined at 800°C, and the obtained barium calcium titanate powder was used to analyze Ca atoms using an electron probe microanalyzer (EPMA) (manufactured by JEOL Ltd., JXA8500F). Mapping analysis was performed. The results are shown in Figure 1. From the results shown in FIG. 1, it was found that in the obtained barium calcium titanate powder, no segregation of Ca atoms was observed, and Ca was uniformly dispersed. Moreover, as a result of elemental analysis of the obtained barium calcium titanate powder, Ca/Ba was 0.020 and (Ba+Ca)/Ti was 0.994.
Furthermore, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanyl oxalate obtained by adding liquid A to liquid B, the barium oxalate obtained in Example 1 was determined. Calcium titanyl was found to be (Ba 0.080 Ca 0.020 ) 0.994 TiO(C 2 O 4 ) 2.4H 2 O. The results of X-ray diffraction analysis are 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)
40.0 g of barium chloride dihydrate, 20.0 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 designated as liquid A. Note that Table 1 shows the molar ratio of each element in Liquid A.
Next, 70.0 g of oxalic acid was dissolved in 500 ml of 30° C. warm water to prepare an oxalic acid aqueous solution, which was used as Solution B.
Next, while maintaining the B solution (the reaction solution after starting the dropwise addition) at 30°C, the A solution was added at a rate of 4.2 ml/min over 120 minutes with stirring, and the mixture was further stirred at 30°C for 60 minutes. Aged.
The subsequent operations were performed in the same manner as in Example 1. The physical properties of the obtained barium calcium titanyl oxalate powder were as shown in Table 1. Further, the obtained barium calcium titanyl oxalate powder was calcined, and the obtained barium calcium titanate powder was subjected to Ca atom mapping analysis using EPMA. The results are shown in FIG. From the results shown in FIG. 3, it was found that in the obtained barium calcium titanate powder, no segregation of Ca atoms was observed, and Ca was uniformly dispersed. Moreover, as a result of elemental analysis of the obtained barium calcium titanate powder, Ca/Ba was 0.05 and (Ba+Ca)/Ti was 0.998.
Furthermore, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanyl oxalate obtained by adding liquid A to liquid B, the barium oxalate obtained in Example 2 was determined. Calcium titanyl was found to be (Ba 0.08 Ca 0.05 ) 0.998 TiO(C 2 O 4 ) 2.4H 2 O. The results of X-ray diffraction analysis are 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)
40.0 g of barium chloride dihydrate, 7.5 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 designated as liquid A. Note that Table 1 shows the molar ratio of each element in Liquid A.
Next, 70.0 g of oxalic acid was dissolved in 500 ml of 30° C. warm water to prepare an oxalic acid aqueous solution, which was used as Solution B.
Next, while maintaining the B solution (the reaction solution after starting the dropwise addition) at 30°C, the A solution was added at a rate of 4.2 ml/min over 120 minutes with stirring, and the mixture was further stirred at 30°C for 60 minutes. Aged.
The subsequent operations were performed in the same manner as in Example 1. The physical properties of the obtained barium calcium titanyl oxalate powder were as shown in Table 1. Further, the obtained barium calcium titanyl oxalate powder was calcined, and the obtained barium calcium titanate powder was subjected to Ca atom mapping analysis using EPMA. The results are shown in FIG. From the results shown in FIG. 4, it was found that in the obtained barium calcium titanate powder, no segregation of Ca atoms was observed, and Ca was uniformly dispersed. Moreover, as a result of elemental analysis of the obtained barium calcium titanate powder, Ca/Ba was 0.02 and (Ba+Ca)/Ti was 0.991.
Furthermore, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanyl oxalate obtained by adding liquid A to liquid B, the barium oxalate obtained in Example 3 was determined. Calcium titanyl was found to be (Ba 0.08 Ca 0.02 ) 0.991 TiO(C 2 O 4 ) 2.4H 2 O. The results of X-ray diffraction analysis are 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 designated as liquid A. Note that Table 1 shows the molar ratio of each element in Liquid A.
Next, 70.0 g of oxalic acid was dissolved in 420 ml of 30° C. warm water to prepare an oxalic acid aqueous solution, which was used as Solution B.
Next, while maintaining the B solution (the reaction solution after starting the dropwise addition) at 30°C, the A solution was added at a rate of 3.5 ml/min over 120 minutes with stirring, and the mixture was further stirred at 30°C for 60 minutes. Aged. After cooling, it was filtered to recover barium calcium titanyl oxalate powder.
Next, the recovered barium calcium titanyl oxalate powder was repulped and washed with distilled water. Then, it was dried at 80° C. to obtain barium calcium titanyl oxalate powder. The physical properties of the obtained barium calcium titanyl oxalate powder were as shown in Table 1. In addition, the obtained barium calcium titanate powder was calcined at 800°C, and the obtained barium calcium titanate powder was used to analyze Ca atoms using an electron probe microanalyzer (EPMA) (manufactured by JEOL Ltd., JXA8500F). Mapping analysis was performed. The results are shown in FIG. From the results shown in FIG. 5, it was found that in the obtained barium calcium titanate powder, no segregation of Ca atoms was observed, and Ca was uniformly dispersed. Moreover, as a result of elemental analysis of the obtained barium calcium titanate powder, Ca/Ba was 0.026 and (Ba+Ca)/Ti was 0.998.
In addition, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanyl oxalate obtained by adding liquid A to liquid B, the barium oxalate obtained in Example 4 was determined. Calcium titanyl was found to be (Ba 0.08 Ca 0.03 ) 0.998 TiO(C 2 O 4 ) 2.4H 2 O. The results of X-ray diffraction analysis are 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 designated as liquid A. Note that Table 1 shows the molar ratio of each element in Liquid A.
Next, 504.0 g of oxalic acid was dissolved in 3600 ml of 30° C. warm water to prepare an oxalic acid aqueous solution, which was used as Solution B.
Next, while maintaining the B solution (the reaction solution after starting the dropwise addition) at 30°C, the A solution was added at a rate of 30 ml/min over 120 minutes with stirring, and the mixture was further aged at 30°C for 60 minutes with stirring. . After cooling, it was filtered to recover barium calcium titanyl oxalate powder.
Next, the recovered barium calcium titanyl oxalate powder was repulped and washed with distilled water. Then, it was dried at 80° C. to obtain barium calcium titanyl oxalate powder. The physical properties of the obtained barium calcium titanyl oxalate powder were as shown in Table 1. In addition, the obtained barium calcium titanate powder was calcined at 800°C, and the obtained barium calcium titanate powder was used to analyze Ca atoms using an electron probe microanalyzer (EPMA) (manufactured by JEOL Ltd., JXA8500F). Mapping analysis was performed. The results are shown in FIG. From the results shown in FIG. 6, it was found that in the obtained barium calcium titanate powder, no segregation of Ca atoms was observed, and Ca was uniformly dispersed. Moreover, as a result of elemental analysis of the obtained barium calcium titanate powder, Ca/Ba was 0.025 and (Ba+Ca)/Ti was 0.994.
Furthermore, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanyl oxalate obtained by adding liquid A to liquid B, the barium oxalate obtained in Example 5 was determined. Calcium titanyl was found to be (Ba 0.08 Ca 0.02 ) 0.994 TiO(C 2 O 4 ) 2.4H 2 O. The results of X-ray diffraction analysis are 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 designated as liquid A. Note that Table 1 shows the molar ratio of each element in Liquid A.
Next, 70.0 g of oxalic acid was dissolved in 500 ml of 30° C. warm water to prepare an oxalic acid aqueous solution, which was used as Solution B.
Next, while maintaining Solution B at 30° C., Solution A was added at a rate of 4.2 ml/min over 120 minutes with stirring, and the mixture was further aged at 30° C. for 60 minutes with stirring. After cooling, it was filtered to recover barium calcium titanyl oxalate powder.
The subsequent operations were performed in the same manner as in Example 1. The physical properties of the obtained barium calcium titanyl oxalate powder were as shown in Table 1. Further, the obtained barium calcium titanyl oxalate powder was calcined, and the obtained barium calcium titanate powder was subjected to Ca atom mapping analysis using EPMA. The results are shown in FIG. From the results shown in FIG. 7, it was found that Ca atoms were segregated in the obtained barium calcium titanate 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.
Furthermore, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanyl oxalate obtained by adding liquid A to liquid B, it was found that the barium oxalate obtained in Comparative Example 1 Calcium titanyl was found 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 designated as liquid A. Note that Table 1 shows the molar ratio of each element in Liquid A.
Next, 32.5 g of oxalic acid was dissolved in 140 ml of 55° C. warm water to prepare an oxalic acid aqueous solution, which was used as Solution B.
Next, while maintaining Solution B at 55° C., Solution A was added at a rate of 1.5 ml/min over 120 minutes with stirring, and the mixture was further aged at 55° C. for 60 minutes with stirring. After cooling, it was filtered to recover barium calcium titanyl oxalate powder.
The subsequent operations were performed in the same manner as in Example 1. The physical properties of the obtained barium calcium titanyl oxalate powder were as shown in Table 1. Further, the obtained barium calcium titanyl oxalate powder was calcined, and the obtained barium calcium titanate powder was subjected to Ca atom mapping analysis using EPMA. The results are shown in FIG. From the results shown in FIG. 8, it was found that Ca atoms were segregated in the obtained barium calcium titanate 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 0.999.
In addition, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of barium calcium titanyl oxalate obtained by adding liquid A to liquid B, the barium oxalate obtained in Comparative Example 2 Calcium titanyl was found 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 in Table 1 and Figures 1 to 8, the barium calcium titanate obtained from the barium calcium titanyl oxalate of the example has a higher calcium titanate content than the barium calcium titanate obtained from the barium calcium titanyl oxalate 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 organic acid barium titanyl in which a part of the Ba site is replaced with a Me element (Me represents at least one selected from Ca, Sr, and Mg);
The molar ratio of the sum of Ba and Me elements 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. be less than or equal to
A Me element-substituted organic acid barium titanyl powder characterized by:
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 (liquid A) obtained by mixing a barium compound, a Me element compound (Me represents at least one selected from Ca, Sr, and Mg) and a titanium compound in water is used as an organic acid aqueous solution (liquid B). A method for producing barium titanyl Me element-substituted organic acid powder, which obtains barium titanyl Me element-substituted organic acid by adding to
In the liquid A, the molar ratio of the 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 liquid A and liquid B is 10 to 50°C,
A method for producing a Me element-substituted organic acid barium titanyl powder, characterized by:
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| 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 |
| 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 |
| 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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| US20110044876A1 (en) | 2007-11-26 | 2011-02-24 | Rutgers University | Low temperature metal oxide synthesis |
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| JP2016199456A (en) | 2015-04-07 | 2016-12-01 | 日本化学工業株式会社 | Dielectric ceramic material, manufacturing method therefor and composite dielectric material |
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| JP2002060219A (en) | 2000-08-11 | 2002-02-26 | Murata Mfg Co Ltd | Barium titanate fine powder, calcium-modified barium titanate fine powder and its manufacturing method |
| JP2005500239A (en) | 2001-08-14 | 2005-01-06 | サムソン ファイン ケミカルズ カンパニー リミテッド | Method for producing barium titanate powder |
| JP2006188469A (en) | 2005-01-07 | 2006-07-20 | Nippon Chem Ind Co Ltd | Method for producing barium titanyl oxalate powder and method for producing titanium perovskite type ceramic raw material powder |
| US20110044876A1 (en) | 2007-11-26 | 2011-02-24 | Rutgers University | Low temperature metal oxide synthesis |
| JP2011517652A (en) | 2008-04-03 | 2011-06-16 | サッチェム，インコーポレイテッド | Preparation method of advanced ceramic powder using onium dicarboxylate |
| JP2016199456A (en) | 2015-04-07 | 2016-12-01 | 日本化学工業株式会社 | Dielectric ceramic material, manufacturing method therefor and composite dielectric material |
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