TWI850426B - Titanium barium oxalate powder substituted with Me element, its production method and titanium-based calcium titanite-type ceramic raw material powder production method - Google Patents
Titanium barium oxalate powder substituted with Me element, its production method and titanium-based calcium titanite-type ceramic raw material powder production method Download PDFInfo
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- TWI850426B TWI850426B TW109123753A TW109123753A TWI850426B TW I850426 B TWI850426 B TW I850426B TW 109123753 A TW109123753 A TW 109123753A TW 109123753 A TW109123753 A TW 109123753A TW I850426 B TWI850426 B TW I850426B
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- 239000000843 powder Substances 0.000 title claims abstract description 241
- 239000010936 titanium Substances 0.000 title claims abstract description 87
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 61
- 239000000919 ceramic Substances 0.000 title claims description 40
- 229910052719 titanium Inorganic materials 0.000 title claims description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 36
- 239000002994 raw material Substances 0.000 title claims description 35
- YWJHUQQPWSXFTC-UHFFFAOYSA-H barium(2+) oxalate titanium(4+) Chemical compound [Ti+4].[Ba++].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O YWJHUQQPWSXFTC-UHFFFAOYSA-H 0.000 title claims description 28
- 239000011575 calcium Substances 0.000 title description 101
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title description 33
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 73
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims description 101
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 97
- 239000002245 particle Substances 0.000 claims description 36
- 235000006408 oxalic acid Nutrition 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- 238000004458 analytical method Methods 0.000 claims description 18
- 238000013507 mapping Methods 0.000 claims description 15
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 15
- 150000001553 barium compounds Chemical class 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 150000003609 titanium compounds Chemical class 0.000 claims description 13
- 239000000523 sample Substances 0.000 claims description 9
- 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
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
- VKJLWXGJGDEGSO-UHFFFAOYSA-N barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ba+2] VKJLWXGJGDEGSO-UHFFFAOYSA-N 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
- 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 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000010191 image analysis Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 105
- 229910052788 barium Inorganic materials 0.000 abstract description 71
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 59
- 238000000034 method Methods 0.000 abstract description 32
- XBYNNYGGLWJASC-UHFFFAOYSA-N barium titanium Chemical compound [Ti].[Ba] XBYNNYGGLWJASC-UHFFFAOYSA-N 0.000 abstract description 25
- 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 35
- 229960005069 calcium Drugs 0.000 description 31
- 238000005204 segregation Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 28
- VIQRPVONNZUBTL-UHFFFAOYSA-F C(C(=O)[O-])(=O)[O-].[Ba+2].[Ca+2].[Ti+4].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-] Chemical compound C(C(=O)[O-])(=O)[O-].[Ba+2].[Ca+2].[Ti+4].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-] VIQRPVONNZUBTL-UHFFFAOYSA-F 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 238000000921 elemental analysis Methods 0.000 description 14
- 239000012295 chemical reaction liquid Substances 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- -1 organic acid titanium barium oxide Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 238000001914 filtration Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- WNLOJEUKHREVLZ-UHFFFAOYSA-N [Ba].[Ti].[O] Chemical compound [Ba].[Ti].[O] WNLOJEUKHREVLZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- JLRVHARDDHTXMN-UHFFFAOYSA-N calcium tantalum Chemical compound [Ca][Ta] JLRVHARDDHTXMN-UHFFFAOYSA-N 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
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- 229920005989 resin Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 101000827703 Homo sapiens Polyphosphoinositide phosphatase Proteins 0.000 description 2
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- 102100023591 Polyphosphoinositide phosphatase Human genes 0.000 description 2
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000005416 organic matter Substances 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
- 238000000790 scattering method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 229910052861 titanite Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 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
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 238000009825 accumulation Methods 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
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
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- 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
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- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
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- 150000003891 oxalate salts Chemical class 0.000 description 1
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- 229910052706 scandium Inorganic materials 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
本發明提供一種經Me元素取代的有機酸氧鈦鋇粉末及鈦酸鋇粉末，以及提供一種工業上有利地製造該有機酸氧鈦鋇或該鈦酸鋇粉末的方法，所述經Me元素取代的有機酸氧鈦鋇粉末及鈦酸鋇粉末為Ba位的一部分經其他元素(Me元素)取代的有機酸氧鈦鋇及鈦酸鋇，取代元素不偏析，且均勻地分佈於有機酸氧鈦鋇粉末整體或鈦酸鋇粉末整體。一種經Me元素取代的有機酸氧鈦鋇粉末，其為將Ba位的一部分取代為Me元素(Me表示選自Ca、Sr及Mg中的至少一種)的經Me元素取代的有機酸氧鈦鋇，所述經Me元素取代的有機酸氧鈦鋇粉末的特徵在於：Ba與Me元素的合計相對於Ti的莫耳比((Ba+Me)/Ti)為0.980以上且未滿0.999，Me元素相對於Ba的莫耳比(Me/Ba)為0.001以上且0.250以下。 The present invention provides an organic acid oxytitanium barium powder and a barium titanate powder substituted with the Me element, and provides an industrially advantageous method for manufacturing the organic acid oxytitanium barium or the barium titanate powder. The organic acid oxytitanium barium powder and the barium titanate powder substituted with the Me element are organic acid oxytitanium barium and barium titanate in which a part of the Ba position is substituted with other elements (Me element), and the substituted elements are not segregated and are uniformly distributed in the organic acid oxytitanium barium powder or the barium titanate powder as a whole. A Me-substituted organic acid titanium barium powder, wherein a portion of the Ba position is substituted with Me (Me represents at least one selected from Ca, Sr and Mg), wherein the Me-substituted organic acid titanium barium powder is characterized in that the molar ratio of the total Ba and Me elements to Ti ((Ba+Me)/Ti) is greater than 0.980 and less than 0.999, and the molar ratio of Me element to Ba (Me/Ba) is greater than 0.001 and less than 0.250.
Description
本發明是有關於一種可有效用作介電體、壓電體、光電子材料、半導體、感測器等功能性陶瓷的原料的利用其他元素取代鋇元素的一部分的有機酸氧鈦鋇及其製造方法。 The present invention relates to an organic acid titanium barium oxide that can be effectively used as a raw material for functional ceramics such as dielectrics, piezoelectrics, optoelectronic materials, semiconductors, sensors, etc., in which a part of the barium element is replaced by other elements, and a method for producing the same.
積層陶瓷晶片電容器(多層式陶瓷電容器(multi-layer ceramic capacitor，MLCC))的介電體層一般是採用包括作為主要原料的鈦酸鋇與微量的添加劑的多成分體系的形態。例如，鈣是作為添加劑經常使用的成分，但已知藉由對鈦酸鋇中的鋇位進行取代固溶，具有作為使介電體的相對介電常數的溫度特性變得平滑的抑制劑的效果、或者作為成為燒結助劑的玻璃的成分使用等。 The dielectric layer of a multi-layer ceramic chip capacitor (MLCC) generally adopts a multi-component system including barium titanate as the main raw material and a trace amount of additives. For example, calcium is a component often used as an additive, but it is known that calcium has the effect of a suppressor that makes the temperature characteristics of the relative dielectric constant of the dielectric smooth by replacing the barium site in barium titanate, or is used as a component of glass that serves as a sintering aid, etc.
採用所述多成分體系的形態的鈦酸鋇藉由使用自先前以來已知的固相法、草酸鹽法、水熱合成法、醇鹽法等並添加微量成分來獲得。該些中，草酸鹽法是藉由對濕式合成的草酸鹽前驅物進行熱處理並進行脫草酸來合成鈦酸鋇的製法。而且，草酸鹽法的最大特徵在於根據前驅物結晶中的鋇與鈦的組成比(Ba/Ti)來獲得高品質、化學當量的鈦酸鋇。 The barium titanium oxide in the form of the multi-component system is obtained by using the previously known solid phase method, oxalate method, hydrothermal synthesis method, alkoxide method, etc. and adding trace components. Among these, the oxalate method is a method of synthesizing barium titanium oxide by heat treating a wet-synthesized oxalate precursor and performing deoxalation. Moreover, the greatest feature of the oxalate method is that high-quality, chemically equivalent barium titanium oxide is obtained according to the composition ratio of barium to titanium (Ba/Ti) in the precursor crystal.
對於草酸鹽法而言，報告有若干個製程，但於工業上一 般是將氯化鈦與氯化鋇的混合液添加至草酸水溶液中進行反應的方法。且提出有使用該草酸鹽法來製造利用其他金屬元素取代鋇元素的一部分的草酸氧鈦鋇的方法。 For the oxalate method, several processes have been reported, but in industry, the method generally involves adding a mixture of titanium chloride and barium chloride to an aqueous solution of oxalic acid for reaction. A method has also been proposed for using the oxalate method to produce titanium barium oxalate in which a portion of the barium element is replaced by other metal elements.
例如，於專利文獻1中記載有如下方法：使氯化鈦、氯化鋇的混合液中含有取代的其他鹼土金屬化合物，並將其添加至草酸水溶液中來進行。但是，由於難以定量地進行反應，故存在工業上不利的缺點。 For example, Patent Document 1 describes the following method: a mixture of titanium chloride and barium chloride contains a substituted alkali earth metal compound and adds it to an aqueous oxalic acid solution. However, since it is difficult to carry out the reaction quantitatively, there is an industrial disadvantage.
因此，為了定量地進行反應，於專利文獻2中記載有如下內容：將含有四氯化鈦與草酸的溶液添加至含有鋇化合物、與包含取代的其他元素的化合物的溶液中進行反應時，反應性提高，獲得與鋇進行取代的其他元素的取代率高的草酸氧鈦鋇。 Therefore, in order to carry out the reaction quantitatively, Patent Document 2 states that when a solution containing titanium tetrachloride and oxalic acid is added to a solution containing a barium compound and a compound containing other elements to be substituted, the reactivity is improved, and titanium barium oxalate having a high substitution rate of other elements substituted with barium is obtained.
另外，於專利文獻3中記載有如下內容：藉由將包含草酸與鈦的第一水溶液滴加至包含氨與選自鈣、鋇及鍶中的至少一種的第二水溶液中並混合，可獲得鋇、鈣之類的鹼土金屬及鈦的分散性良好、均勻性優異的陶瓷原料微粉末。 In addition, Patent Document 3 states that: By dropping a first aqueous solution containing oxalic acid and titanium into a second aqueous solution containing ammonia and at least one selected from calcium, barium and strontium and mixing, a ceramic raw material fine powder with good dispersion and excellent uniformity of alkaline earth metals such as barium and calcium and titanium can be obtained.
[現有技術文獻] [Prior art literature]
[專利文獻] [Patent Literature]
[專利文獻1] 日本專利特開2003-212543號公報 [Patent document 1] Japanese Patent Publication No. 2003-212543
[專利文獻2] 日本專利特開2006-188469號公報 [Patent document 2] Japanese Patent Publication No. 2006-188469
[專利文獻3] 日本專利特開平4-292455號公報 [Patent document 3] Japanese Patent Publication No. 4-292455
但是，於引用文獻2記載的方法中，可使鈣等其他元素以高概率於鋇位上進行取代，但由於反應性過高，故存在難以使取代元素均勻地分佈於草酸氧鈦鋇整體的問題。 However, in the method described in Reference 2, other elements such as calcium can be substituted at the barium site with a high probability, but due to the high reactivity, it is difficult to evenly distribute the substitution element throughout the titanium barium oxalate.
另外，根據引用文獻3的實施例，記載可獲得與投入組成相應的組成的生成物，但並無關於均勻性的評價，且亦有時使用氨來進行pH調整，不能說是於工業上有利的方法。 In addition, according to the embodiment of cited document 3, it is described that a product with a composition corresponding to the input composition can be obtained, but there is no evaluation on uniformity, and ammonia is sometimes used for pH adjustment, which cannot be said to be an industrially beneficial method.
因而，本發明的目的在於提供一種經Me元素取代的有機酸氧鈦鋇粉末及鈦酸鋇粉末，以及提供一種工業上有利地製造該有機酸氧鈦鋇或該鈦酸鋇粉末的方法，所述經Me元素取代的有機酸氧鈦鋇粉末及鈦酸鋇粉末為Ba位的一部分經其他元素(Me元素)取代的有機酸氧鈦鋇及鈦酸鋇，取代元素不偏析，且均勻地分佈於有機酸氧鈦鋇粉末整體或鈦酸鋇粉末整體。 Therefore, the purpose of the present invention is to provide an organic acid oxytitanium barium powder and barium titanate powder substituted with Me element, and to provide an industrially advantageous method for manufacturing the organic acid oxytitanium barium or the barium titanate powder. The organic acid oxytitanium barium powder and barium titanate powder substituted with Me element are organic acid oxytitanium barium and barium titanate in which a part of the Ba position is substituted with other elements (Me element), and the substituted elements are not segregated and are uniformly distributed in the organic acid oxytitanium barium powder or the barium titanate powder as a whole.
本發明者等人鑑於所述實際情況而反覆努力研究，結果發現：藉由將有機酸氧鈦鋇的Ba及Me元素的合計相對於Ti的莫耳比設為較1稍小的範圍即0.980~0.999，且將Me元素相對於Ba的莫耳比的範圍設為0.001~0.200，可獲得偏析少的有機酸氧鈦鋇粉末，從而完成了本發明。 In view of the above actual situation, the inventors of the present invention have repeatedly made efforts to study and found that by setting the molar ratio of the total Ba and Me elements of organic acid titanium barium to Ti to a range slightly smaller than 1, that is, 0.980~0.999, and setting the molar ratio of the Me element to Ba to 0.001~0.200, organic acid titanium barium powder with less segregation can be obtained, thereby completing the present invention.
即，本發明(1)提供一種經Me元素取代的有機酸氧鈦鋇粉末，其為將Ba位的一部分取代為Me元素(Me表示選自Ca、Sr及Mg中的至少一種)的經Me元素取代的有機酸氧鈦鋇，所述經Me元素取代的有機酸氧鈦鋇粉末的特徵在於： Ba與Me元素的合計相對於Ti的莫耳比((Ba+Me)/Ti)為0.980以上且未滿0.999，Me元素相對於Ba的莫耳比(Me/Ba)為0.001以上且0.250以下。 That is, the present invention (1) provides an organic acid oxytitanium barium powder substituted with the Me element, which is an organic acid oxytitanium barium powder substituted with the Me element in which a part of the Ba position is substituted with the Me element (Me represents at least one selected from Ca, Sr and Mg), and the organic acid oxytitanium barium powder substituted with the Me element is characterized in that: The molar ratio of the total Ba and Me elements to Ti ((Ba+Me)/Ti) is greater than 0.980 and less than 0.999, and the molar ratio of Me element to Ba (Me/Ba) is greater than 0.001 and less than 0.250.
另外，本發明(2)提供如(1)所述的經Me元素取代的有機酸氧鈦鋇粉末，其中於電子探針顯微分析儀(electron probe micro analyzer，EPMA)分析中，所述Me元素均勻地分佈於煆燒所述經Me元素取代的有機酸氧鈦鋇粉末而獲得的經Me元素取代的鈦酸鋇粉末的粒子上。 In addition, the present invention (2) provides the organic acid oxytitanium barium powder substituted with Me element as described in (1), wherein in the electron probe micro analyzer (EPMA) analysis, the Me element is uniformly distributed on the particles of the barium titanate powder substituted with Me element obtained by calcining the organic acid oxytitanium barium powder substituted with Me element.
另外，本發明(3)提供如(1)所述的經Me元素取代的有機酸氧鈦鋇粉末，其中使用電子探針顯微分析儀(EPMA)分析，於煆燒所述經Me元素取代的有機酸氧鈦鋇粉末而獲得的經Me元素取代的鈦酸鋇的壓粉體的表面上，以成為一邊為205μm的正方形的範圍的方式以0.8μm間隔進行縱橫256點的映射分析，於所獲得的圖像解析中，Ca的變異係數(coefficient of variation，CV)值(標準偏差/平均值)為0.4以下。 In addition, the present invention (3) provides an organic acid oxytitanium barium powder substituted with Me as described in (1), wherein an electron probe microanalyzer (EPMA) is used to analyze the surface of a pressed powder of barium titanate substituted with Me obtained by calcining the organic acid oxytitanium barium powder substituted with Me, and a mapping analysis of 256 points in the vertical and horizontal directions is performed in a manner that forms a square range with a side of 205 μm at an interval of 0.8 μm. In the obtained image analysis, the coefficient of variation (CV) value (standard deviation/average value) of Ca is less than 0.4.
另外，本發明(4)提供一種經Me元素取代的有機酸氧鈦鋇粉末的製造方法，藉由在有機酸水溶液(B液)中添加於水中混合鋇化合物、Me元素化合物及鈦化合物而獲得的水溶液(A液)，來獲得經Me元素取代的有機酸氧鈦鋇，所述經Me元素取代的有機酸氧鈦鋇粉末的製造方法的特徵在於：該A液中，以原子換算計，Me元素相對於Ba的莫耳比(Me/Ba)為0.020以上且5.000以下，Ba相對於Ti的莫耳比 (Ba/Ti)為0.300以上且1.200以下，且A液與B液的混合溫度為10℃~50℃。 In addition, the present invention (4) provides a method for producing organic acid titanium barium oxygen powder substituted with Me element, wherein an aqueous solution (liquid A) obtained by mixing a barium compound, a Me element compound and a titanium compound in water is added to an organic acid aqueous solution (liquid B) to obtain organic acid titanium barium oxygen powder substituted with Me element. The method for producing organic acid titanium barium oxygen powder substituted with Me element is characterized in that: in the liquid A, the molar ratio of Me element to Ba (Me/Ba) is greater than 0.020 and less than 5.000, and the molar ratio of Ba to Ti (Ba/Ti) is greater than 0.300 and less than 1.200, and the mixing temperature of the liquid A and the liquid B is 10°C to 50°C.
另外，本發明(5)提供如(4)所述的經Me元素取代的有機酸氧鈦鋇粉末的製造方法，其中所述鋇化合物為選自由氯化鋇、碳酸鋇及氫氧化鋇所組成的群組中的至少一種。 In addition, the present invention (5) provides a method for producing organic acid titanium barium powder substituted with Me element as described in (4), wherein the barium compound is at least one selected from the group consisting of barium chloride, barium carbonate and barium hydroxide.
另外，本發明(6)提供如(4)或(5)所述的經Me元素取代的有機酸氧鈦鋇粉末的製造方法，其中所述Me元素化合物為選自由Me元素的氯化物、Me元素的碳酸鹽及Me元素的氫氧化物所組成的群組中的至少一種。 In addition, the present invention (6) provides a method for producing organic acid titanium barium powder substituted with Me element as described in (4) or (5), wherein the Me element compound is at least one selected from the group consisting of chloride of Me element, carbonate of Me element and hydroxide of Me element.
另外，本發明(7)提供如(4)至(6)中任一項所述的經Me元素取代的有機酸氧鈦鋇粉末的製造方法，其中所述鈦化合物為選自四氯化鈦及乳酸鈦中的至少一種。 In addition, the present invention (7) provides a method for producing organic acid oxytitanium barium powder substituted with Me element as described in any one of (4) to (6), wherein the titanium compound is at least one selected from titanium tetrachloride and titanium lactate.
另外，本發明(8)提供如(4)至(7)中任一項所述的經Me元素取代的有機酸氧鈦鋇粉末的製造方法，其中所述有機酸為選自由草酸、檸檬酸、丙二酸及琥珀酸所組成的群組中的至少一種。 In addition, the present invention (8) provides a method for producing an organic acid titanium-barium oxide powder substituted with Me as described in any one of (4) to (7), wherein the organic acid is at least one selected from the group consisting of oxalic acid, citric acid, malonic acid and succinic acid.
另外，本發明(9)提供一種鈦系鈣鈦礦型陶瓷原料粉末的製造方法，其特徵在於：藉由煆燒如(1)至(3)中任一項所述的經Me元素取代的有機酸氧鈦鋇粉末，來獲得經Me元素取代的鈦酸鋇。 In addition, the present invention (9) provides a method for producing a titanium-based calcite-titanic ceramic raw material powder, characterized in that barium titanate substituted with Me element is obtained by calcining the organic acid titanium barium powder substituted with Me element as described in any one of (1) to (3).
另外，本發明(10)提供一種鈦系鈣鈦礦型陶瓷原料粉末的製造方法，其特徵在於：藉由煆燒進行如(4)至(8)中任 一項所述的經Me元素取代的有機酸氧鈦鋇粉末的製造方法而獲得的經Me元素取代的有機酸氧鈦鋇粉末，來獲得經Me元素取代的鈦酸鋇粉末。 In addition, the present invention (10) provides a method for producing a titanium-based calcite-titanic ceramic raw material powder, characterized in that: barium titanate powder substituted with Me element is obtained by calcining the organic acid titanium barium powder substituted with Me element obtained by the method for producing organic acid titanium barium powder substituted with Me element as described in any one of (4) to (8).
根據本發明，可提供一種經Me元素取代的有機酸氧鈦鋇粉末及鈦酸鋇粉末，以及提供一種工業上有利地製造該有機酸氧鈦鋇或該鈦酸鋇粉末的方法，所述經Me元素取代的有機酸氧鈦鋇粉末及鈦酸鋇粉末為Ba位的一部分經其他元素(Me元素)取代的有機酸氧鈦鋇及鈦酸鋇，取代元素不偏析，且均勻地分佈於有機酸氧鈦鋇粉末整體或鈦酸鋇粉末整體。 According to the present invention, an organic acid oxytitanium barium powder and a barium titanate powder substituted with the Me element can be provided, as well as a method for industrially advantageously manufacturing the organic acid oxytitanium barium or the barium titanate powder. The organic acid oxytitanium barium powder and the barium titanate powder substituted with the Me element are organic acid oxytitanium barium and barium titanate in which a part of the Ba position is substituted with other elements (Me element), and the substituted elements are not segregated and are uniformly distributed in the organic acid oxytitanium barium powder or the barium titanate powder as a whole.
圖1是實施例1中獲得的鈦酸鋇鈣粉末的基於EPMA的Ca原子的映射分析結果。 Figure 1 is the EPMA-based Ca atom mapping analysis result of the calcium barium titanate powder obtained in Example 1.
圖2是實施例1~實施例5及比較例1~比較例2中獲得的草酸氧鈦鋇鈣的XRD分析結果。 Figure 2 is the XRD analysis result of calcium barium titanium oxalate obtained in Example 1 to Example 5 and Comparative Example 1 to Comparative Example 2.
圖3是實施例2中獲得的鈦酸鋇鈣粉末的基於EPMA的Ca原子的映射分析結果。 Figure 3 is the EPMA-based mapping analysis result of Ca atoms of the calcium barium titanate powder obtained in Example 2.
圖4是實施例3中獲得的鈦酸鋇鈣粉末的基於EPMA的Ca原子的映射分析結果。 Figure 4 is the EPMA-based Ca atom mapping analysis result of the calcium barium titanate powder obtained in Example 3.
圖5是實施例4中獲得的鈦酸鋇鈣粉末的基於EPMA的Ca原子的映射分析結果。 Figure 5 is the EPMA-based mapping analysis result of Ca atoms of the calcium barium titanate powder obtained in Example 4.
圖6是實施例5中獲得的鈦酸鋇鈣粉末的基於EPMA的Ca原子的映射分析結果。 Figure 6 is the EPMA-based Ca atom mapping analysis result of the calcium barium titanate powder obtained in Example 5.
圖7是比較例1中獲得的鈦酸鋇鈣粉末的基於EPMA的Ca原子的映射分析結果。 Figure 7 is the EPMA-based Ca atom mapping analysis result of the calcium barium titanate powder obtained in Comparative Example 1.
圖8是比較例2中獲得的鈦酸鋇鈣粉末的基於EPMA的Ca原子的映射分析結果。 Figure 8 is the EPMA-based Ca atom mapping analysis result of the calcium barium titanate powder obtained in Comparative Example 2.
本發明的經Me元素取代的有機酸氧鈦鋇粉末為將Ba位的一部分取代為Me元素(Me表示選自Ca、Sr及Mg中的至少一種)的經Me元素取代的有機酸氧鈦鋇，所述經Me元素取代的有機酸氧鈦鋇粉末的特徵在於： Ba與Me元素的合計相對於Ti的莫耳比((Ba+Me)/Ti)為0.980以上且未滿0.999，Me元素相對於Ba的莫耳比(Me/Ba)為0.001以上且0.250以下。 The organic acid titanium barium powder substituted with Me element of the present invention is an organic acid titanium barium powder substituted with Me element in which a part of Ba position is substituted with Me element (Me represents at least one selected from Ca, Sr and Mg). The organic acid titanium barium powder substituted with Me element is characterized in that: The molar ratio of the total Ba and Me elements to Ti ((Ba+Me)/Ti) is greater than 0.980 and less than 0.999, and the molar ratio of Me element to Ba (Me/Ba) is greater than 0.001 and less than 0.250.
本發明的經Me元素取代的有機酸氧鈦鋇粉末為粉末狀，且為Ba位的一部分經Me元素取代的有機酸氧鈦鋇粒子的集合物。 The organic acid titanium barium oxide powder substituted with Me element of the present invention is in powder form and is a collection of organic acid titanium barium oxide particles in which a part of the Ba position is substituted with Me element.
於本發明的經Me元素取代的有機酸氧鈦鋇粉末中，對有機酸氧鈦鋇的Ba位的一部分進行取代的Me元素為選自Ca、Sr及Mg中的至少一種元素，較佳為Ca、Sr，特佳為Ca。Me可為一種，亦可為兩種以上。 In the organic acid titanium barium powder substituted with the Me element of the present invention, the Me element that replaces part of the Ba position of the organic acid titanium barium is at least one element selected from Ca, Sr and Mg, preferably Ca and Sr, and particularly preferably Ca. Me can be one or more.
本發明的經Me元素取代的有機酸氧鈦鋇粉末中，有機 酸為選自由草酸、檸檬酸、丙二酸及琥珀酸所組成的群組中的至少一種，較佳為草酸、檸檬酸，特佳為草酸。 In the organic acid titanium barium oxide powder substituted with Me element 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, and particularly preferably oxalic acid.
本發明的經Me元素取代的有機酸氧鈦鋇粉末中的Ba與Me元素的合計相對於Ti的莫耳比((Ba+Me)/Ti)為0.980以上且未滿0.999，較佳為0.983以上且0.998以下，特佳為0.985以上且0.997以下。藉由(Ba+Me)/Ti處於所述範圍，可獲得Me元素均勻地分佈於粉末整體、Me元素的偏析少的經Me元素取代的有機酸氧鈦鋇粉末，且藉由煆燒，可獲得Me元素均勻地分佈於粉末整體、Me元素的偏析少的經Me元素取代的鈦酸鋇粉末。另一方面，若(Ba+Me)/Ti未滿所述範圍，則難以獲得具有所需的特性的經Me元素取代的鈦酸鋇，且若超過所述範圍，則容易引起Me元素的偏析。 The molar ratio of the total Ba and Me elements to Ti in the organic acid oxytitanium barium powder substituted with Me element ((Ba+Me)/Ti) of the present invention is 0.980 or more and less than 0.999, preferably 0.983 or more and 0.998 or less, and particularly preferably 0.985 or more and 0.997 or less. When (Ba+Me)/Ti is within the above range, the organic acid oxytitanium barium powder substituted with Me element can be obtained in which the Me element is uniformly distributed throughout the powder and the segregation of the Me element is small, and by calcination, the barium titanate powder substituted with Me element can be obtained in which the Me element is uniformly distributed throughout the powder and the segregation of the Me element is small. On the other hand, if (Ba+Me)/Ti is less than the above range, it is difficult to obtain barium titanate substituted with Me element having the desired properties, and if it exceeds the above range, segregation of Me element is likely to occur.
本發明的經Me元素取代的有機酸氧鈦鋇粉末中的Me元素相對於Ba的莫耳比(Me/Ba)為0.001以上且0.250以下，較佳為0.005以上且0.150以下。藉由Me/Ba處於所述範圍，可獲得Me元素均勻地分佈於粉末整體、Me元素的偏析少的經Me元素取代的有機酸氧鈦鋇，且藉由煆燒，可獲得Me元素均勻地分佈於粒子整體、Me元素的偏析少的經Me元素取代的鈦酸鋇。另一方面，若Me/Ba未滿所述範圍，則難以獲得具有所需的特性的經Me元素取代的鈦酸鋇，且若超過所述範圍，則容易引起Me元素的偏析。 The molar ratio of Me element to Ba (Me/Ba) in the organic acid oxytitanium barium powder substituted with Me element of the present invention is 0.001 or more and 0.250 or less, preferably 0.005 or more and 0.150 or less. When Me/Ba is within the above range, organic acid oxytitanium barium substituted with Me element can be obtained in which Me element is uniformly distributed in the whole powder and Me element segregation is less, and by calcination, Me element can be obtained in which Me element is uniformly distributed in the whole particle and Me element segregation is less. On the other hand, if Me/Ba is less than the above range, it is difficult to obtain Me element substituted barium titanate having the desired characteristics, and if it exceeds the above range, Me element segregation is easily caused.
本發明的經Me元素取代的有機酸氧鈦鋇粉末中，作為 有機酸為草酸者，例如可列舉下述通式(1)：(Ba1-pMep)qTiO(C2O4)2．nH2O (1) In the organic acid oxytitanium barium powder substituted with Me element of the present invention, when the organic acid is oxalic acid, for example, the following general formula (1) can be cited: (Ba 1-p Me p ) q TiO(C 2 O 4 ) 2 ． nH 2 O (1)
(式中，Me表示選自Ca、Sr及Mg中的至少一種元素，p為0.001≦p≦0.200，q為0.980≦q<0.999，n為1~8的整數) (In the formula, Me represents at least one element selected from Ca, Sr and Mg, p is 0.001≦p≦0.200, q is 0.980≦q<0.999, and n is an integer from 1 to 8)
所表示的經Me元素取代的草酸氧鈦鋇粉末。 The indicated titanium barium oxalate powder substituted with Me element.
通式(1)中，Me為選自Ca、Sr及Mg中的至少一種元素，較佳為Ca、Sr，特佳為Ca。Me可為一種，亦可為兩種以上。即，通式(1)所表示的經Me元素取代的草酸氧鈦鋇粉末中，Ba位的一部分經選自Ca、Sr及Mg中的一種或兩種以上取代。 In the general formula (1), Me is at least one element selected from Ca, Sr and Mg, preferably Ca and Sr, and particularly preferably Ca. Me may be one or more. That is, in the titanium barium oxalate powder substituted with the Me element represented by the general formula (1), a part of the Ba position is substituted with one or more elements selected from Ca, Sr and Mg.
通式(1)中，q的值相當於原子換算的Ba與Me元素的合計相對於Ti的莫耳比((Ba+Me)/Ti)。q為0.980以上且未滿0.999，較佳為0.983以上且0.998以下，特佳為0.985以上且0.997以下。藉由q處於所述範圍，可獲得Me元素均勻地分佈於粉末整體、Me元素的偏析少的經Me元素取代的草酸氧鈦鋇粉末，且藉由煆燒，可獲得Me元素均勻地分佈於粉末整體、Me元素的偏析少的經Me元素取代的鈦酸鋇粉末。另一方面，若q未滿所述範圍，則難以獲得具有所需的特性的經Me元素取代的鈦酸鋇，且若超過所述範圍，則容易引起Me元素的偏析。 In the general formula (1), the value of q is equivalent to the molar ratio of the total of Ba and Me elements to Ti in terms of atomic conversion ((Ba+Me)/Ti). q is 0.980 or more and less than 0.999, preferably 0.983 or more and 0.998 or less, and particularly preferably 0.985 or more and 0.997 or less. When q is within the above range, a titanium barium oxalate powder substituted with Me element can be obtained in which Me element is uniformly distributed throughout the powder and Me element segregation is less, and a barium titanate powder substituted with Me element can be obtained by calcining in which Me element is uniformly distributed throughout the powder and Me element segregation is less. On the other hand, if q is less than the above range, it is difficult to obtain barium titanate substituted with Me element having the desired properties, and if it exceeds the above range, segregation of Me element is likely to occur.
通式(1)中，p相當於原子換算的Me元素相對於Ba的莫耳比(Me/Ba)。p為0.001以上且0.200以下，較佳為0.005以上且0.150以下。藉由p處於所述範圍，可獲得Me元素均勻地分佈於粉末整體、Me元素的偏析少的經Me元素取代的草酸氧鈦 鋇，且藉由煆燒，可獲得Me元素均勻地分佈於粒子整體、Me元素的偏析少的經Me元素取代的鈦酸鋇。另一方面，若p未滿所述範圍，則難以獲得具有所需的特性的經Me元素取代的鈦酸鋇，且若超過所述範圍，則容易引起Me元素的偏析。 In the general formula (1), p is equivalent to the molar ratio of Me element to Ba in terms of atomic conversion (Me/Ba). p is greater than 0.001 and less than 0.200, preferably greater than 0.005 and less than 0.150. When p is within the above range, Me element is uniformly distributed throughout the powder and Me element segregation is less, and Me element-substituted barium titanate is obtained, and Me element is uniformly distributed throughout the particles and Me element segregation is less, and Me element-substituted barium titanate is obtained by calcination. On the other hand, if p is less than the above range, it is difficult to obtain Me element-substituted barium titanate having the desired characteristics, and if it exceeds the above range, Me element segregation is easily caused.
通式(1)中，n為1~8的整數。n較佳為3~7的整數。 In general formula (1), n is an integer from 1 to 8. Preferably, n is an integer from 3 to 7.
再者，關於通式(1)所表示的經Me元素取代的草酸氧鈦鋇中的Ti、Ba、Me的各原子的莫耳比，可基於螢光X射線分析裝置(理學(Rigaku)股份有限公司製造、ZSX100e)的測定值來算出。另外，關於通式(1)所表示的經Me元素取代的草酸氧鈦鋇中的Ti、Ba、Me的各原子的莫耳比，亦可基於利用螢光X射線分析裝置(理學(Rigaku)股份有限公司製造、ZSX100e)測定經Me元素取代的鈦酸鋇而獲得的值來算出，所述經Me元素取代的鈦酸鋇是對經Me元素取代的草酸氧鈦鋇進行煆燒而獲得。 Furthermore, the molar ratio of each atom of Ti, Ba, and Me in the titanium barium oxalate substituted with Me represented by the general formula (1) can be calculated based on the measured value of a fluorescent X-ray analyzer (manufactured by Rigaku Co., Ltd., ZSX100e). In addition, the molar ratio of each atom of Ti, Ba, and Me in the titanium barium oxalate substituted with Me represented by the general formula (1) can also be calculated based on the value obtained by measuring the barium titanate substituted with Me using a fluorescent X-ray analyzer (manufactured by Rigaku Co., Ltd., ZSX100e), wherein the barium titanate substituted with Me is obtained by calcining the titanium barium oxalate substituted with Me.
本發明的經Me元素取代的有機酸氧鈦鋇粉末的平均粒徑並無特別限制，較佳為0.1μm~300μm，特佳為0.5μm~200μm。再者，於本發明中，經Me元素取代的有機酸氧鈦鋇粉末的平均粒徑是指藉由雷射繞射-散射法求出的粒度分佈中的體積累計50%的粒徑(D50)。 The average particle size of the organic acid titanium barium powder substituted with Me element of the present invention is not particularly limited, preferably 0.1μm~300μm, particularly preferably 0.5μm~200μm. Furthermore, in the present invention, the average particle size of the organic acid titanium barium powder substituted with Me element refers to the particle size (D50) of 50% of the volume accumulation in the particle size distribution obtained by laser diffraction-scattering method.
將本發明的經Me元素取代的有機酸氧鈦鋇粉末於600℃~1200℃、較佳為650℃~1100℃下煆燒而獲得的煆燒物為鈦系鈣鈦礦型複合氧化物，且為Ba位的一部分經Me元素取代的鈦酸鋇。即，本發明的經Me元素取代的有機酸氧鈦鋇粉末的煆燒 物為下述通式(2)：(Ba1-xMex)yTiO3 (2) The calcined product obtained by calcining the organic acid oxy-barium powder substituted with Me element of the present invention at 600°C to 1200°C, preferably 650°C to 1100°C is a titanium-based calcite-titanoite-type composite oxide, and is barium titanate in which a part of the Ba position is substituted with Me element. That is, the calcined product of the organic acid oxy-barium powder substituted with Me element of the present invention is the following general formula (2): (Ba 1-x Me x ) y TiO 3 (2)
所表示的經Me元素取代的鈦酸鋇粉末。通式(2)中，Me為選自Ca、Sr及Mg中的至少一種。x為0.001≦x≦0.200，較佳為0.010≦x≦0.150。另外，y為0.980≦y<0.999，較佳為0.983≦y≦0.998，特佳為0.985≦y≦0.997。 The barium titanate powder represented by the above is substituted by the Me element. In the general formula (2), Me is at least one selected from Ca, Sr and Mg. x is 0.001≦x≦0.200, preferably 0.010≦x≦0.150. In addition, y is 0.980≦y<0.999, preferably 0.983≦y≦0.998, and particularly preferably 0.985≦y≦0.997.
於藉由將本發明的經Me元素取代的有機酸氧鈦鋇粉末於600℃~1200℃、較佳為650℃~1100℃下煆燒而獲得的經Me元素取代的鈦酸鋇粉末中，於各粒子中，Me元素均勻地分佈於粒子。再者，於本發明中，Me元素均勻地分佈於經Me元素取代的鈦酸鋇的粒子是指：使用電子探針顯微分析儀(EPMA)分析，於經Me元素取代的鈦酸鋇的壓粉體的表面上，以成為一邊為205μm的正方形的範圍的方式以0.8μm間隔進行縱橫256點的映射分析，於所獲得的圖像解析中，算出Ca的CV值(標準偏差/平均值)，該值為0.4以下。 In the barium titanate powder substituted with Me element obtained by calcining the organic acid oxytitanium barium powder substituted with Me element of the present invention at 600°C to 1200°C, preferably 650°C to 1100°C, in each particle, the Me element is uniformly distributed in the particles. Furthermore, in the present invention, the Me element is uniformly distributed in the particles of the barium titanate substituted with the Me element, which means that: using an electron probe microanalyzer (EPMA) analysis, a mapping analysis of 256 points in the vertical and horizontal directions is performed in a square range of 205 μm on one side at an interval of 0.8 μm on the surface of the pressed powder of the barium titanate substituted with the Me element, and in the obtained image analysis, the CV value (standard deviation/average value) of Ca is calculated, and the value is less than 0.4.
本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法中，藉由在有機酸水溶液(B液)中添加於水中混合鋇化合物、Me元素化合物(Me表示選自Ca、Sr及Mg中的至少一種)及鈦化合物而獲得的水溶液(A液)，來獲得經Me元素取代的有機酸氧鈦鋇，所述經Me元素取代的有機酸氧鈦鋇粉末的製造方法的特徵在於：該A液中，以原子換算計，Me元素相對於Ba的莫耳比 (Me/Ba)為0.020以上且5.000以下，原子換算的Ba相對於Ti的莫耳比(Ba/Ti)為0.300以上且1.200以下，且A液向B液的添加速度為2.0ml/min以上。 In the method for producing organic acid oxytitanium barium powder substituted with Me element of the present invention, 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 added to an organic acid aqueous solution (liquid B) to obtain organic acid oxytitanium barium substituted with Me element. The method for producing organic acid oxytitanium barium powder substituted with Me element is characterized in that: in the liquid A, the molar ratio of Me element to Ba (Me/Ba) in terms of atomic conversion is 0.020 or more and 5.000 or less, the molar ratio of Ba to Ti in terms of atomic conversion (Ba/Ti) is 0.300 or more and 1.200 or less, and the addition rate of liquid A to liquid B is 2.0 ml/min or more.
本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法為如下的經Me元素取代的有機酸氧鈦鋇的製造方法，即，首先，向反應容器中放入反應中使用的B液的總量，繼而向反應容器中供給A液，並將A液添加至B液中，藉此進行經Me元素取代的有機酸氧鈦鋇的生成反應。 The method for producing organic acid oxytitanium barium powder substituted with Me element of the present invention is the following method for producing organic acid oxytitanium barium substituted with Me element, that is, first, the total amount of B liquid used in the reaction is placed in a reaction container, then A liquid is supplied to the reaction container, and A liquid is added to B liquid, thereby performing a generation reaction of organic acid oxytitanium barium substituted with Me element.
本發明的經Me元素取代的有機酸氧鈦鋇的製造方法中的A液為於水中混合鋇化合物、Me元素化合物及鈦化合物而獲得的水溶液。 In the method for producing organic acid titanium barium oxygen substituted with Me element of the present invention, liquid A is an aqueous solution obtained by mixing barium compound, Me element compound and titanium compound in water.
作為本發明的經Me元素取代的有機酸氧鈦鋇的製造方法中的鋇化合物，並無特別限制，可列舉：氯化鋇、碳酸鋇、氫氧化鋇、乙酸鋇、硝酸鋇等。鋇化合物可為一種，亦可併用兩種以上。作為鋇化合物，較佳為選自由氯化鋇、碳酸鋇及氫氧化鋇所組成的群組中的一種或兩種以上。 The barium compound used in the method for producing organic acid titanium barium substituted with Me element of the present invention is not particularly limited, and examples thereof include: barium chloride, barium carbonate, barium hydroxide, barium acetate, barium nitrate, etc. The barium compound may be one or more. The barium compound is preferably one or more selected from the group consisting of barium chloride, barium carbonate and barium hydroxide.
作為本發明的經Me元素取代的有機酸氧鈦鋇的製造方法中的Me元素化合物，並無特別限制，可列舉：包含選自由Ca、Sr及Mg所組成的群組中的一種或兩種以上元素的氯化物、氫氧化物、碳酸鹽、乙酸鹽、硝酸鹽等。Me元素化合物可為一種，亦可併用兩種以上。作為Me元素化合物，較佳為選自由Me元素的氯化物、Me元素的碳酸鹽及Me元素的氫氧化物所組成的群組中 的一種或兩種以上。 The Me element compound used in the method for producing organic acid oxytitanium barium substituted by the Me element of the present invention is not particularly limited, and can be exemplified by chlorides, hydroxides, carbonates, acetates, nitrates, etc. of one or more elements selected from the group consisting of Ca, Sr and Mg. The Me element compound can be one or more. As the Me element compound, it is preferably one or more selected from the group consisting of chlorides of the Me element, carbonates of the Me element and hydroxides of the Me element.
作為本發明的經Me元素取代的有機酸氧鈦鋇的製造方法中的鈦化合物，並無特別限制，可列舉四氯化鈦、乳酸鈦等。鈦化合物可為一種，亦可併用兩種以上。作為鈦化合物，較佳為四氯化鈦。 The titanium compound used in the method for producing organic acid oxytitanium barium substituted with Me element of the present invention is not particularly limited, and examples thereof include titanium tetrachloride, titanium lactate, etc. The titanium compound may be one type, or two or more types may be used in combination. Titanium tetrachloride is preferred as the titanium compound.
作為本發明的經Me元素取代的有機酸氧鈦鋇的製造方法中的有機酸，可列舉：草酸、檸檬酸、丙二酸及琥珀酸等。有機酸可為一種，亦可併用兩種以上。作為有機酸，較佳為草酸。 As organic acids in the method for producing organic acid titanium barium oxide substituted with Me element of the present invention, oxalic acid, citric acid, malonic acid and succinic acid can be listed. The organic acid can be one kind or two or more kinds can be used in combination. As the organic acid, oxalic acid is preferred.
而且，於本發明中，就反應性高且以高產率獲得穩定的品質者的方面而言，較佳為作為鋇化合物使用氯化鋇，作為Me元素化合物使用Me元素的氯化物，作為鈦化合物使用四氯化鈦，作為有機酸使用草酸。 Moreover, in the present invention, in terms of high reactivity and obtaining stable quality with high yield, it is preferred to use barium chloride as the barium compound, Me chloride as the Me element compound, titanium tetrachloride as the titanium compound, and oxalic acid as the organic acid.
A液中，原子換算的Me元素相對於Ba的莫耳比(Me/Ba)為0.020以上且5.000以下，較佳為0.050以上且4.000以下。藉由A液中的原子換算的Me元素相對於Ba的莫耳比(Me/Ba)處於所述範圍，可獲得Me元素均勻地分佈於粉末整體、Me元素的偏析少的經Me元素取代的有機酸氧鈦鋇粉末，且藉由煆燒，可獲得Me元素均勻地分佈於粉末整體、Me元素的偏析少的經Me元素取代的鈦酸鋇粉末。另一方面，若A液中的原子換算的Ba相對於Ti的莫耳比(Ba/Ti)未滿所述範圍，則Me元素的取代難以進行，且若超過所述範圍，則容易引起Me元素的偏析。 In liquid A, the molar ratio of Me element to Ba in terms of atomic conversion (Me/Ba) is 0.020 or more and 5.000 or less, preferably 0.050 or more and 4.000 or less. When the molar ratio of Me element to Ba in liquid A in terms of atomic conversion (Me/Ba) is within the above range, an organic acid oxytitanium barium powder substituted with Me element can be obtained, in which Me element is uniformly distributed throughout the powder and Me element segregation is less, and by calcination, a barium titanate powder substituted with Me element can be obtained, in which Me element is uniformly distributed throughout the powder and Me element segregation is less. On the other hand, if the molar ratio of Ba to Ti in liquid A in terms of atomic conversion (Ba/Ti) is less than the above range, substitution of Me element is difficult to perform, and if it exceeds the above range, segregation of Me element is easily caused.
A液中，原子換算的Ba相對於Ti的莫耳比(Ba/Ti)為 0.300以上且1.200以下，較佳為0.350以上且1.150以下。藉由A液中的原子換算的Ba相對於Ti的莫耳比(Ba/Ti)處於所述範圍，可獲得Me元素均勻地分佈於粒子整體、Me元素的偏析少的經Me元素取代的有機酸氧鈦鋇，且藉由煆燒，可獲得Me元素均勻地分佈於粒子整體、Me元素的偏析少的經Me元素取代的鈦酸鋇。另一方面，若A液中的原子換算的Ba相對於Ti的莫耳比(Ba/Ti)未滿所述範圍，則Me元素的取代難以進行，且若超過所述範圍，則容易引起Me元素的偏析。 In liquid A, the molar ratio of Ba to Ti in terms of atomic conversion (Ba/Ti) is 0.300 or more and 1.200 or less, preferably 0.350 or more and 1.150 or less. When the molar ratio of Ba to Ti in terms of atomic conversion (Ba/Ti) in liquid A is within the above range, organic acid titanium barium substituted with Me element can be obtained, in which Me element is uniformly distributed in the whole particle and Me element segregation is less, and barium titanate substituted with Me element can be obtained by calcination, in which Me element is uniformly distributed in the whole particle and Me element segregation is less. On the other hand, if the molar ratio of Ba to Ti in liquid A in terms of atomic conversion (Ba/Ti) is less than the above range, substitution of Me element is difficult, and if it exceeds the above range, segregation of Me element is easily caused.
A液中的Ba濃度並無特別限制，以原子換算計較佳為0.05mol/L~1.00mol/L，特佳為0.10mol/L~0.90mol/L。 There is no particular limit to the Ba concentration in solution A. The preferred concentration is 0.05 mol/L to 1.00 mol/L in terms of atomic conversion, and the most preferred concentration is 0.10 mol/L to 0.90 mol/L.
A液中的Me元素濃度並無特別限制，以原子換算計較佳為0.002mol/L~6.50mol/L，特佳為0.10mol/L~6.00mol/L。 There is no particular restriction on the concentration of Me element in liquid A. The preferred concentration is 0.002mol/L~6.50mol/L in terms of atomic conversion, and the most preferred concentration is 0.10mol/L~6.00mol/L.
A液中的Ti濃度並無特別限制，以原子換算計較佳為0.05mol/L~1.35mol/L，特佳為0.10mol/L~1.30mol/L。 There is no particular limit to the Ti concentration in liquid A. The preferred concentration is 0.05mol/L~1.35mol/L in terms of atomic conversion, and the most preferred concentration is 0.10mol/L~1.30mol/L.
本發明的經Me元素取代的有機酸氧鈦鋇的製造方法中的B液為將有機酸溶解於水中而獲得的有機酸水溶液。 The liquid B in the method for producing organic acid titanium barium oxide substituted with Me element of the present invention is an organic acid aqueous solution obtained by dissolving an organic acid in water.
A液中的原子換算的Ba、Me元素及Ti的合計莫耳數相對於B液中的有機酸根離子的莫耳數之比為0.800以上且1.400以下，較佳為0.850以上且1.300以下，特佳為0.900以上且1.250以下。藉由A液中的原子換算的Ba、Me元素及Ti的合計莫耳數相對於B液中的有機酸根離子的莫耳數之比處於所述範圍，可獲得Me元素均勻地分佈於粒子整體、Me元素的偏析少的經Me元 素取代的有機酸氧鈦鋇。 The ratio of the total molar number of Ba, Me and Ti in solution A to the molar number of organic acid radical ions in solution B is 0.800 or more and 1.400 or less, preferably 0.850 or more and 1.300 or less, and particularly preferably 0.900 or more and 1.250 or less. When the ratio of the total molar number of Ba, Me and Ti in solution A to the molar number of organic acid radical ions in solution B is within the above range, organic acid titanium barium substituted with Me element can be obtained in which Me element is uniformly distributed throughout the particles and Me element segregation is less.
B液中的有機酸根離子的濃度並無特別限制，較佳為0.10mol/L~5.00mol/L，特佳為0.50mol/L~3.00mol/L。 The concentration of organic acid radical ions in liquid B is not particularly limited, but is preferably 0.10mol/L~5.00mol/L, and particularly preferably 0.50mol/L~3.00mol/L.
於本發明的經Me元素取代的有機酸氧鈦鋇的製造方法中，首先，向反應容器中放入B液的總量，繼而向反應容器中供給A液，並將A液添加至B液中，藉此於反應容器內進行經Me元素取代的有機酸氧鈦鋇的生成反應。 In the method for producing organic acid titanium barium substituted with Me element of the present invention, first, the total amount of liquid B is placed in a reaction container, then liquid A is supplied to the reaction container, and liquid A is added to liquid B, thereby performing a reaction to generate organic acid titanium barium substituted with Me element in the reaction container.
將A液添加至B液時的A液的添加速度亦取決於實施的規模，但例如於0.5L規模的實驗室水準下，較佳為2.0ml/min以上，特佳為3.0ml/min以上。藉由以所述添加速度將A液添加至B液，可獲得Me元素均勻地分佈於粒子整體、Me元素的偏析少的經Me元素取代的有機酸氧鈦鋇。再者，只要滿足所述添加速度，則上限並無特別限制。 The addition rate of liquid A when adding liquid A to liquid B also depends on the scale of implementation, but for example, at the laboratory level of 0.5L scale, it is preferably 2.0ml/min or more, and particularly preferably 3.0ml/min or more. By adding liquid A to liquid B at the above addition rate, organic acid titanium barium substituted with Me element can be obtained, in which Me element is evenly distributed throughout the particles and Me element segregation is less. Furthermore, as long as the above addition rate is met, there is no particular upper limit.
將A液添加至B液時的混合溫度、即將A液添加至反應容器中時的A液及反應容器內的反應液(或B液)的溫度通常為10℃~50℃，較佳為15℃~45℃。藉由在所述混合溫度下將A液添加至B液，可獲得Me元素均勻地分佈於粒子整體、Me元素的偏析少的經Me元素取代的有機酸氧鈦鋇。 The mixing temperature when adding liquid A to liquid B, i.e., the temperature of liquid A and the reaction liquid (or liquid B) in the reaction container when liquid A is added to the reaction container, is usually 10°C to 50°C, preferably 15°C to 45°C. By adding liquid A to liquid B at the mixing temperature, organic acid titanium barium substituted with Me element can be obtained in which the Me element is evenly distributed throughout the particles and the segregation of the Me element is small.
於將A液總量添加至B液後，可藉由立即冷卻反應液、或者藉由以過濾等去除反應液來使反應結束，或者亦可將A液總量添加至B液後，進行將反應液於規定的溫度下維持一定時間的熟化。於進行熟化的情況下，熟化溫度較佳為10℃以上，特佳為 20℃~80℃，熟化時間較佳為0.1小時以上，特佳為0.2小時以上。 After adding the total amount of liquid A to liquid B, the reaction can be terminated by immediately cooling the reaction liquid or removing the reaction liquid by filtering, etc., or after adding the total amount of liquid A to liquid B, the reaction liquid can be aged at a specified temperature for a certain period of time. When the aging is performed, the aging temperature is preferably above 10°C, particularly preferably 20°C to 80°C, and the aging time is preferably above 0.1 hours, particularly preferably above 0.2 hours.
於將A液添加至B液時，較佳為一面攪拌反應液(或B液)一面進行A液向B液中的添加。另外，於將A液總量添加至B液後進行熟化的情況下，較佳為一面攪拌反應液一面進行熟化。攪拌速度並無特別限制，於開始向B液中添加A液至結束添加A液總量為止進行熟化的情況下，至熟化結束為止的期間，生成的包含經Me元素取代的有機酸氧鈦鋇的反應液是成為始終流動的狀態的攪拌速度即可。 When adding liquid A to liquid B, it is preferred to stir the reaction liquid (or liquid B) while adding liquid A to liquid B. In addition, when aging is performed after the total amount of liquid A is added to liquid B, it is preferred to stir the reaction liquid while aging. There is no particular restriction on the stirring speed. When aging is performed from the start of adding liquid A to liquid B to the end of adding the total amount of liquid A, the stirring speed can be such that the reaction liquid containing organic acid oxytitanium barium substituted with Me element is always flowing during the period until the end of aging.
向B液中添加A液總量後，進行熟化的情況下，於熟化結束後，利用常規方法進行反應液的固液分離，繼而對固體成分進行水洗。作為水洗方法，並無特別限制，就清洗效率高的方面而言，較佳為藉由再製漿等進行清洗。於清洗後，乾燥固體成分，視需要進行粉碎，從而獲得經Me元素取代的有機酸氧鈦鋇，即Ba位的一部分經Me元素取代的有機酸氧鈦鋇。 After adding the total amount of A liquid to B liquid and aging, after aging, the reaction liquid is separated into solid and liquid by conventional methods, and then the solid components are washed with water. There is no particular limitation on the washing method, and it is preferably washed by re-slurrying, etc. in terms of high washing efficiency. After washing, the solid components are dried and crushed as needed to obtain organic acid titanium barium substituted with Me element, that is, organic acid titanium barium substituted with Me element at a part of Ba position.
如此，進行本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法而獲得的經Me元素取代的有機酸氧鈦鋇粉末是Ba位的一部分經Me元素取代的有機酸氧鈦鋇，Ba與Me元素的合計相對於Ti的莫耳比((Ba+Me)/Ti)為0.980以上且未滿0.999，Me元素相對於Ba的莫耳比(Me/Ba)為0.001以上且0.250以下。 Thus, the organic acid titanium barium powder substituted with Me element obtained by the method for producing organic acid titanium barium powder substituted with Me element of the present invention is organic acid titanium barium in which a part of the Ba position is substituted with Me element, the molar ratio of the total Ba and Me elements to Ti ((Ba+Me)/Ti) is greater than 0.980 and less than 0.999, and the molar ratio of Me element to Ba (Me/Ba) is greater than 0.001 and less than 0.250.
於進行本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法而獲得的經Me元素取代的有機酸氧鈦鋇中，Me元素表示選自Ca、Sr及Mg中的至少一種元素，較佳為Ca、Sr，特佳為 Ca，Ba與Me元素的合計相對於Ti的莫耳比((Ba+Me)/Ti)為0.980以上且未滿0.999，較佳為0.983以上且0.998以下，特佳為0.985以上且0.997以下，Me元素相對於Ba的莫耳比(Me/Ba)為0.001以上且0.250以下，較佳為0.005以上且0.150以下。 In the organic acid titanium barium substituted with Me element obtained by the method for producing organic acid titanium barium substituted with Me element powder of the present invention, the Me element represents at least one element selected from Ca, Sr and Mg, preferably Ca and Sr, and particularly preferably Ca, 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, preferably 0.983 or more and 0.998 or less, 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.
進行本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法而獲得的經Me元素取代的有機酸氧鈦鋇粉末的平均粒徑並無特別限制，較佳為0.1μm~300μm，特佳為0.5μm~200μm。 The average particle size of the organic acid titanium barium powder substituted with Me element obtained by the method for producing the organic acid titanium barium powder substituted with Me element of the present invention is not particularly limited, and is preferably 0.1μm~300μm, and particularly preferably 0.5μm~200μm.
於本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法中，可獲得Me元素均勻地分佈於粉末整體、Me元素的偏析少的經Me元素取代的有機酸氧鈦鋇粉末。再者，Me元素均勻地分佈於經Me元素取代的有機酸氧鈦鋇粉末整體，Me元素的偏析少的情況可藉由如下方式來確認：對於進行本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法而獲得的經Me元素取代的有機酸氧鈦鋇粉末，於600℃~1200℃下進行煆燒，利用EPMA對獲得的經Me元素取代的鈦酸鋇進行映射分析。 In the method for producing organic acid oxy-barium powder substituted with Me element of the present invention, organic acid oxy-barium powder substituted with Me element can be obtained, in which Me element is evenly distributed in the whole powder and Me element segregation is small. Furthermore, the fact that Me element is evenly distributed in the whole powder substituted with Me element and Me element segregation is small can be confirmed by the following method: the organic acid oxy-barium powder substituted with Me element obtained by the method for producing organic acid oxy-barium powder substituted with Me element of the present invention is calcined at 600℃~1200℃, and the obtained barium titanate substituted with Me element is mapped and analyzed by EPMA.
另外，藉由對進行本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法而獲得的經Me元素取代的有機酸氧鈦鋇粉末，於600℃~1200℃、較佳為650℃~1100℃下進行煆燒，於所獲得的經Me元素取代的鈦酸鋇中，Me元素均勻地分佈於粒子表面。另外，於進行本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法而獲得的經Me元素取代的有機酸氧鈦鋇粉末中，Me元素均勻地分佈於粒子的深度方向。 In addition, the organic acid oxy-barium titanium powder substituted with Me element obtained by the method for producing organic acid oxy-barium titanium powder substituted with Me element of the present invention is calcined at 600℃~1200℃, preferably 650℃~1100℃, and in the obtained barium titanate substituted with Me element, the Me element is uniformly distributed on the particle surface. In addition, in the organic acid oxy-barium titanium powder substituted with Me element obtained by the method for producing organic acid oxy-barium titanium powder substituted with Me element of the present invention, the Me element is uniformly distributed in the depth direction of the particle.
關於將本發明的經Me元素取代的有機酸氧鈦鋇粉末、及進行本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法而獲得的經Me元素取代的有機酸氧鈦鋇粉末加以煆燒來獲得的經Me元素取代的鈦酸鋇粉末，可較佳地用作介電體陶瓷材料的鈦系鈣鈦礦型陶瓷原料粉末。即，對於本發明的經Me元素取代的有機酸氧鈦鋇粉末、或進行本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法而獲得的經Me元素取代的有機酸氧鈦鋇粉末，於600℃~1200℃、較佳為650℃~1100℃下進行煆燒，藉此可獲得鈦系鈣鈦礦型陶瓷原料粉末。 The organic acid oxytitanium barium powder substituted with Me element of the present invention and the barium titanate powder substituted with Me element obtained by calcining the organic acid oxytitanium barium powder substituted with Me element obtained by the method for producing the organic acid oxytitanium barium powder substituted with Me element of the present invention can be preferably used as a titanium-based calcium titanite-type ceramic raw material powder of a dielectric ceramic material. That is, the organic acid oxytitanium barium powder substituted with Me element of the present invention, or the organic acid oxytitanium barium powder substituted with Me element obtained by the method for producing the organic acid oxytitanium barium powder substituted with Me element of the present invention, is calcined at 600℃~1200℃, preferably 650℃~1100℃, thereby obtaining a titanium-based calcite-titano-type ceramic raw material powder.
將本發明的經Me元素取代的有機酸氧鈦鋇粉末、及進行本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法而獲得的經Me元素取代的有機酸氧鈦鋇粉末加以煆燒來獲得的經Me元素取代的鈦酸鋇粉末為由下述通式(2)：(Ba1-xMex)yTiO3 (2) The Me-substituted organic acid titanium barium powder of the present invention and the Me-substituted organic acid titanium barium powder obtained by calcining the Me-substituted organic acid titanium barium powder obtained by the method for producing the Me-substituted organic acid titanium barium powder of the present invention are represented by the following general formula (2): (Ba 1-x Me x ) y TiO 3 (2)
所表示的經Me元素取代的鈦酸鋇粉末。通式(2)中，Me為選自Ca、Sr及Mg中的至少一種。x為0.001≦x≦0.200，較佳為0.005≦x≦0.150。另外，y為0.980≦y<0.999，較佳為0.983≦y≦0.998，特佳為0.985≦y≦0.997。 The barium titanate powder represented by the above is substituted by the Me element. In the general formula (2), Me is at least one selected from Ca, Sr and Mg. x is 0.001≦x≦0.200, preferably 0.005≦x≦0.150. In addition, y is 0.980≦y<0.999, preferably 0.983≦y≦0.998, and particularly preferably 0.985≦y≦0.997.
於進行所述煆燒之前，視需要可以經Me元素取代的有機酸氧鈦鋇的平均粒徑較佳為4μm以下、特佳為0.02μm~0.5μm的方式，利用球磨機、珠磨機等進行經Me元素取代的有機酸氧鈦鋇粉末的濕式粉碎處理，以使得即便於微細且低溫區域進行煆燒 亦可獲得結晶性高的鈦系鈣鈦礦型陶瓷原料粉末。於該情況下，作為濕式粉碎處理中使用的溶媒，可使用對於經Me元素取代的有機酸氧鈦鋇而言為惰性的溶媒，例如可列舉：水、甲醇、乙醇、丙醇、丁醇、甲苯、二甲苯、丙酮、二氯甲烷、乙酸乙酯、二甲基甲醯胺及二乙醚等。其中，作為濕式粉碎處理用溶媒，就可獲得結晶性高的鈦系鈣鈦礦型陶瓷原料粉末的方面而言，較佳為甲醇、乙醇、丙醇、丁醇、甲苯、二甲苯、丙酮、二氯甲烷、乙酸乙酯、二甲基甲醯胺及二乙醚等作為有機溶媒且Ba元素、Ti元素及Me元素的溶出少的溶媒。 Before the calcination, the organic acid titanium barium substituted with Me element may be subjected to wet pulverization treatment using a ball mill, a bead mill, etc. in such a manner that the average particle size of the organic acid titanium barium substituted with Me element is preferably 4 μm or less, particularly preferably 0.02 μm to 0.5 μm, so that a titanium-based calcite-titano-type ceramic raw material powder with high crystallinity can be obtained even when calcined in a fine and low temperature region. In this case, as a solvent used in the wet pulverization treatment, a solvent that is inert to the organic acid titanium barium substituted with Me element can be used, for example, water, methanol, ethanol, propanol, butanol, toluene, xylene, acetone, dichloromethane, ethyl acetate, dimethylformamide, and diethyl ether. Among them, as a solvent for wet pulverization, methanol, ethanol, propanol, butanol, toluene, xylene, acetone, dichloromethane, ethyl acetate, dimethylformamide and diethyl ether are preferred as organic solvents and solvents with less elution of Ba, Ti and Me elements in terms of obtaining titanium-based calcium titanite-type ceramic raw material powder with high crystallinity.
本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法的特徵在於：對於本發明的經Me元素取代的有機酸氧鈦鋇粉末、或進行本發明的經Me元素取代的有機酸氧鈦鋇粉末的製造方法而獲得的經Me元素取代的有機酸氧鈦鋇粉末進行煆燒，藉此獲得經Me元素取代的鈦酸鋇。 The manufacturing method of the titanium-based calcium titanite-type ceramic raw material powder of the present invention is characterized in that the organic acid oxytitanium barium powder substituted with the Me element of the present invention or the organic acid oxytitanium barium powder substituted with the Me element obtained by the manufacturing method of the organic acid oxytitanium barium powder substituted with the Me element of the present invention is calcined to obtain the barium titanate substituted with the Me element.
經Me元素取代的有機酸氧鈦鋇粉末中所含的源於有機酸的有機物損害材料的介電體特性的同時，成為用以陶瓷化的熱步驟中的行為不穩定的因素，因此欠佳。因而，於本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法中，藉由煆燒經Me元素取代的有機酸氧鈦鋇粉末，對含Me元素的有機酸氧鈦鋇進行熱分解，從而獲得作為目標鈦系鈣鈦礦型陶瓷原料粉末的經Me元素取代的鈦酸鋇，同時去除源於有機酸的有機物。 The organic matter derived from the organic acid contained in the organic acid oxytitanium barium powder substituted with the Me element damages the dielectric properties of the material and becomes a factor of instability in the thermal step for ceramicization, so it is not good. Therefore, in the method for manufacturing the titanium-based calcium titanite type ceramic raw material powder of the present invention, the organic acid oxytitanium barium powder substituted with the Me element is calcined to thermally decompose the organic acid oxytitanium barium containing the Me element, thereby obtaining the barium titanate substituted with the Me element as the target titanium-based calcium titanite type ceramic raw material powder, and at the same time removing the organic matter derived from the organic acid.
於本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法 中，煆燒時的煆燒溫度為600℃~1200℃，較佳為650℃~1100℃。若煆燒溫度未滿所述範圍，則難以獲得單一相的鈦系鈣鈦礦型陶瓷原料粉末，且若超過所述範圍，則粒徑的偏差變大。於本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法中，煆燒時的煆燒時間較佳為0.2小時~30小時，特佳為0.5小時~20小時。於本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法中，煆燒時的煆燒環境並無特別限制，可為大氣環境下或惰性氣體環境下的任一種。 In the method for producing titanium-based calcium-tantalum-based ceramic raw material powder of the present invention, the sintering temperature is 600°C to 1200°C, preferably 650°C to 1100°C. If the sintering temperature is less than the above range, it is difficult to obtain a single-phase titanium-based calcium-tantalum-based ceramic raw material powder, and if it exceeds the above range, the deviation of the particle size becomes larger. In the method for producing titanium-based calcium-tantalum-based ceramic raw material powder of the present invention, the sintering time is preferably 0.2 hours to 30 hours, and particularly preferably 0.5 hours to 20 hours. In the method for manufacturing titanium-based calcium titanite-type ceramic raw material powder of the present invention, the sintering environment during sintering is not particularly limited and can be either an atmospheric environment or an inert gas environment.
於本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法中，可僅進行一次煆燒，亦可視需要反覆進行兩次以上。於反覆進行煆燒的情況下，為了使粉體特性均勻，亦可將煆燒一次而成者粉碎後進行下一次煆燒。 In the method for manufacturing titanium-based calcite-titanic ceramic raw material powder of the present invention, calcination may be performed only once, or may be repeated twice or more as needed. In the case of repeated calcination, in order to make the powder properties uniform, the powder calcined once may be crushed and then calcined again.
於本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法中，於煆燒後適宜冷卻，視需要進行粉碎，藉此獲得作為鈦系鈣鈦礦型複合氧化物且適合作為鈦系鈣鈦礦型陶瓷原料粉末的經Me元素取代的鈦酸鋇粉末。再者，視需要進行的粉碎是於煆燒而獲得的經Me元素取代的鈦酸鋇粉末為脆性結合的塊狀的粉末的情況下等適宜進行，經Me元素取代的鈦酸鋇粉末的粒子本身具有特定的平均粒徑、布厄特(Brunauer Emmett and Teller，BET)比表面積。即，進行本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法而獲得的經Me元素取代的鈦酸鋇粉末中，藉由掃描式電子顯微鏡(scanning electron microscope，SEM)求出的平均粒徑為0.01μm~4μm，較佳為0.02μm~0.5μm，BET比表面積為0.25m2/g~100 m2/g，較佳為2m2/g~50m2/g，組成的偏差少。再者，於本發明中，關於經Me元素取代的鈦酸鋇粉末的平均粒徑，利用掃描式電子顯微鏡(SEM)照片任意地測定200個粒子，將其平均值作為平均粒徑。 In the method for producing a titanium-based calcite-titanate type ceramic raw material powder of the present invention, the calcite-titanate type composite oxide is appropriately cooled after calcining, and pulverized as needed to obtain a barium titanate powder substituted with Me element, which is suitable as a titanium-based calcite-titanate type ceramic raw material powder. Furthermore, the pulverization as needed is appropriately performed when the barium titanate powder substituted with Me element obtained by calcining is a brittle and bonded block-shaped powder, and the particles of the barium titanate powder substituted with Me element themselves have a specific average particle size and Brunauer Emmett and Teller (BET) specific surface area. That is, the barium titanate powder substituted with Me element obtained by the method for producing titanium-based calcite-titanic ceramic raw material powder of the present invention has an average particle size of 0.01 μm to 4 μm, preferably 0.02 μm to 0.5 μm, and a BET specific surface area of 0.25 m 2 /g to 100 m 2 /g, preferably 2 m 2 /g to 50 m 2 /g, and has little compositional variation. Furthermore, in the present invention, regarding the average particle size of the barium titanate powder substituted with Me element, 200 particles are randomly measured using a scanning electron microscope (SEM) photograph, and the average value thereof is taken as the average particle size.
再者，於進行本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法而獲得的鈦系鈣鈦礦型陶瓷原料粉末中，視需要出於調整介電特性或溫度特性的目的，可於該鈦系鈣鈦礦型陶瓷原料粉末中添加含有含副成分元素的化合物。作為可使用的含副成分元素的化合物，例如可列舉包含選自由Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu的稀土元素、Li、Bi、Zn、Mn、Al、Si、Co、Ni、Cr、Fe、Ti、V、Nb、Mo、W及Sn所組成的群組中的至少一種元素的化合物。 Furthermore, in the titanium-based calcite-titania-type ceramic raw material powder obtained by carrying out the manufacturing method of the titanium-based calcite-titania-type ceramic raw material powder of the present invention, a compound containing a secondary component element can be added to the titanium-based calcite-titania-type ceramic raw material powder as needed for the purpose of adjusting the dielectric properties or temperature properties. As the usable compound containing a secondary component element, for example, a compound containing at least one element selected from the group consisting of rare earth elements such as Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Li, Bi, Zn, Mn, Al, Si, Co, Ni, Cr, Fe, Ti, V, Nb, Mo, W and Sn can be listed.
含副成分元素的化合物可為無機物或有機物的任一種，例如可列舉：包含所述元素的氧化物、氫氧化物、氯化物、硝酸鹽、草酸鹽、羧酸鹽及醇鹽等。再者，於含副成分元素的化合物為含有Si元素的化合物的情況下，除所述氧化物等以外，亦可使用氧化矽溶膠或矽酸鈉等。所述含副成分元素的化合物可適宜組合使用一種或兩種以上，其添加量或添加化合物的組合可根據目的來適宜選擇。 The compound containing the accessory element may be any inorganic or organic substance, for example, oxides, hydroxides, chlorides, nitrates, oxalates, carboxylates and alkoxides of the element. Furthermore, when the compound containing the accessory element is a compound containing Si, in addition to the oxide, silicon oxide sol or sodium silicate may also be used. The compound containing the accessory element may be used in combination of one or more, and the amount of addition or the combination of the added compounds may be appropriately selected according to the purpose.
使鈦系鈣鈦礦型陶瓷原料粉末中含有副成分元素的方法例如可列舉：將進行本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法而獲得的鈦系鈣鈦礦型陶瓷原料粉末與含副成分元素的化 合物均勻混合後進行煆燒的方法、或者將本發明的有機酸氧鈦鋇粉末或進行本發明的有機酸氧鈦鋇粉末的製造方法而獲得的本發明的有機酸氧鈦鋇粉末與含副成分元素的化合物均勻混合後，進行煆燒的方法。 Methods for making titanium-based calcite-titania-type ceramic raw material powder contain accessory elements include, for example, a method of uniformly mixing the titanium-based calcite-titania-type ceramic raw material powder obtained by the method for producing titanium-based calcite-titania-type ceramic raw material powder of the present invention with a compound containing accessory elements and then calcining, or a method of uniformly mixing the organic acid oxytitanium-barium powder of the present invention or the organic acid oxytitanium-barium powder of the present invention obtained by the method for producing organic acid oxytitanium-barium powder of the present invention with a compound containing accessory elements and then calcining.
將進行本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法而獲得的鈦系鈣鈦礦型陶瓷原料粉末，例如包含副成分元素在內，與先前公知的添加劑、有機系黏合劑、塑化劑、分散劑等調配劑一起混合分散於適當的溶媒中，加以漿料化，並進行片成形，藉此可獲得用於製造積層陶瓷電容器的陶瓷片。 The titanium-based calcium-titanic ore-type ceramic raw material powder obtained by the method for producing the titanium-based calcium-titanic ore-type ceramic raw material powder of the present invention, including auxiliary component elements, is mixed and dispersed in a suitable solvent together with a previously known additive, an organic binder, a plasticizer, a dispersant and other formulation agents, slurried, and sheet-formed to obtain a ceramic sheet for manufacturing a multilayer ceramic capacitor.
於由陶瓷片製作積層陶瓷電容器時，首先於陶瓷片的一面印刷內部電極形成用導電膏，乾燥後積層多枚陶瓷片，並於厚度方向壓接，藉此製成積層體。其次，對該積層體進行加熱處理，並進行脫黏合劑處理，加以煆燒而獲得煆燒體。進而若於燒結體上塗佈Ni膏、Ag膏、鎳合金膏、銅膏、銅合金膏等並燒製，則可獲得積層陶瓷電容器。 When making a multilayer ceramic capacitor from ceramic sheets, first, a conductive paste for forming an internal electrode is printed on one side of the ceramic sheet, and after drying, multiple ceramic sheets are stacked and pressed together in the thickness direction to form a multilayer body. Next, the multilayer body is subjected to a heat treatment, a debonding agent treatment, and sintering to obtain a sintered body. If Ni paste, Ag paste, nickel alloy paste, copper paste, copper alloy paste, etc. are applied to the sintered body and sintered, a multilayer ceramic capacitor can be obtained.
另外，例如將進行本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法而獲得的鈦系鈣鈦礦型陶瓷原料粉末調配於環氧樹酯、聚酯樹脂、聚醯亞胺樹脂等樹脂，製成樹脂片、樹脂膜、接著劑等時，可較佳地用作印刷配線板或多層印刷配線板等的材料，且亦可用作用以抑制內部電極與介電體層的收縮差的共同材料、電極陶瓷電路基板、玻璃陶瓷電路基板、電路周邊材料及無機EL用等的介電體材料。 In addition, for example, when the titanium-based calcium-titanate type ceramic raw material powder obtained by the method for manufacturing the titanium-based calcium-titanate type ceramic raw material powder of the present invention is mixed with resins such as epoxy resins, polyester resins, and polyimide resins to make resin sheets, resin films, adhesives, etc., it can be preferably used as a material for printed wiring boards or multilayer printed wiring boards, and can also be used as a common material for suppressing the shrinkage difference between internal electrodes and dielectric layers, electrode ceramic circuit substrates, glass ceramic circuit substrates, circuit peripheral materials, and dielectric materials for inorganic EL, etc.
另外，亦可將進行本發明的鈦系鈣鈦礦型陶瓷原料粉末的製造方法而獲得的鈦系鈣鈦礦型陶瓷原料粉末較佳地用作排氣去除、化學合成等反應時所使用的觸媒或者賦予防靜電、清潔效果的印刷色粉的表面改質材料。 In addition, the titanium-based calcium-titanate type ceramic raw material powder obtained by the method for manufacturing the titanium-based calcium-titanate type ceramic raw material powder of the present invention can also be preferably used as a catalyst used in reactions such as exhaust removal and chemical synthesis, or as a surface modification material for printing toners that imparts antistatic and cleaning effects.
以下，藉由實施例來詳細地說明本發明，但本發明並不限定於該些實施例。 The present invention is described in detail below through examples, but the present invention is not limited to these examples.
[實施例] [Implementation example]
於實施例中，藉由以下方法來測定特性。 In the embodiment, the characteristics are measured by the following method.
(1)Ba原子、Ca原子及Ti原子的莫耳比 (1) Molar ratio of Ba atoms, Ca atoms and Ti atoms
基於螢光X射線分析裝置(理學(Rigaku)股份有限公司製造、ZSX100e)的測定值來算出各原子的莫耳比。 The molar ratio of each atom was calculated based on the measured value of a fluorescent X-ray analyzer (ZSX100e, manufactured by Rigaku Co., Ltd.).
(2)經Me元素取代的草酸氧鈦鋇粉末的平均粒徑 (2) Average particle size of titanium barium oxalate powder substituted with Me element
使用麥奇克拜耳(microtrac-bel)公司製造的MT3000，藉由雷射繞射-散射法測定粒度分佈，將該粒度分佈中的體積累計50%的粒徑(D50)作為平均粒徑。 The particle size distribution was measured by laser diffraction-scattering method using MT3000 manufactured by Microtrac-Bel, and the particle size (D50) with 50% cumulative volume in the particle size distribution was taken as the average particle size.
(3)經Me元素取代的鈦酸鋇的平均粒徑 (3) Average particle size of barium titanium oxide substituted by Me element
使用日立高新技術(Hitachi High-technologies)公司製造的S4800，利用掃描式電子顯微鏡(SEM)照片，任意地測定200個粒子，將其平均值作為平均粒徑。 Using S4800 manufactured by Hitachi High-technologies, 200 particles were randomly measured using scanning electron microscope (SEM) photographs, and the average value was taken as the average particle size.
(4)基於EPMA的Ca原子映射分析 (4) Ca atom mapping analysis based on EPMA
使用電子探針顯微分析儀(EPMA)(日本電子股份有限公司製造、JXA8500F)，對Ca原子進行映射分析。 Ca atoms were mapped using an electron probe microanalyzer (EPMA) (manufactured by JEOL Ltd., JXA8500F).
(5)經Me元素取代的草酸氧鈦鋇粉末的X射線繞射分析 (5) X-ray diffraction analysis of titanium barium oxalate powder substituted with Me element
使用理學(Rigaku)股份有限公司製造的UltimaIV，進行X射線繞射分析。 X-ray diffraction analysis was performed using UltimaIV manufactured by Rigaku Co., Ltd.
(實施例1) (Implementation Example 1)
將氯化鋇二水鹽50.0g、氯化鈣二水鹽10.0g及四氯化鈦120.0g溶解於純水500ml中，製備混合水溶液，將其作為A液。再者，將A液中的各元素的莫耳比示於表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 referred to as liquid A. The molar ratio of each element in liquid A is shown in Table 1.
繼而，將草酸70.0g溶解於30℃的溫水500ml中，製備草酸水溶液，將其作為B液。 Next, 70.0 g of oxalic acid was dissolved in 500 ml of warm water at 30°C to prepare an oxalic acid aqueous solution, which was used as liquid B.
繼而，一面將B液(滴加開始後為反應液)保持在30℃，一面於攪拌下花費120分鐘以4.2ml/min的速度添加A液，進而於30℃下攪拌60分鐘下熟化。於冷卻後，進行過濾來回收草酸氧鈦鋇鈣粉末。 Next, while keeping liquid B (reaction liquid after the dropwise addition) at 30°C, liquid A was added at a rate of 4.2 ml/min for 120 minutes under stirring, and then matured at 30°C for 60 minutes under stirring. After cooling, the titanium barium calcium oxalate powder was recovered by filtration.
繼而，利用蒸餾水將回收的草酸氧鈦鋇鈣粉末再製漿並加以清洗。繼而，於80℃下乾燥來獲得草酸氧鈦鋇鈣粉末。所獲得的草酸氧鈦鋇鈣粉末的物性值如表1般。另外，於800℃下對所獲得的草酸氧鈦鋇鈣粉末進行煆燒，對於所獲得的鈦酸鋇鈣粉末，使用電子探針顯微分析儀(EPMA)(日本電子股份有限公司製造、JXA8500F)，對Ca原子進行映射分析。將其結果示於圖1。根據圖1的結果可知，於所獲得的鈦酸鋇鈣粉末中，未看到Ca原子的偏析，Ca均勻地分散。另外，對所獲得的鈦酸鋇鈣粉末進行元素分析的結果為Ca/Ba為0.020，(Ba+Ca)/Ti為0.994。 Then, the recovered titanium barium calcium oxalate powder was re-slurried and washed with distilled water. Then, it was dried at 80°C to obtain titanium barium calcium oxalate powder. The physical properties of the obtained titanium barium calcium oxalate powder are shown in Table 1. In addition, the obtained titanium barium calcium oxalate powder was calcined at 800°C, and the obtained titanium barium calcium oxalate powder was mapped and analyzed for Ca atoms using an electron probe microanalyzer (EPMA) (manufactured by JEOL Ltd., JXA8500F). The results are shown in Figure 1. According to the results in Figure 1, no segregation of Ca atoms was observed in the obtained barium calcium titanate powder, and Ca was uniformly dispersed. In addition, the results of elemental analysis of the obtained barium calcium titanate powder showed that Ca/Ba was 0.020 and (Ba+Ca)/Ti was 0.994.
再者，根據所獲得的鈦酸鋇鈣粉末的元素分析結果及將A液添加至B液中而獲得的草酸氧鈦鋇鈣的X射線繞射分析，確認到本實施例1中獲得的草酸氧鈦鋇鈣為(Ba0.080Ca0.020)0.994TiO(C2O4)2．4H2O。將X射線繞射分析的結果示於圖2。 Furthermore, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanate oxalate obtained by adding Solution A to Solution B, it was confirmed that the barium calcium titanate oxalate obtained in Example 1 was (Ba 0.080 Ca 0.020 ) 0.994 TiO(C 2 O 4 ) 2 ． 4H 2 O. The results of the X-ray diffraction analysis are shown in FIG. 2 .
(實施例2) (Example 2)
將氯化鋇二水鹽40.0g、氯化鈣二水鹽20.0g及四氯化鈦120.0g溶解於純水500ml中，製備混合水溶液，將其作為A液。再者，將A液中的各元素的莫耳比示於表1。 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 referred to as liquid A. The molar ratio of each element in liquid A is shown in Table 1.
繼而，將草酸70.0g溶解於30℃的溫水500ml中，製備草酸水溶液，將其作為B液。 Next, 70.0 g of oxalic acid was dissolved in 500 ml of warm water at 30°C to prepare an oxalic acid aqueous solution, which was used as liquid B.
繼而，一面將B液(滴加開始後為反應液)保持在30℃，一面於攪拌下花費120分鐘以4.2ml/min的速度添加A液，進而於30℃下攪拌60分鐘下熟化。 Next, while keeping liquid B (reaction liquid after the dropwise addition) at 30°C, liquid A was added at a rate of 4.2 ml/min over 120 minutes under stirring, and then matured at 30°C under stirring for 60 minutes.
以後的操作利用與實施例1相同的方法進行。所獲得的草酸氧鈦鋇鈣粉末的物性值如表1般。另外，對所獲得的草酸氧鈦鋇鈣粉末進行煆燒，對於所獲得的鈦酸鋇鈣粉末，使用EPMA，進行Ca原子的映射分析。將其結果示於圖3。根據圖3的結果可知，於所獲得的鈦酸鋇鈣粉末中，未看到Ca原子的偏析，Ca均勻地分散。另外，對所獲得的鈦酸鋇鈣粉末進行元素分析的結果為Ca/Ba為0.05，(Ba+Ca)/Ti為0.998。 Subsequent operations were performed using the same method as in Example 1. The physical properties of the obtained barium titanate calcium powder are shown in Table 1. In addition, the obtained barium titanate calcium powder was calcined, and the obtained barium titanate calcium powder was subjected to Ca atom mapping analysis using EPMA. The results are shown in FIG3 . According to the results of FIG3 , no segregation of Ca atoms was observed in the obtained barium titanate calcium powder, and Ca was uniformly dispersed. In addition, the results of elemental analysis of the obtained barium titanate calcium powder were as follows: Ca/Ba was 0.05, and (Ba+Ca)/Ti was 0.998.
再者，根據所獲得的鈦酸鋇鈣粉末的元素分析結果及將A液 添加至B液中而獲得的草酸氧鈦鋇鈣的X射線繞射分析，確認到本實施例2中獲得的草酸氧鈦鋇鈣為(Ba0.08Ca0.05)0.998TiO(C2O4)2．4H2O。將X射線繞射分析的結果示於圖2。 Furthermore, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanate oxalate obtained by adding Solution A to Solution B, it was confirmed that the barium calcium titanate oxalate obtained in Example 2 was (Ba 0.08 Ca 0.05 ) 0.998 TiO(C 2 O 4 ) 2 ． 4H 2 O. The results of the X-ray diffraction analysis are shown in FIG. 2 .
(實施例3) (Implementation Example 3)
將氯化鋇二水鹽40.0g、氯化鈣二水鹽7.5g及四氯化鈦120.0g溶解於純水500ml中，製備混合水溶液，將其作為A液。再者，將A液中的各元素的莫耳比示於表1。 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 referred to as liquid A. The molar ratio of each element in liquid A is shown in Table 1.
繼而，將草酸70.0g溶解於30℃的溫水500ml中，製備草酸水溶液，將其作為B液。 Next, 70.0 g of oxalic acid was dissolved in 500 ml of warm water at 30°C to prepare an oxalic acid aqueous solution, which was used as liquid B.
繼而，一面將B液(滴加開始後為反應液)保持在30℃，一面於攪拌下花費120分鐘以4.2ml/min的速度添加A液，進而於30℃下攪拌60分鐘下熟化。 Next, while keeping liquid B (reaction liquid after the dropwise addition) at 30°C, liquid A was added at a rate of 4.2 ml/min over 120 minutes under stirring, and then matured at 30°C under stirring for 60 minutes.
以後的操作利用與實施例1相同的方法進行。所獲得的草酸氧鈦鋇鈣粉末的物性值如表1般。另外，對所獲得的草酸氧鈦鋇鈣粉末進行煆燒，對於所獲得的鈦酸鋇鈣粉末，使用EPMA，進行Ca原子的映射分析。將其結果示於圖4。根據圖4的結果可知，於所獲得的鈦酸鋇鈣粉末中，未看到Ca原子的偏析，Ca均勻地分散。另外，對所獲得的鈦酸鋇鈣粉末進行元素分析的結果為Ca/Ba為0.02，(Ba+Ca)/Ti為0.991。 Subsequent operations were performed using the same method as in Example 1. The physical properties of the obtained barium titanate calcium powder are shown in Table 1. In addition, the obtained barium titanate calcium powder was calcined, and the obtained barium titanate calcium powder was subjected to Ca atom mapping analysis using EPMA. The results are shown in FIG4 . According to the results of FIG4 , no segregation of Ca atoms was observed in the obtained barium titanate calcium powder, and Ca was uniformly dispersed. In addition, the results of elemental analysis of the obtained barium titanate calcium powder were as follows: Ca/Ba was 0.02, and (Ba+Ca)/Ti was 0.991.
再者，根據所獲得的鈦酸鋇鈣粉末的元素分析結果及將A液添加至B液中而獲得的草酸氧鈦鋇鈣的X射線繞射分析，確認到 本實施例3中獲得的草酸氧鈦鋇鈣為(Ba0.08Ca0.02)0.991TiO(C2O4)2．4H2O。將X射線繞射分析的結果示於圖2。 Furthermore, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanate obtained by adding Solution A to Solution B, it was confirmed that the barium calcium titanate obtained in Example 3 was (Ba 0.08 Ca 0.02 ) 0.991 TiO(C 2 O 4 ) 2 ． 4H 2 O. The results of the X-ray diffraction analysis are shown in FIG. 2 .
(實施例4) (Implementation Example 4)
將碳酸鋇52.0g、碳酸鈣4.7g及四氯化鈦120.0g溶解於純水420ml中，製備混合水溶液，將其作為A液。再者，將A液中的各元素的莫耳比示於表1。 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 referred to as liquid A. The molar ratio of each element in liquid A is shown in Table 1.
繼而，將草酸70.0g溶解於30℃的溫水420ml中，製備草酸水溶液，將其作為B液。 Next, 70.0 g of oxalic acid was dissolved in 420 ml of warm water at 30°C to prepare an oxalic acid aqueous solution, which was used as liquid B.
繼而，一面將B液(滴加開始後為反應液)保持在30℃，一面於攪拌下花費120分鐘以3.5ml/min的速度添加A液，進而於30℃下攪拌60分鐘下熟化。於冷卻後，進行過濾來回收草酸氧鈦鋇鈣粉末。 Next, while keeping liquid B (reaction liquid after the dropwise addition) at 30°C, liquid A was added at a rate of 3.5 ml/min for 120 minutes under stirring, and then matured at 30°C for 60 minutes under stirring. After cooling, the titanium barium calcium oxalate powder was recovered by filtration.
繼而，利用蒸餾水將回收的草酸氧鈦鋇鈣粉末再製漿並加以清洗。繼而，於80℃下乾燥來獲得草酸氧鈦鋇鈣粉末。所獲得的草酸氧鈦鋇鈣粉末的物性值如表1般。另外，於800℃下對所獲得的草酸氧鈦鋇鈣粉末進行煆燒，對於所獲得的鈦酸鋇鈣粉末，使用電子探針顯微分析儀(EPMA)(日本電子股份有限公司製造、JXA8500F)，對Ca原子進行映射分析。將其結果示於圖5。根據圖5的結果可知，於所獲得的鈦酸鋇鈣粉末中，未看到Ca原子的偏析，Ca均勻地分散。另外，對所獲得的鈦酸鋇鈣粉末進行元素分析的結果為Ca/Ba為0.026，(Ba+Ca)/Ti為0.998。 Then, the recovered titanium barium calcium oxalate powder was re-slurried and washed with distilled water. Then, it was dried at 80°C to obtain titanium barium calcium oxalate powder. The physical properties of the obtained titanium barium calcium oxalate powder are shown in Table 1. In addition, the obtained titanium barium calcium oxalate powder was calcined at 800°C, and the obtained titanium barium calcium oxalate powder was mapped and analyzed for Ca atoms using an electron probe microanalyzer (EPMA) (manufactured by JEOL Ltd., JXA8500F). The results are shown in FIG5 . According to the results of Figure 5, no segregation of Ca atoms was observed in the obtained barium calcium titanate powder, and Ca was uniformly dispersed. In addition, the results of elemental analysis of the obtained barium calcium titanate powder were that Ca/Ba was 0.026 and (Ba+Ca)/Ti was 0.998.
再者，根據所獲得的鈦酸鋇鈣粉末的元素分析結果及將A液添加至B液中而獲得的草酸氧鈦鋇鈣的X射線繞射分析，確認到本實施例4中獲得的草酸氧鈦鋇鈣為(Ba0.08Ca0.03)0.998TiO(C2O4)2．4H2O。將X射線繞射分析的結果示於圖2。 Furthermore, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanate oxalate obtained by adding Solution A to Solution B, it was confirmed that the barium calcium titanate oxalate obtained in Example 4 was (Ba 0.08 Ca 0.03 ) 0.998 TiO(C 2 O 4 ) 2 ． 4H 2 O. The results of the X-ray diffraction analysis are shown in FIG. 2 .
(實施例5) (Example 5)
將氯化鋇二水鹽360.0g、氯化鈣二水鹽72.0g及四氯化鈦864.0g溶解於純水3600ml中，製備混合水溶液，將其作為A液。再者，將A液中的各元素的莫耳比示於表1。 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 referred to as liquid A. The molar ratio of each element in liquid A is shown in Table 1.
繼而，將草酸504.0g溶解於30℃的溫水3600ml中，製備草酸水溶液，將其作為B液。 Next, 504.0 g of oxalic acid was dissolved in 3600 ml of warm water at 30°C to prepare an oxalic acid aqueous solution, which was used as liquid B.
繼而，一面將B液(滴加開始後為反應液)保持在30℃，一面於攪拌下花費120分鐘以30ml/min的速度添加A液，進而於30℃下攪拌60分鐘下熟化。於冷卻後，進行過濾來回收草酸氧鈦鋇鈣粉末。 Next, while keeping liquid B (reaction liquid after the dropwise addition) at 30°C, liquid A was added at a rate of 30 ml/min for 120 minutes under stirring, and then matured under stirring at 30°C for 60 minutes. After cooling, the titanium barium calcium oxalate powder was recovered by filtration.
繼而，利用蒸餾水將回收的草酸氧鈦鋇鈣粉末再製漿並加以清洗。繼而，於80℃下乾燥來獲得草酸氧鈦鋇鈣粉末。所獲得的草酸氧鈦鋇鈣粉末的物性值如表1般。另外，於800℃下對所獲得的草酸氧鈦鋇鈣粉末進行煆燒，對於所獲得的鈦酸鋇鈣粉末，使用電子探針顯微分析儀(EPMA)(日本電子股份有限公司製造、JXA8500F)，對Ca原子進行映射分析。將其結果示於圖6。根據圖6的結果可知，於所獲得的鈦酸鋇鈣粉末中，未看到Ca原子的 偏析，Ca均勻地分散。另外，對所獲得的鈦酸鋇鈣粉末進行元素分析的結果為Ca/Ba為0.025，(Ba+Ca)/Ti為0.994。 Then, the recovered titanium barium calcium oxalate powder was re-slurried and washed with distilled water. Then, it was dried at 80°C to obtain titanium barium calcium oxalate powder. The physical properties of the obtained titanium barium calcium oxalate powder are shown in Table 1. In addition, the obtained titanium barium calcium oxalate powder was calcined at 800°C, and the obtained titanium barium calcium oxalate powder was mapped and analyzed for Ca atoms using an electron probe microanalyzer (EPMA) (manufactured by JEOL Ltd., JXA8500F). The results are shown in FIG6 . According to the results of Figure 6, no segregation of Ca atoms was observed in the obtained barium calcium titanate powder, and Ca was uniformly dispersed. In addition, the results of elemental analysis of the obtained barium calcium titanate powder were that Ca/Ba was 0.025 and (Ba+Ca)/Ti was 0.994.
再者，根據所獲得的鈦酸鋇鈣粉末的元素分析結果及將A液添加至B液中而獲得的草酸氧鈦鋇鈣的X射線繞射分析，確認到本實施例5中獲得的草酸氧鈦鋇鈣為(Ba0.08Ca0.02)0.994TiO(C2O4)2．4H2O。將X射線繞射分析的結果示於圖2。 Furthermore, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanate oxalate obtained by adding Solution A to Solution B, it was confirmed that the barium calcium titanate oxalate obtained in Example 5 was (Ba 0.08 Ca 0.02 ) 0.994 TiO(C 2 O 4 ) 2 ． 4H 2 O. The results of the X-ray diffraction analysis are shown in FIG. 2 .
(比較例1) (Comparison Example 1)
將氯化鋇二水鹽150.0g、氯化鈣二水鹽10.0g及四氯化鈦120.0g溶解於純水500ml中，製備混合水溶液，將其作為A液。再者，將A液中的各元素的莫耳比示於表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 referred to as liquid A. The molar ratio of each element in liquid A is shown in Table 1.
其次，將草酸70.0g溶解於30℃的溫水500ml中，製備草酸水溶液，將其作為B液。 Next, dissolve 70.0 g of oxalic acid in 500 ml of warm water at 30°C to prepare an oxalic acid aqueous solution, which is used as liquid B.
繼而，一面將B液保持在30℃，一面於攪拌下花費120分鐘以4.2ml/min的速度添加A液，進而於30℃下攪拌60分鐘下熟化。於冷卻後，進行過濾來回收草酸氧鈦鋇鈣粉末。 Then, while keeping liquid B at 30°C, liquid A was added at a rate of 4.2 ml/min for 120 minutes under stirring, and then matured at 30°C for 60 minutes under stirring. After cooling, the titanium barium calcium oxalate powder was recovered by filtration.
以後的操作利用與實施例1相同的方法進行。所獲得的草酸氧鈦鋇鈣粉末的物性值如表1般。另外，對所獲得的草酸氧鈦鋇鈣粉末進行煆燒，對於所獲得的鈦酸鋇鈣粉末，使用EPMA，進行Ca原子的映射分析。將其結果示於圖7。根據圖7的結果可知，於所獲得的鈦酸鋇鈣粉末中，Ca原子偏析。另外，對所獲得的鈦酸鋇鈣粉末進行元素分析的結果為Ca/Ba為0.020，(Ba+Ca)/Ti 為1.000。 Subsequent operations were performed using the same method as in Example 1. The physical properties of the obtained barium titanate calcium powder are shown in Table 1. In addition, the obtained barium titanate calcium powder was calcined, and the obtained barium titanate calcium powder was subjected to Ca atom mapping analysis using EPMA. The results are shown in FIG7 . According to the results of FIG7 , Ca atoms are segregated in the obtained barium titanate calcium powder. In addition, the elemental analysis results of the obtained barium titanate calcium powder were Ca/Ba = 0.020, (Ba+Ca)/Ti = 1.000.
再者，根據所獲得的鈦酸鋇鈣粉末的元素分析結果及將A液添加至B液中而獲得的草酸氧鈦鋇鈣的X射線繞射分析，確認到本比較例1中獲得的草酸氧鈦鋇鈣為(Ba0.080Ca0.020)1.000TiO(C2O4)2．4H2O。 Furthermore, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the barium calcium titanate oxalate obtained by adding Solution A to Solution B, it was confirmed that the barium calcium titanate oxalate obtained in Comparative Example 1 was (Ba 0.080 Ca 0.020 ) 1.000 TiO(C 2 O 4 ) 2 ． 4H 2 O.
(比較例2) (Comparison Example 2)
將氯化鋇二水鹽27.0g、氯化鈣二水鹽5.4g及四氯化鈦64.1g溶解於純水180ml中，製備混合水溶液，將其作為A液。再者，將A液中的各元素的莫耳比示於表1。 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 referred to as liquid A. The molar ratio of each element in liquid A is shown in Table 1.
其次，將草酸32.5g溶解於55℃的溫水140ml中，製備草酸水溶液，將其作為B液。 Next, dissolve 32.5 g of oxalic acid in 140 ml of warm water at 55°C to prepare an oxalic acid aqueous solution, which is used as Solution B.
繼而，一面將B液保持在55℃，一面於攪拌下花費120分鐘以1.5ml/min的速度添加A液，進而於55℃下攪拌60分鐘下熟化。於冷卻後，進行過濾來回收草酸氧鈦鋇鈣粉末。 Then, while keeping liquid B at 55°C, liquid A was added at a rate of 1.5 ml/min for 120 minutes under stirring, and then matured at 55°C for 60 minutes under stirring. After cooling, the titanium barium calcium oxalate powder was recovered by filtration.
以後的操作利用與實施例1相同的方法進行。所獲得的草酸氧鈦鋇鈣粉末的物性值如表1般。另外，對所獲得的草酸氧鈦鋇鈣粉末進行煆燒，對於所獲得的鈦酸鋇鈣粉末，使用EPMA，進行Ca原子的映射分析。將其結果示於圖8。根據圖8的結果可知，於所獲得的鈦酸鋇鈣粉末中，Ca原子偏析。另外，對所獲得的鈦酸鋇鈣粉末進行元素分析的結果為Ca/Ba為0.020，(Ba+Ca)/Ti為0.999。 Subsequent operations were performed using the same method as in Example 1. The physical properties of the obtained barium titanate calcium powder are shown in Table 1. In addition, the obtained barium titanate calcium powder was calcined, and the obtained barium titanate calcium powder was subjected to Ca atom mapping analysis using EPMA. The results are shown in FIG8 . According to the results of FIG8 , Ca atoms are segregated in the obtained barium titanate calcium powder. In addition, the elemental analysis results of the obtained barium titanate calcium powder were Ca/Ba was 0.020, and (Ba+Ca)/Ti was 0.999.
再者，根據所獲得的鈦酸鋇鈣粉末的元素分析結果及將A液 添加至B液中而獲得的草酸氧鈦鋇鈣的X射線繞射分析，確認到本比較例2中獲得的草酸氧鈦鋇鈣為(Ba0.080Ca0.020)0.999TiO(C2O4)2．4H2O。 Furthermore, from the elemental analysis results of the obtained barium calcium titanate powder and the X-ray diffraction analysis of the titanium barium calcium oxalate obtained by adding solution A to solution B, it was confirmed that the titanium barium calcium oxalate obtained in Comparative Example 2 was (Ba 0.080 Ca 0.020 ) 0.999 TiO(C 2 O 4 ) 2 ． 4H 2 O.
[表1]
根據表1及圖1~圖8的結果理解，與由比較例的草酸氧鈦鋇鈣獲得的鈦酸鋇鈣相比，由實施例的草酸氧鈦鋇鈣獲得的鈦酸鋇鈣中鈣原子不偏析，均勻地分佈。 According to the results in Table 1 and Figures 1 to 8, compared with the barium calcium titanate obtained from the comparative example, the barium calcium titanate obtained from the barium calcium titanate of the embodiment does not segregate calcium atoms but is evenly distributed.
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