CN102649640B - 钙钛矿型复合氧化物的制造方法 - Google Patents
钙钛矿型复合氧化物的制造方法 Download PDFInfo
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- CN102649640B CN102649640B CN201210040768.2A CN201210040768A CN102649640B CN 102649640 B CN102649640 B CN 102649640B CN 201210040768 A CN201210040768 A CN 201210040768A CN 102649640 B CN102649640 B CN 102649640B
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- composite oxide
- perovskite composite
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- calcium
- green sheet
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- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 45
- 239000011575 calcium Substances 0.000 claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229940043430 calcium compound Drugs 0.000 claims abstract description 25
- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003985 ceramic capacitor Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910001863 barium hydroxide Inorganic materials 0.000 claims abstract description 12
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 27
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 12
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 8
- 239000001639 calcium acetate Substances 0.000 claims description 8
- 229960005147 calcium acetate Drugs 0.000 claims description 8
- 235000011092 calcium acetate Nutrition 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 description 19
- 239000006104 solid solution Substances 0.000 description 14
- 229910002113 barium titanate Inorganic materials 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000006166 lysate Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 125000000266 alpha-aminoacyl group Chemical group 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 150000001553 barium compounds Chemical class 0.000 description 2
- 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 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- -1 calcium compounds Calcium carbonate Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004531 microgranule Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
-
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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- B32—LAYERED PRODUCTS
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- B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
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Abstract
本发明提供高效率且经济地制造微细、结晶性高的钙钛矿型复合氧化物的方法,其可以适用于介电体层的层叠数多、薄层化的层叠陶瓷电容器的介电体层等。包括至少使氧化钛、钙化合物和氢氧化钡在浆液中反应,从而钙钛矿型复合氧化物生成的反应工序,并且,作为钙化合物,使用碳酸钙,以(Ba1?xCax)mTiO3表示钙钛矿型复合氧化物时,得到x处于0<x≤0.125的范围的钙钛矿型复合氧化物。另外,作为钙化合物,使用水溶性的钙化合物,以(Ba1?xCax)mTiO3表示钙钛矿型复合氧化物时,得到x处于0<x≤0.20的范围的钙钛矿型复合氧化物。
Description
技术领域
本发明涉及复合氧化物的制造方法,详细地说,是涉及可以适合作为陶瓷电子元件用的陶瓷原料使用的钙钛矿型复合氧化物的制造方法。
背景技术
作为由通式ABO3所代表的钙钛矿型复合氧化物之一的钛酸钡系陶瓷,其作为具有优异的介电特性的材料,被广泛用于层叠陶瓷电容器等用途。
而且,作为具有由通式ABO3所代表的钙钛矿结构的复合氧化物粉末的制造方法,例如提出有一种复合氧化物粉末的制造方法,其具有如下工序,即,将含有结晶水的构成A部位成分的元素的氢氧化物,和具有250m2/g以上的比表面积的氧化钛粉末加以混合的混合处理工序,混合处理工序包括:溶解液生成工序,是通过进行加热处理,只由结晶水的水分,生成A部位成分溶解的溶解液的工序;反应工序,是氧化钛粉末和溶解液发生反应而生成反应合成物的工序,使溶解液生成工序和反应工序连续地进行(专利文献1的权利要求1)。另外,在专利文献1中还公开,预烧所得到的复合氧化物(专利文献1的权利要求7)。
于是,根据该专利文献1的发明的方法,认为能够得到异相少,超微粒且结晶性优异的复合氧化物,通过对其进行预烧处理,晶系从立方晶系复合氧化物转移,能够制作结晶性优异的正方晶系的复合氧化物。
另外,作为其他的复合氧化物的制造方法,还提出有一种钛酸钡粉末的制造方法,其具有如下反应工序:在不存在二氧化碳的气氛下,使氧化钛粒子和水溶性钡化合物,对于前述氧化钛粒子的摩尔数,以等摩尔添加前述水溶性钡化合物,在pH为11.5以上、13.0以下的水溶液中,在100℃以下的温度使之反应(专利文献2的权利要求2)。
根据该专利文献2的发明的方法,可知既能够防止氯化物杂质的混入,又能够经济地制造粒度分布窄的钛酸钡粉末。
另一方面,作为介电体层的构成材料,在使用了上述这样的钛酸钡(复合氧化物)系的材料的层叠陶瓷电容器中,小型、大容量化推进,直至介电体层的厚度为1μm左右,层叠数超过800层这样的层叠电容器得到实用化。
而且,为了使层叠陶瓷电容器更小型化,需要进行薄层化而使介电体层的厚度达到1μm以下的亚微米的区域,但为了实现亚微米厚度的介电体层,需要使构成介电体层的陶瓷烧结体的粒径微细至100nm以下。为此,就要求用于形成介电体层的烧结前的原料粉末(例如,钛酸钡系材料的预烧粉末)本身的粒径很小。
若从上述的观点出发,则上述的专利文献1和2的发明,虽然可以得到微粒的钛酸钡粉末,是有意义的,但为了应对今后更进一步的薄层化,实际情况是,要求有一种高效率地制造更微细、并具有高可靠性的钙钛矿型复合氧化物的方法。
【先行技術文献】
【专利文献】
【专利文献1】日本专利第4200427号公报
【专利文献2】日本专利第4057475号公报
发明内容
本发明是解决上述课题的,其目的在于,提供在制造将薄层化的介电体层(陶瓷层)多层层叠而成的层叠陶瓷电容器时,高效率而且经济性地制造可以适合作为上述介电体层的构成材料等使用的、微细而结晶性高的钙钛矿型复合氧化物的制造方法,以及使用由该方法制造的钙钛矿型复合氧化物来制造层叠陶瓷电容器的方法。
为了解决上述课题,本发明的钙钛矿型复合氧化物的制造方法,是由ABO3(A至少包括Ba和Ca,B至少包括Ti)所代表的钙钛矿型复合氧化物的制造方法,其中,包括如下反应工序:至少使氧化钛、钙化合物和氢氧化钡在浆液中反应,由此使钙钛矿型复合氧化物生成,
所述钙化合物为碳酸钙,
由(Ba1-xCax)mTiO3表示所述钙钛矿型复合氧化物时,x处于0<x≤0.125的范围。
另外,本发明的钙钛矿型复合氧化物的制造方法,是由ABO3(A至少包括Ba和Ca,B至少包括Ti)所代表的钙钛矿型复合氧化物的制造方法,其中,至少包括使氧化钛、钙化合物和氢氧化钡在浆液中反应的反应工序
所述钙化合物为水溶性的钙化合物,
由(Ba1-xCax)mTiO3表示所述钙钛矿型复合氧化物时,x处于0<x≤0.20的范围。
另外,在本发明中,所述水溶性的钙化合物优选醋酸钙或硝酸钙。
另外,在本发明中,优选还具有对于在所述反应工序中生成的钙钛矿型复合氧化物进行热处理的工序。
另外,本发明的层叠陶瓷电容器的制造方法,其特征在于,具有如下工序:
将根据第四发明所述的制造方法制造的钙钛矿型复合氧化物与添加成分进行调配,调制陶瓷生片原料的工序;
成形所述陶瓷生片原料而制作陶瓷生片薄片制作工序;
在所述薄片制作工序中制作的所述陶瓷生片上,涂布内部电极形成用的导电胶而形成内部电极图案的工序;
经过将形成有所述内部电极图案的所述陶瓷生片层叠规定层数的工序而制作层叠体的工序,该层叠体具有经由所述陶瓷生片,在内部层叠有规定层数的所述内部电极图案的结构;
烧成所述层叠体的工序。
本发明的钙钛矿型复合氧化物的制造方法,至少包括使氧化钛、钙化合物和氢氧化钡在浆液中反应,由此使钙钛矿型复合氧化物生成的反应工序,并且,作为钙化合物使用碳酸钙,因此能够高效率地制造以(Ba1-xCax)mTiO3表示所述钙钛矿型复合氧化物时,x处于0<x≤0.125的范围的钙钛矿型复合氧化物。
即,根据本发明的方法,能够高效率地制造微细、结晶性高、可靠性优异的钙钛矿型复合氧化物。
另外,本发明的钙钛矿型复合氧化物的制造方法,至少包括使氧化钛、钙化合物和氢氧化钡在浆液中反应的反应工序,并且,作为钙化合物使用水溶性的钙化合物,因此能够高效率地制造以(Ba1-xCax)mTiO3表示钙钛矿型复合氧化物时,x处于0<x≤0.20的范围的钙钛矿型复合氧化物。
即,根据本发明的方法,能够高效率地制造微细、结晶性高、可靠性优异的钙钛矿型复合氧化物。
另外,作为水溶性的钙化合物,通过使用醋酸钙或硝酸钙,可以高效率地制造由(Ba1-xCax)mTiO3表示钙钛矿型复合氧化物时,x处于0<x≤0.20的范围的钙钛矿型复合氧化物,能够使本发明更有实效。
即,与作为Ca原料使用CaCO3的情况相比,通过使用醋酸钙、硝酸钙等的水溶性的钙化合物,反应性提高,Ca向BaTiO3晶格的固溶得到进一步促进。
另外,通过对于在反应工序中生成的钙钛矿型复合氧化物进行热处理,能够提高c/a轴比,得到结晶性高的钙钛矿型复合氧化物。
例如,通过以800~1000℃的温度进行热处理,可以得到c/a轴比大的(超过1)正方晶的钙钛矿型复合氧化物。
另外,本发明的层叠陶瓷电容器的制造方法的发明,通过在对于含有根据第四发明所述的方法制造的钙钛矿型复合氧化物和添加成分的陶瓷生片原料进行了成形的陶瓷生片上,涂布内部电极形成用的导电胶而形成内部电极图案,层叠形成有该内部电极图案的陶瓷生片,从而制作具有经由陶瓷生片而在内部层叠有规定层数的内部电极图案的结构的层叠体,因为经过如上工序而制造层叠陶瓷电容器,所以可以确实地制造厚度薄的介电体层被多层层叠的小型而高特性的层叠陶瓷电容器。
附图说明
图1是表示在本发明的一个实施例中制作的钙钛矿型复合氧化物中,以Ca置换A部位的Ba的一部分时的Ca置换量(Ca添加量)与晶格容积的关系的简图。
图2是表示将本发明的钙钛矿型复合氧化物用于介电体层的层叠陶瓷电容器的结构的剖面图。
图3是表示将本发明的钙钛矿型复合氧化物用于介电体层的层叠陶瓷电容器,其钙钛矿型复合氧化物中的Ca置换量(Ca添加量)与平均故障发生时间(MTTF)的关系的简图。
符号说明
11 层叠陶瓷元件
12 陶瓷层(介电体层)
13a、13b 内部电极
14a、14b 层叠陶瓷元件的端面
15a、15b 外部电极
20 层叠陶瓷电容器
具体实施方式
以下显示本发明的实施例,更详细地说明本发明的特征。
【实施例1】
[1]钙钛矿型复合氧化物粉末的制作
首先,作为钙钛矿型复合氧化物的原料,准备下述的(a)~(e)。
(a)比表面积为300m2/g的氧化钛(TiO2)粉末;
(b)比表面积が30m2/g的、不含化合水的氢氧化钡(Ba(OH)2)粉末;
(c)CaCO3粉末;
(d)作为水溶性的钙化合物的醋酸钙((CH3COO)2Ca)、
(e)作为水溶性的钙化合物的硝酸钙(Ca(NO3)2)
然后,设化学式为(Ba1-xCax)TiO3时,使x=0、0.025、0.05、0.075、0.1、0.125、0.15、0.175、0.2、0.25而进行称量。
还有,作为钙原料,将上述(c)、(d)、(e)的各原料择一使用。
然后,将称量的上述的氧化钛(TiO2)粉末放入容积为5升的玻璃容器中,加入规定量的纯水,制作氧化钛(TiO2)的含有率为20重量%的浆料。
接着,一边搅拌所得到的浆料,一边择一添加上述(c)、(d)、(e)的各Ca化合物。
然后,加热浆料,在浆料温度达到70℃的时刻投入氢氧化钡(Ba(OH)2)粉末,一边在85℃以上搅拌1小时一边使之发生反应。
接着,排出得到的浆料,用干燥机进行干燥。然后,以1050℃的温度对于干燥粉末进行热处理,由此得到用钙进行了改性的钛酸钡粉末(钙钛矿型复合氧化物粉末)。
对于得到的钛酸钡粉末,采用X射线衍射法(XRD)测量晶格常数,计算晶格容量。其结果显示在图1中。
如图1所示,作为Ca原料使用CaCO3时,以及作为Ca原料使用水溶性Ca时的任意一种情况下,伴随着Ca的固溶量的增加,晶格容积均会减小。这是由于,Ba的离子半径为1.61埃,相对于此,Ca的离子半径小,为1.34埃,因此若Ca的固溶量(置换量)增加,则整体上晶格容积变小。
但是,作为Ca原料使用CaCO3时,确认到Ca的添加量在Ba与Ca的合计量为1时,以摩尔比计达到0.125,晶格容积虽然变小,但若Ca添加量进一步增加,则晶格容积的减少倾向急剧降低,作为Ca原料使用CaCO3时的固溶限度,以摩尔比计为0.125(Ca/(Ba+Ca))。即,以(Ba1-xCax)mTiO3表示钙钛矿型复合氧化物时,确认到在x为0<x≤0.125这一范围,Ca在BaTiO3中固溶。
另外,由图1还确认到,作为Ca原料,使用水溶性钙化合物(醋酸钙((CH3COO)2Ca)或硝酸钙(Ca(NO3)2))时的固溶限度,以摩尔比计高达0.20(Ca/(Ba+Ca))。即,以(Ba1-xCax)mTiO3表示钙钛矿型复合氧化物时,在x为0<x≤0.20这一范围,确认到Ca在BaTiO3中固溶。
这被认为是由于,作为Ca原料,通过使用醋酸钙、硝酸钙等的水溶性的钙化合物,与作为Ca原料使用CaCO3的情况相比,反应性提高,因此Ca向BaTiO3晶格的固溶量增加。
[2]层叠陶瓷电容器的制作
以如上述这样制作的钙钛矿型复合氧化物(Ca改性的钛酸钡)作为介电体层(陶瓷层)的原料使用,制作层叠陶瓷电容器。
首先,对于以上述方式制作的钛酸钡粉末100摩尔,分别以如下方式称量并添加MgO、Dy2O3、SiO2和MnCO3作为添加物,
MgO:1.0摩尔
Dy2O3:0.8摩尔
SiO2:1.3摩尔
MnCO3:0.05摩尔。
另外,使A/B比成为1.007而添加摩尔比调整用的BaCO3。
其后,将该调配物、有机粘合剂(在该实施例中为聚乙烯醇缩丁醛树脂)、有机溶剂(在该实施例中为乙醇)投入球磨机,使用直径为2mm的PSZ介质进行混合、粉碎。
接着,使用刮浆法,使薄片厚度在烧成后达到0.8μm而进行薄片成型,将其冲压成规定的大小,得到矩形的陶瓷生片。
接着,准备以Ni为主成分的内部电极形成用的导电胶,在上述的陶瓷生片上进行丝网印刷,形成在烧成后构成内部电极的内部电极图案。
然后,将具有内部电极图案的陶瓷生片按规定层数、规定的顺序进行层叠,并且作为最外层,层叠没有形成内部电极图案的陶瓷生片,之后通过压合,制作压合块。
然后,将通过切削该压合块而得到的层叠体在规定的条件下地行烧成后,在烧成后的层叠体涂布外部电极形成用的导电胶并进行烘烤,由此制作具有图2所示这种构造的层叠陶瓷电容器20。
还有,该层叠陶瓷电容器20具有的构造如下:在层叠陶瓷元件11中,经由陶瓷层(介电体层)12,多个内部电极13a、13b被层叠,并且,彼此相对的内部电极13a、13b被交替此出到层叠陶瓷元件11不同侧的端面14a、14b,与形成于该端面14a、14b上的外部电极15a、15b连接。
还有,在本实施例中,使层叠陶瓷电容器20的元件厚度(位于彼此相对的内部电极13a、13b间的陶瓷层12的厚度)为0.8μm,使介电体层12的层叠数为100层。
[评价]
对于以上述方式制作的层叠陶瓷电容器,在周围温度175℃下,外加24V的直流电压,进行加速寿命试验(HALT)。绝缘电阻(LogIR)降低至100kΩ的时间作为故障时间,求得平均故障发生时间(MTTF)。其结果显示在表1和图3中。
还有,在表1中,Ca添加量的值表示,Ca相对于来自作为Ba原料的Ba(OH)2的Ba和添加的Ca的合计量的比例,即,Ca/(Ba+Ca)(摩尔比)。
另外,在表1中,作为Ca原料使用水溶性Ca的情况,表示的是作为Ca原料,使用上述(d)的作为水溶性的钙化合物的醋酸钙((CH3COO)2Ca),和上述(e)的作为水溶性的钙化合物的硝酸钙(Ca(NO3)2)的情况,无论使用上述(d)、(e)哪一种的情况,关于平均故障发生时间(MTTF),均得到相同的结果,由此,作为“作为Ca原料使用水溶性Ca的情况”一并显示在表1中。
【表1】
如表1所示,作为Ca原料使用CaCO3时,和作为Ca原料使用水溶性Ca时的任意一种情况下,伴随着Ca的固溶量的增加,至故障发生的时间(MTTF)的值均变大,可知可靠性(耐久性)提高。
这被认为是由于,通过在ABO3所代表的钙钛矿型复合氧化物(在本实施例中为BaTiO3)的A部位(Ba部位)使Ca固溶,晶格应变,氧缺陷等的移动受到抑制,由此稳定性提高,至故障发生的时间(MTTF)延长。
但是,作为Ca原料使用CaCO3时,向钙钛矿型复合氧化物(BaTiO3)的固溶量,如先前基于图1说明的,以摩尔比计在0.125(Ca/(Ba+Ca))(12.5mol%)时达到极限,因此如果添加CaCO3超过12.5mol%,则将存在没有固溶的Ca,至故障发生的时间(MTTF)反而缩短,确认到可靠性降低。
另一方面,作为Ca原料,使用水溶性Ca(CH3COO)2Ca或Ca(NO3)2)时,如先前基于图1说明的,与作为Ca原料使用CaCO3的情况相比,固溶量增大,以摩尔比计Ca固溶直至0.20(Ca/(Ba+Ca))(20mol%),因此Ca添加量达到20mol%,可确认至故障发生的时间(MTTF)延长,可靠性提高。
还有,在本实施例中,作为氢氧化钡,以固体状态使用不含化合水的Ba(OH)2,直接添加到分散有TiO2等的浆料中,但是如上述,以固体状态将不含化合水的Ba(OH)2添加到70℃的浆料中时,由于其溶解热,导致浆料的温度急剧上升至100℃附近,合成反应被促进。
因此,作为Ba源,优选使用不含化合水的氢氧化钡。但是,当然也可以使用含有化合水的氢氧化钡。
还有,本发明并不限定于上述实施例,关于使氧化钛粉末分散在水中氧化钛浆料的固体成分浓度、在氧化钛浆料中添加氢氧化钡而使之反应时的反应温度和反应时间等的条件、作为原料的氧化钛粉末的比表面积的范围、以Ca置换A部位的一部分时的置换比例、对于在反应工序中生成的钙钛矿型复合氧化物进行热处理时的条件、制造层叠陶瓷电容器时的具体的条件等,可以在发明的范围内,施加各种应用、变形。
Claims (5)
1.一种钙钛矿型复合氧化物的制造方法,其特征在于,是由ABO3表示的钙钛矿型复合氧化物的制造方法,其中,A至少包括Ba和Ca,B至少包括Ti,
在所述钙钛矿型复合氧化物的制造方法中包括如下的反应工序:在仅含有氧化钛、钙化合物的浆液中投入不含化合水的氢氧化钡在浆液中反应,由此生成钙钛矿型复合氧化物的工序,
所述钙化合物为碳酸钙,
在由(Ba1-xCax)mTiO3表示所述钙钛矿型复合氧化物时,x处于0<x≤0.125的范围。
2.一种钙钛矿型复合氧化物的制造方法,其特征在于,是由ABO3表示的钙钛矿型复合氧化物的制造方法,其中,A至少包括Ba和Ca,B至少包括Ti,
在所述钙钛矿型复合氧化物的制造方法中,包括在仅含有氧化钛、钙化合物的浆液中投入不含化合水的氢氧化钡在浆液中反应的反应工序,
所述钙化合物为水溶性的钙化合物,
在由(Ba1-xCax)mTiO3表示所述钙钛矿型复合氧化物时,x处于0<x≤0.20的范围。
3.根据权利要求2所述的钙钛矿型复合氧化物的制造方法,其特征在于,所述水溶性的钙化合物为醋酸钙或硝酸钙。
4.根据权利要求1~3中任一项所述的钙钛矿型复合氧化物的制造方法,其特征在于,还具有对在所述反应工序中生成的钙钛矿型复合氧化物进行热处理的工序。
5.一种层叠陶瓷电容器的制造方法,其特征在于,具有如下工序:
将根据权利要求4所述的制造方法制造的钙钛矿型复合氧化物与添加成分进行调配,调制陶瓷生片原料的工序;
成形所述陶瓷生片原料而制作陶瓷生片的薄片制作工序;
在所述薄片制作工序中制作的所述陶瓷生片上,涂布内部电极形成用的导电胶而形成内部电极图案的工序;
经过将形成有所述内部电极图案的所述陶瓷生片层叠规定层数的工序而制作层叠体的工序,该层叠体具有经由所述陶瓷生片在内部层叠有规定层数的所述内部电极图案的结构;
烧成所述层叠体的工序。
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