CN1134381C - 钙钛矿结构的氧化物、钛酸钡及其制造方法,介电陶瓷和陶瓷电子元件 - Google Patents
钙钛矿结构的氧化物、钛酸钡及其制造方法,介电陶瓷和陶瓷电子元件 Download PDFInfo
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- CN1134381C CN1134381C CNB011108851A CN01110885A CN1134381C CN 1134381 C CN1134381 C CN 1134381C CN B011108851 A CNB011108851 A CN B011108851A CN 01110885 A CN01110885 A CN 01110885A CN 1134381 C CN1134381 C CN 1134381C
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- barium titanate
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 68
- 239000000919 ceramic Substances 0.000 title claims description 64
- 238000000034 method Methods 0.000 title claims description 34
- 239000000843 powder Substances 0.000 claims abstract description 73
- 239000002245 particle Substances 0.000 claims abstract description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 30
- 239000011812 mixed powder Substances 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 50
- 238000007669 thermal treatment Methods 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 20
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 230000005621 ferroelectricity Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 2
- 239000003985 ceramic capacitor Substances 0.000 description 17
- 229910044991 metal oxide Inorganic materials 0.000 description 13
- 150000004706 metal oxides Chemical class 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IDIJOAIHTRIPRC-UHFFFAOYSA-J hexaaluminum;sodium;2,2,4,4,6,6,8,8,10,10,12,12-dodecaoxido-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane;iron(2+);triborate;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Fe+2].[Fe+2].[Fe+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-][Si]1([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si]([O-])([O-])O1 IDIJOAIHTRIPRC-UHFFFAOYSA-J 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910000246 schorl Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
提供一种钙钛矿结构的氧化物(如钛酸钡),其粒径小至0.03-0.2微米。晶格中OH的量小于0.2重量%,c/a轴之比高至1.003或更高并呈现了明显的铁电性。钛酸钡是通过混合BaCO3和比表面积为10m2/g的TiO2粉末并热处理而制得的。当氧分压降至2×103Pa或更低但高于2×102Pa时,热处理温度为700-1100℃,当氧分压降至2×102Pa或更低时,热处理温度为600-1100℃。
Description
本发明涉及一种具有钙钛矿结构的氧化物、钛酸钡及其制造方法,介电陶瓷和陶瓷电子元件。
钙钛矿结构的氧化物(如钛酸钡)已作为介电材料用作电子元件(如电容器)。近来,要求具有钙钛矿结构的氧化物是粒径较小的粉末。
例如,在单块陶瓷电容器中,通过降低介电陶瓷层的厚度来小型化和提高电容量,出于该目的,要求具有钙钛矿结构的氧化物(例如钛酸钡)不仅具有高的电容量,而且具有小的粒径。至今为止,已经用湿法(如水解法和水热合成法)制得粒径为0.2微米或更小的钛酸钡。
但是,在常规湿法合成的钛酸钡中,存在颗粒中含0.2-3重量%OH基团的问题,尽管粒径较小,但是晶体体系是立方体系或四边形体系,晶格中a轴与c轴之比(即c/a轴之比(x))较小不能满足关系式x≥1+(k-1)×0.3(其中k代表c/a轴之比的理论值,对于钛酸钡,k=1.011,x≥1.0033),因此电容器材料不能呈现足够的铁电现象。
为了解决上述问题,目前尝试对合成的钛酸钡进行再加热以除去OH基团,制得具有大c/a轴之比并表现足够的铁电现象的钛酸钡。
但是,由于在OH基团的位置产生空穴并且在再加热过程中钛酸钡颗粒发生生长,因此产生难以制得粒径小至0.2微米或更小的钛酸钡的问题。同时,在使用这种钛酸钡的叠层陶瓷电子元件(例如单块陶瓷电容器)中,当其介电陶瓷层的厚度降至数微米或更小时,还会产生短路和其它可靠性下降的问题。
因此,本发明的目的是提供一种具有钙钛矿结构的的氧化物(如钛酸钡)的制造方法,该氧化物具有小的粒径、具有很少量的OH基团、具有大的c/a轴之比并表现出明显的铁电现象;以及提供一种用所述制造方法制得的具有钙钛矿结构的氧化物(如钛酸钡),用这种氧化物制得的粉末制成的介电陶瓷以及使用这种介电陶瓷制得的叠层陶瓷电子元件。
本发明具有钙钛矿结构的氧化物的制造方法包括下列步骤:制得比表面积为10m2/g或更高的一种金属氧化物粉末并制得一种金属碳酸盐粉末,将该金属氧化物粉末与该金属碳酸盐粉末混合在一起,在2×103Pa或更小的氧气分压下热处理形成的粉末混合物。
所述方法中可至少分别使用两种金属氧化物粉末和金属碳酸盐粉末。
本发明还涉及一种具有钙钛矿结构的氧化物。这种氧化物较好是粒径为0.03-0.2微米并且晶格中OH基团小于0.2重量%的粉末。
该氧化物晶格中用x表示的c/a轴之比的测定值与用k表示的c/a轴之比的理论值较好满足关系式x≥1+(k-1)×0.3。
上述具有钙钛矿结构的氧化物较好利用如上所述的制造方法合成。
本发明具有钙钛矿结构的氧化物的制造方法特定地用于制造钛酸钡。
具体用于制造钛酸钡的方法包括下列步骤:制得比表面积为10m2/g或更高的TiO2粉末,并制得BaCO3粉末,将氧化钛粉末与碳酸钡粉末混合在一起,以及热处理形成的粉末混合物。
在氧气分压为2×103Pa或更小但超过2×102Pa的情况下进行上述热处理步骤时,可采用的热处理温度为700-1100℃。在氧气分压为2×102Pa或更小的情况下进行上述热处理步骤时,可采用的热处理温度为600-1100℃。
本发明还涉及钛酸钡。这种钛酸钡最好是粒径为0.03-0.2微米,并且晶格中OH基团的量小于0.2重量%的粉末。
这种钛酸钡的c/a轴之比以1.0033或更高为好。
所述钛酸钡较好用如上所述之制造方法制得。
本发明还涉及一种介电陶瓷,它是通过对具有钙钛矿结构的氧化物或钛酸钡制得的上述粉末进行烧制而成的。
本发明还涉及一种陶瓷电子元件,它包括上述介电陶瓷和相互间用该介电陶瓷隔开的对置的电极。
本发明还涉及一种叠层陶瓷电子元件,它包括由许多叠合的介电陶瓷层和沿该介电陶瓷层之间的特定界面形成的内导体组成的层叠物。本文中,上述介电陶瓷层是由本发明介电陶瓷制成的。
在本发明叠层陶瓷电子元件中,所述介电陶瓷层可由粒径为0.03-0.1微米、由钙钛矿结构的氧化物或钛酸钡制成的粉末烧制而成的介电陶瓷制得。介电陶瓷层的厚度以1微米或更小比较好。
在上述叠层陶瓷电子元件的一个具体实例中,电子元件还带有多个外电极,所述外电极排列在所述层叠物端面的相互不同的位置上,许多内导体的一个顶端伸出叠层物的所述端面,分别与所述外电极中的一个电气相连。叠层陶瓷电子元件的结构例如可作为单块陶瓷电容器。
图1本发明一个实例的单块陶瓷电容器1的剖面图。
图1是作为本发明叠层陶瓷电子元件的一个例子给出单块陶瓷电容器1的剖面图。
单块陶瓷电容器1带有叠层物3,所述叠层物包括许多叠合的介电陶瓷层2和分别形成在叠层物3的第一端面4和第二端面5上的第一外电极6和第二外电极7。
第一内电极8和第二内电极9交替地排列在叠层物3中作为内导体。第一内电极8沿许多介电陶瓷层2的特定界面之间排列,其每个边缘露出第一端面4以便与第一外电极6电气相连。第二内电极9沿许多介电陶瓷层2的特定界面之间排列,其每个边缘露出第二端面5以便与第二外电极7电气相连。
如有必要,外电极6和7可分别涂覆由镍、铜、镍-铜合金等制成的第一镀层10和11,并可分别在第一镀层10和11上形成由焊剂、锡等形成的第二镀层12和13。
在上述单块陶瓷电容器1中,叠层物3带有介电陶瓷层2,该介电陶瓷层是由本发明钙钛矿结构的氧化物制成的粉末烧制得到的介电陶瓷构成的。下面将详细说明该具有钙钛矿结构的氧化物。
为制造内电极8和9,例如可使用主要含镍的导电胶。
例如外电极6和7可通过涂覆含B2O3-Li2O-SiO2-BaO玻璃料的银糊浆并在减压气氛下焙烧该银糊浆而制成。
用作内电极8和9以及外电极6和7的材料不具体限于上述材料。例如,外电极6和7可由与组成内电极8和9的相同的材料制成。
根据本发明,具有钙钛矿结构的氧化物可通过混合至少一种比表面积为10m2/g或更高的金属氧化物和至少一种金属碳酸盐粉末,随后在2×103Pa或更低的氧分压下热处理形成的混合粉末而制得。
如上所述,在热处理过程中通过降低氧气的分压,在低温下金属碳酸盐可分解成基本材料,从而合成高活性的氧化物。得到的高活性氧化物与预先加入的金属氧化物反应,形成具有钙钛矿结构的氧化物。在所述反应中,与热解法和水热合成法不同,在反应过程中不含有OH基团。因此,合成后晶格中存在的OH基团限于作为基本材料的金属碳酸盐和金属氧化物中所含的OH基团,从而可将OH基团的量控制在0.2重量%或更低。
上述OH基团的量是根据150℃或更高的温度下的热损耗,通过合成后试样的热重量分析测定的。
为了在较低的温度下通过热处理制造具有钙钛矿结构的小粒径氧化物,较好进行热处理的氧气分压取2×103Pa或更低,取2×102Pa或更低的氧气分压更好。如果氧气分压超过2×103Pa,制得的具有钙钛矿结构的氧化物的粒径会增大,因此是不可取的。
为了生产具有钙钛矿结构的小粒径氧化物,较好使用作为基本材料的金属氧化物其比表面积为10m2/g或更高,更好15m2/g或更高。当金属氧化物的比表面积小于10m2/g时,金属氧化物的活性不够。从而,在合成具有钙钛矿结构的氧化物时,需要较高的的热处理温度,合成的具有钙钛矿结构的氧化物的粒径会增加,因此是不可取的。
由于金属碳酸盐的分解温度随金属碳酸盐的种类不同而不同,因此金属碳酸盐和金属氧化物的组合方式,或者氧气分压,热处理的温度和时间无特别的限制。最好根据低氧气分压下的热分析等预先决定热处理温度和时间最佳条件。
例如,在使用TiO2和BaCO3合成钛酸钡的情况下,当氧气的分压为2×103Pa或更低但超过2×102Pa并且热处理的温度小于700℃时,或者当氧气的分压为2×102Pa或更低并且热处理的温度小于600℃时,钛酸钡的合成反应不能充分地进行并且c/a轴之比未提高。另一方面,在上述任何一种氧气分压下当热处理的温度超过1100℃时,在合成的钛酸钡中会发生颗粒生长和颗粒之间的烧结,从而增加了粒径。
因此,当氧气分压为2×103Pa或更低但超过2×102Pa时,热处理的温度较好在700-1100℃之间,当氧气的分压为2×102Pa或更低时,热处理的温度较好在600-1100℃之间。
当在相同的金属氧化物粉末粒径和氧气分压条件下进行热处理时,随着热处理温度增加,制得的具有钙钛矿结构的氧化物的粒径会增大,尽管c/a轴之比会进一步增加。
根据上述本发明的制造方法,可制得具有钙钛矿结构并且粒径为0.03-0.2微米的氧化物粉末。
根据本发明的制造方法,可制得晶格中OH基团少于0.2重量%的钙钛矿结构的氧化物。当具有钙钛矿结构的氧化物的晶格中OH基团的量为0.2重量%或更高时,作为介电陶瓷使用需要进一步热处理,否则用这种氧化物制得的电子元件中会发生短路或其它可靠性下降。
在用本发明制造方法制得的钙钛矿结构的氧化物中,用x表示的该氧化物晶格中c/a轴之比的测量值,用k表示该氧化物的c/a轴之比的理论值满足关系式x≥1+(k-1)×0.3。特别是钛酸钡的c/a轴之比为1.0033或更高。当由于缺乏作为电子元件的铁电性,氧化物不能满足上述公式表示的条件,或者钛酸钡中c/a轴之比小于1.0033时,需要进一步热处理以提高c/a轴之比,从而发生颗粒的生长。
本发明具有钙钛矿结构的氧化物不限于其中金属碳酸盐中所含金属原子(A)与金属氧化物中所含金属原子(B)之比(即原子比A/B)为1的氧化物。根据所需的用途,具有钙钛矿结构的氧化物可具有不同的原子比A/B,例如0.95-1.05。具体地说,原子比A/B较好为1.000-1.035,以制得非还原性并具有钙钛矿结构的氧化物。
上述具有钙钛矿结构的氧化物粉末烧制而成的介电陶瓷可以是根据所需性能在上述具有钙钛矿结构的氧化物中加入钙、稀土元素、添加剂(如Zr、Mn、Mg、Si、Gd、Dy、Ho和Er或者由Mg、Mn和Si组成的烧结促进剂)而制成的介电陶瓷。
在上面描述中,将使用TiO2和BaCO3合成的钛酸钡作为本发明具有钙钛矿结构的氧化物的一个例子,尽管本发明可使用其它金属氧化物和碳酸盐的组合来合成具有钙钛矿结构的氧化物(如钛酸钙、钛酸锶、钛酸铅和锆酸铅),以及合成其混合物和固溶体。
下面根据使用TiO2和BaCO3合成钛酸钡的具体实例来专门说明本发明。
实施例1
制得BaCO3粉末和比表面积为30m2/g的TiO2粉末作为原料。
称重这些原料使得以摩尔计的Ba/Ti之比为1.00,并湿混之。
对形成的混合物进行蒸发并干燥,随后在压力分别控制在1×102Pa、1×103Pa、1×104Pa和一个大气压(即氧气分压分别为2×101Pa、2×102Pa、2×103Pa和2×104Pa)的分层式烘炉中800℃热处理5小时,制得钛酸钡粉末。
对于制得的钛酸钡粉末,使用电子显微镜观测其粒径,用热重量分析法测定OH基团的量,用x-射线衍射分析法和Rietveld分析测定c/a轴之比。结果和总的评价结果列于表1。
表1
试样 | TiO2比表面积(m2/g) | 氧分压(Pa) | 热处理温度(℃) | 粒径(nm) | OH基团量(重量%) | c/a轴之比 | 评价 |
1 | 30 | 2×101 | 800 | 53 | 0.05 | 1.005 | ○ |
2 | 2×102 | 54 | 0.06 | 1.005 | ○ | ||
3 | 2×103 | 65 | 0.08 | 1.006 | ○ | ||
4 | 2×104 | 210 | 0.08 | 1.009 | × |
如表1所示,分别在2×101Pa、2×102Pa和2×103Pa氧分压下进行热处理的试样1-3表明可制得粒径为0.03-0.2微米,OH含量小于0.2重量%并且c/a轴之比为1.0033或更高的钛酸钡粉末。
另一方面,在氧气分压为2×104Pa(超过2×103Pa)下进行热处理的试样4表明颗粒生长至粒径超过0.2微米。
实施例2
制得BaCO3粉末和比表面积分别为5m2/g、10m2/g、15m2/g、20m2/g和30m2/g的TiO2粉末作为原料。
称重这些原料使得以摩尔计的Ba/Ti之比为1.00,并湿混之。
对形成的混合物进行蒸发并干燥,随后在压力为1×103Pa(即氧气分压为2×102Pa)温度为800℃的分层式烘炉中热处理5小时,制得钛酸钡粉末。
对于形成的钛酸钡粉末,使用如实施例1所示的方法测定粒径,OH基团的量,和c/a轴之比。结果和总的评价结果列于表2。
表2
试样 | TiO2比表面积(m2/g) | 氧分压(Pa) | 热处理温度(℃) | 粒径(nm) | OH基团量(重量%) | c/a轴之比 | 评价 |
5 | 5 | 2×102 | 800 | 361 | 0.06 | 1.009 | × |
6 | 10 | 181 | 0.06 | 1.008 | ○ | ||
7 | 15 | 121 | 0.05 | 1.007 | ○ | ||
8 | 20 | 90 | 0.05 | 1.006 | ○ | ||
9 | 30 | 54 | 0.06 | 1.005 | ○ |
如表2所示,分别使用比表面积为10m2/g、15m2/g、20m2/g和30m2/g的TiO2的试样6-9表明可制得粒径为0.03-0.2微米,OH含量小于0.2重量%并且c/a轴之比为1.0033或更高的钛酸钡粉末。
另一方面,使用比表面积为5m2/g(小于10m2/g)的TiO2的试样5表明颗粒生长至粒径超过0.2微米。
实施例3
制得BaCO3粉末和比表面积为30m2/g的TiO2粉末作为原料。
称重这些原料使得以摩尔计的Ba/Ti之比为1.00,并湿混之。
对形成的混合物进行蒸发并干燥,随后在压力为1×103Pa(即氧气分压为2×102Pa),温度分别为500℃、600℃、700℃、800℃、900℃、1000℃、1100℃和1200℃的分层式烘炉中热处理5小时,制得钛酸钡粉末。
对于形成的钛酸钡粉末,使用如实施例1所示的方法测定粒径,OH基团的量,和c/a轴之比。结果和总的评价结果列于表3。
表3
试样 | TiO2比表面积(m2/g) | 氧分压(Pa) | 热处理温度(℃) | 粒径(nm) | OH基团量(重量%) | c/a轴之比 | 评价 |
10 | 30 | 2×102 | 500 | - | - | - | × |
11 | 600 | 43 | 0.18 | 1.004 | ○ | ||
12 | 700 | 45 | 0.10 | 1.004 | ○ | ||
13 | 800 | 54 | 0.06 | 1.005 | ○ | ||
14 | 900 | 74 | 0.05 | 1.006 | ○ | ||
15 | 1000 | 110 | 0.04 | 1.007 | ○ | ||
16 | 1100 | 164 | 0.04 | 1.008 | ○ | ||
17 | 1200 | 246 | 0.04 | 1.009 | × |
如表3所示,分别在600℃、700℃、800℃、900℃、1000℃和1100℃的温度下进行热处理的试样11-16表明可制得粒径为0.03-0.2微米,OH含量小于0.2重量%并且c/a轴之比为1.0033或更高的钛酸钡粉末。
相反,在500℃(低于600℃)进行热处理的试样10,如表3中的“粒径”、“OH基团量”和“c/a轴之比”栏空白所示,表明合成反应不完全。
另一方面,在1200℃(超出1100℃)的温度进行热处理的试样17表明颗粒生长至粒径超过0.2微米。
实施例4
制得BaCo3粉末和比表面积为30m2/g的TiO2粉末作为原料。
称重这些原料使得以摩尔计的Ba/Ti之比为1.00,并湿混之。
对形成的混合物进行蒸发并干燥,随后在压力为1×104Pa(即氧气分压为2×103Pa)温度为600℃、700℃、800℃、900℃、1000℃、1100℃和1200℃的分层式烘炉中热处理5小时,制得钛酸钡粉末。
对于形成的钛酸钡粉末,使用如实施例1所示的方法测定粒径,OH基团的量,和c/a轴之比。结果和总的评价结果列于表4。
表4
试样 | TiO2比表面积(m2/g) | 氧分压(Pa) | 热处理温度(℃) | 粒径(nm) | OH基团量(重量%) | c/a轴之比 | 评价 |
18 | 30 | 2×103 | 600 | - | - | - | × |
19 | 700 | 54 | 0.12 | 1.005 | ○ | ||
20 | 800 | 65 | 0.08 | 1.006 | ○ | ||
21 | 900 | 88 | 0.06 | 1.006 | ○ | ||
22 | 1000 | 132 | 0.06 | 1.007 | ○ | ||
23 | 1100 | 198 | 0.05 | 1.008 | ○ | ||
24 | 1200 | 298 | 0.05 | 1.009 | × |
在上面的实施例3中,在氧气分压为2×102Pa下进行热处理,而在本实施例4中,热处理是在氧气分压为2×103Pa下进行的。
如表4所示,加热温度分别为700℃、800℃、900℃、1000℃和1100℃的试样19-23表明可制得粒径为0.03-0.2微米,OH含量小于0.2重量%并且c/a轴之比为1.0033或更高的钛酸钡粉末。
相反,在600℃(低于700℃)的温度下进行热处理的试样18表明如同表3的试样10那样合成反应不完全。
另一方面,在1200℃(超出1100℃)的温度下进行热处理的试样24表明颗粒生长至粒径超过0.2微米。
实施例5
制得BaCO3粉末和比表面积为30m2/g的TiO2粉末作为原料。
称重这些原料使得以摩尔计的Ba/Ti之比为1.00,并湿混之。
对形成的混合物进行蒸发并干燥,随后在温度为800℃的分层式烘炉中热处理5小时,此时用氮气代替大气,并将氧气分压控制在1Pa,制得试样25的钛酸钡粉末。
另外,对形成的混合物进行蒸发并干燥,在温度为800℃的分层式烘炉中热处理5小时,此时用含95%氮气和5%氢气的混合气体代替大气,并将氧气分压控制在1×10-7Pa,制得试样26的钛酸钡粉末。
对于形成的钛酸钡粉末,使用如实施例1所示的方法测定粒径,OH基团的量,和c/a轴之比。结果和总的评价结果列于表5。
表5
试样 | TiO2比表面积(m2/g) | 氧分压(Pa) | 热处理温度(℃) | 粒径(nm) | OH基团量(重量%) | c/a轴之比 | 评价 |
25 | 30 | 氮/1 | 800 | 58 | 0.05 | 1.005 | ○ |
26 | 氮-氢混合气体/1×10-7 | 55 | 0.04 | 1.005 | ○ |
如表5所示,在加入氮气的情况下以及在加入氮-氢混合气体的情况下进行热处理时,可制得粒径为0.03-0.2微米,OH含量小于0.2重量%并且c/a轴之比为1.0033或更高的钛酸钡粉末。
在上述实施例1-5中,使用锐钛矿相二氧化钛制得的二氧化钛粉末,尽管可使用金红石相二氧化钛,或者锐钛矿相二氧化钛和金红石相二氧化钛的混合物制备二氧化钛以获得相似的性能。
在实施例1-5中,使用比表面积为7m2/g的碳酸钡粉末,尽管在反应过程中碳酸钡分解,分解产生的钡原子扩散至二氧化钛颗粒中合成BaTiO3,在使用具有更大比表面积的碳酸钡粉末情况下,以及使用具有更小比表面积的碳酸钡粉末的情况下,可获得相同的效果。
实施例6
制得BaCO3粉末和比表面积为30m2/g的TiO2粉末作为原料。
称重这些原料使得以摩尔计的Ba/Ti之比为1.01,并湿混之。
对形成的混合物进行蒸发并干燥,随后在压力为1×10-1Pa(即氧气分压为1×10-2Pa)温度为900℃的分层式烘炉中热处理5小时,制得钛酸钡粉末。
对于形成的试样27钛酸钡粉末,使用如实施例1所示的方法测定粒径,OH基团的量,和c/a轴之比。结果和总的评价结果列于表6。
表6
试样 | TiO2比表面积(m2/g) | 氧分压(Pa) | 热处理温度(℃) | 粒径(nm) | OH基团量(重量%) | c/a轴之比 |
27 | 30 | 2×10-2 | 900 | 70 | 0.05 | 1.007 |
另外,还制得表3所示的试样12-14的钛酸钡粉末。
试样12-14和27的粒径为0.03-0.1微米。
将试样12-14和27的各种钛酸钡分散在有机溶剂中,相对1mol钛酸钡,分别加入醇盐化合物形式的0.02mol Dy、0.015mol Mg、0.005mol Mn和0.03molSi烧结促进剂,使之溶解在该有机溶剂中。
除了醇盐化合物以外,确认上述添加剂还可以其它化合物形式(如乙酰基丙酮酸盐或金属皂)加入以便溶解在有机溶剂中。
通过蒸发和干燥从上述方法制得的糊浆中除去有机溶剂,进一步热处理以除去其它有机化合物。
向加有上述各种添加剂的钛酸钡粉末试样中加入聚乙烯醇缩丁醛粘合剂溶液和有机溶剂(如乙醇),使用球磨机进行湿法混合制得陶瓷糊浆。
使用刮刀法施涂将所得的陶瓷糊浆模塑成片,制得厚1.5微米的矩形陶瓷坯料片。
用主要含镍的导电胶网印该坯料片,形成相应于图1所示的内电极8和9的导电胶薄膜。
将许多坯料片叠合在一起,使其涂覆上述导电胶薄膜的侧面以交替的方式排成两排,制得坯料叠层。
在氮气中将该叠层加热至350℃的温度,以烧去粘合剂,随后在由H2-N2-H2O气体组成的还原性气氛中(氧气分压为10-3-10-6Pa),在1050℃下烧制2小时制得烧结的叠层物(如图1所示的叠层物3)。
在该叠层物的两端面涂覆含B2O3-Li2O-SiO2-BaO玻璃料的银糊浆,并在氮气氛中600℃的温度下焙烧,形成相应于图1外电极6和7的外电极。
根据如上制得的试样12-14和27的单块陶瓷电容器的外尺寸为宽5.0mm,长5.7mm,厚2.4mm,插入第一内电极和第二内电极之间的介电陶瓷层的厚度为1.0微米。有效的介电陶瓷层的总数为100,每一层极板(counter electrode)的面积为16.3×10-6m2。
对于制成的各个单块陶瓷电容器,测定其电容量、介电损耗和电阻。根据JIS 5102用自动桥式测量装置测定电容量(C)和介电损耗(tanδ)。使用绝缘电阻试验器在25℃施加10V直流电压2分钟测得绝缘电阻,并由绝缘电阻算得电阻率ρ。
关于评估制成的单块陶瓷电容器的平均寿命。也就是,在150℃施加6V直流电压进行高温负载试验。在该高温负载试验过程中,测定该单块陶瓷电容器的绝缘电阻随时间的变化,并将绝缘电阻(R)的值达到105Ω或更小的时间定为发生故障的时刻。将发生故障的时间间隔视为寿命,其平均值视为平均寿命。
由一系列试样测定故障率,其电气性能不能按照上述方法进行评价。
上述电气性能和故障率的结果如表7所示。
表7
试样 | 热处理温度(℃) | 电容(μF) | 介电损耗tanδ(%) | 电阻率logρ(Ω·cm) | 平均寿命(小时) | 故障率(%) |
12 | 1050 | 25.4 | 3.8 | 12.4 | 61.7 | 0.8 |
13 | 1050 | 27.4 | 3.5 | 12.8 | 63.9 | 0.6 |
14 | 1050 | 29.2 | 3.3 | 12.9 | 70.1 | 0.2 |
27 | 1050 | 31.8 | 2.5 | 13.0 | 72.5 | 0.2 |
如表7所示,根据试样12-14和27的各个单块陶瓷电容器呈现出优良的电气性能。在该单块陶瓷电容器中,即使介电陶瓷层的厚度如上所述小至1.0微米,实施例6中制得的试样的故障率仍低至0.8%或更低。
如上所述,根据本发明具有钙钛矿结构的氧化物或钛酸钡的制造方法,可制得粒径小至0.03-0.2微米,晶格中OH基团的量小于0.2重量%,并且用x表示的氧化物的c/a轴之比的测定值与k表示的氧化物的c/a轴之比的理论值满足关系式x≥1+(K-1)×0.3的具有钙钛矿结构的氧化物或钛酸钡。另外,钛酸钡的c/a轴之比高至1.0033或更高并呈现了明显的铁电性。
因此,使用具有钙钛矿结构的氧化物(例如钛酸钡),可以相对低的烧制温度制得高介电常数并表现出高性能的陶瓷电子元件,例如叠层陶瓷电子元件(如单块陶瓷电容器)。
而且,更准确地说,在本发明用于含叠层物(所述叠层物的结构中许多介电陶瓷层和许多内电极层叠在一起)的叠层陶瓷电子元件(例如单块陶瓷电容器)情况下,可进一步降低介电陶瓷层的厚度。尤其是使用粒径例如为0.03-0.1微米由钙钛矿结构的氧化物或钛酸钡制成的更细的粉末时,即使陶瓷层的厚度降至例如1微米或更小,也能以高可靠性且毫无问题地制得叠层陶瓷电子元件。因此,当将本发明用于单块陶瓷电容器时,可容易地制得小型化和大容量的单块陶瓷电容器。
Claims (12)
1.一种钛酸钡的制造方法,它包括下列步骤:
制得比表面积为10m2/g或更高的TiO2粉末,并制得BaCO3粉末;
将所述TiO2粉末与BaCO3粉末混合在一起;并
在2×103Pa或更低但超过2×102Pa的氧气分压下,在700-1100℃的温度下对形成的混合粉末进行热处理。
2.一种钛酸钡的制造方法,它包括下列步骤:
制得比表面积为10m2/g或更高的TiO2粉末,并制得BaCO3粉末;
将所述TiO2粉末与BaCO3粉末混合在一起;和
在2×102Pa或更低的氧气分压下,在600-1100℃的温度下热处理形成的混合粉末。
3.一种钛酸钡,其特征在于它是按权利要求1或2所述的制造方法合成的粉末,其粒径为0.03-0.2微米。
4.一种钛酸钡,其特征在于它是用权利要求1或2所述的制造方法合成的粉末,其晶格中OH基团的量小于0.2重量%。
5.如权利要求3或4所述的钛酸钡,其特征在于这种钛酸钡的c/a轴之比为1.0033或更高。
6.一种钛酸钡,其特征在于其晶格中OH基团的量小于0.2重量%,并且它是粒径为0.03-0.2微米的粉末。
7.如权利要求6所述的钛酸钡,其特征在于这种钛酸钡的c/a轴之比为1.0033或更高。
8.一种介电陶瓷,它是通过对含有如权利要求3-7中任何一项所述的钛酸钡的粉末进行烧制而成的。
9.一种陶瓷电子元件,它包括:
如权利要求8所述的介电陶瓷;和
相互间用该介电陶瓷隔开的对置的电极。
10.一种含叠层物的叠层陶瓷电子元件,所述叠层物包括:
许多叠合的介电陶瓷层;和
内导体,这些内导体形成在所述介电陶瓷层之间的特定界面上,其中所述介电陶瓷层包括如权利要求8所述的介电陶瓷。
11.如权利要求10所述的叠层陶瓷电子元件,其特征在于所述介电陶瓷层包括介电陶瓷,它是由含有粒径为0.03-0.1微米、具有钙钛矿结构的氧化物或钛酸钡的粉末烧制而成的,所述介电陶瓷层的厚度为1微米或更小。
12.如权利要求10或11所述的叠层陶瓷电子元件,它还包括排列在所述叠层物两端面上不同位置处的多个外电极,每个所述内导体露出所述端面中的一端而与一个所述外电极电气相连。
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JP2001015461A JP3780851B2 (ja) | 2000-03-02 | 2001-01-24 | チタン酸バリウムおよびその製造方法ならびに誘電体セラミックおよびセラミック電子部品 |
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EP (2) | EP1264809A3 (zh) |
JP (1) | JP3780851B2 (zh) |
KR (1) | KR100418599B1 (zh) |
CN (1) | CN1134381C (zh) |
DE (1) | DE60101641T2 (zh) |
TW (3) | TWI306091B (zh) |
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CN1311173A (zh) | 2001-09-05 |
KR100418599B1 (ko) | 2004-02-11 |
EP1264809A2 (en) | 2002-12-11 |
US20010026865A1 (en) | 2001-10-04 |
EP1130004B1 (en) | 2004-01-02 |
TWI301477B (en) | 2008-10-01 |
EP1264809A3 (en) | 2003-08-06 |
DE60101641D1 (de) | 2004-02-05 |
TWI248924B (en) | 2006-02-11 |
DE60101641T2 (de) | 2004-06-17 |
US6485701B2 (en) | 2002-11-26 |
TW200517356A (en) | 2005-06-01 |
TW200624404A (en) | 2006-07-16 |
TWI306091B (en) | 2009-02-11 |
KR20010087238A (ko) | 2001-09-15 |
EP1130004A1 (en) | 2001-09-05 |
JP2001316114A (ja) | 2001-11-13 |
JP3780851B2 (ja) | 2006-05-31 |
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