JPH04219366A - Lanthanum chromite-based double oxide and its use - Google Patents
Lanthanum chromite-based double oxide and its useInfo
- Publication number
- JPH04219366A JPH04219366A JP3067464A JP6746491A JPH04219366A JP H04219366 A JPH04219366 A JP H04219366A JP 3067464 A JP3067464 A JP 3067464A JP 6746491 A JP6746491 A JP 6746491A JP H04219366 A JPH04219366 A JP H04219366A
- Authority
- JP
- Japan
- Prior art keywords
- lanthanum chromite
- double oxide
- oxide
- lanthanum
- perovskite structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- NFYLSJDPENHSBT-UHFFFAOYSA-N chromium(3+);lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+3].[La+3] NFYLSJDPENHSBT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- 150000001342 alkaline earth metals Chemical group 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000001354 calcination Methods 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000011651 chromium Substances 0.000 description 10
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- 229910015133 B2 O3 Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002328 LaMnO3 Inorganic materials 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0215—Glass; Ceramic materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は新規なランタンクロマイ
ト系複合酸化物とその高温導電性材料及び高温型燃料電
池セパレータとしての用途に係る。この新規なランタン
クロマイト系複合酸化物は高導電性かつ緻密であり、高
温型燃料電池、ＭＨＤ発電その他の高温導電性材料に利
用することができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new lanthanum chromite complex oxide and its use as a high temperature conductive material and a high temperature fuel cell separator. This new lanthanum chromite-based composite oxide is highly conductive and dense, and can be used for high-temperature fuel cells, MHD power generation, and other high-temperature conductive materials.
【０００２】0002
【従来の技術】ランタンクロマイト（ＬａＣｒＯ３ ）
は高温において導電性をもち、かつ耐酸化性、耐還元性
に優れるために、高温の腐食性雰囲気で使用する導体材
料として極めて有望視されている酸化物系セラミックス
である。ランタンクロマイトにマグネシウム、カルシウ
ム、ストロンチウム、バリウムなどのアルカリ土類金属
を微量不純物元素として添加することにより、ドーパン
トとして作用し導電率を向上させることができる。ラン
タンクロマイトはペロブスカイト構造（ＡＢＯ３ 〔式
中、Ａ，Ｂは金属元素、Ｏは酸素である。〕）をなして
いる。添加したカルシウム、ストロンチウム、バリウム
はランタンクロマイト格子中ランタン位置に置換固溶し
ており、一方マグネシウムはクロム位置に置換固溶して
いる。[Prior art] Lanthanum chromite (LaCrO3)
is an oxide-based ceramic that is highly promising as a conductive material for use in high-temperature corrosive atmospheres because it has electrical conductivity at high temperatures and has excellent oxidation and reduction resistance. By adding an alkaline earth metal such as magnesium, calcium, strontium, or barium to lanthanum chromite as a trace impurity element, it can act as a dopant and improve electrical conductivity. Lanthanum chromite has a perovskite structure (ABO3 [wherein A and B are metal elements and O is oxygen]). The added calcium, strontium, and barium are substituted in solid solution at the lanthanum position in the lanthanum chromite lattice, while magnesium is substituted in solid solution at the chromium position.
【０００３】0003
【発明が解決しようとする課題】上記、微量元素添加ラ
ンタンクロマイトは導電率の点では十分な性能を有して
いるが、常圧大気中では緻密な焼結が得られにくく空隙
が生じるためにガスを十分に遮断できないという欠点が
ある。したがって、例えば固体電解質燃料電池のセパレ
ータ材料としてランタンクロマイトを用いようとした場
合、燃料ガスと空気を完全に分離することが不可能であ
り、この目的に用いることができなかった。[Problem to be solved by the invention] Although the above-mentioned lanthanum chromite with added trace elements has sufficient performance in terms of electrical conductivity, it is difficult to obtain dense sintering in normal pressure atmosphere, and voids occur. The disadvantage is that the gas cannot be shut off sufficiently. Therefore, for example, when attempting to use lanthanum chromite as a separator material for a solid electrolyte fuel cell, it is impossible to completely separate fuel gas and air, and it cannot be used for this purpose.
【０００４】ランタンクロマイトにおいて容易に緻密な
焼結体が得られないのは、第一に焼成温度において酸化
クロムの蒸気圧が高く、ランタンクロマイトの分解によ
って生じた酸化クロム蒸気が焼結体粒界における気孔の
移動を阻害するため、焼結体中に微細な空隙として残留
するためであり（工業材料１９８７年１１月号別冊、１
８ページ）、第二にイオンの体積拡散がきわめて遅く原
料粉末の界面が移動しにくいためである。[0004] The reason why it is not easy to obtain a dense sintered body in lanthanum chromite is that the vapor pressure of chromium oxide is high at the sintering temperature, and the chromium oxide vapor generated by the decomposition of lanthanum chromite flows into the grain boundaries of the sintered body. This is because they remain as fine voids in the sintered body to inhibit the movement of pores in the sintered body (Industrial Materials, November 1987 issue, special issue, 1).
(page 8), and secondly, the volumetric diffusion of ions is extremely slow and the interface of the raw material powder is difficult to move.
【０００５】そこで、本発明はこの点を解決し緻密な焼
結体を常圧大気中で容易に得られるようにするとともに
、導電率においても従来よりも向上せしめることを目的
とする。The object of the present invention is therefore to solve this problem and to make it possible to easily obtain a dense sintered body in normal pressure atmosphere, as well as to improve the electrical conductivity compared to the conventional one.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記目的
を達成するために、先に、ランタンクロマイトのランタ
ンの１部をアルカリ土類金属で置換し、クロムの１部を
コバルトで置換した新規なランタンクロマイト系複合酸
化物を開示した（特願平１−１９６７８５号）。そして
、上記において、コバルトに代えて、鉄やニッケル等で
クロムの１部を置換した場合にも同様の効果が奏せられ
ることを見い出し、本発明に到達した。[Means for Solving the Problems] In order to achieve the above object, the present inventors first replaced a part of lanthanum in lanthanum chromite with an alkaline earth metal, and replaced a part of chromium with cobalt. A novel lanthanum chromite-based composite oxide has been disclosed (Japanese Patent Application No. 196785/1999). Further, in the above, it has been found that the same effect can be achieved even when a part of chromium is replaced with iron, nickel, etc. instead of cobalt, and the present invention has been achieved.
【０００７】こうして、本発明は、上記目的を達成する
ために、一般式Ｌａ１−ｘ Ｍｘ Ｃｒ１−ｙ Ｍ′ｙ
Ｏ３ （式中、Ｍはマグネシウムを除くアルカリ土類
金属であり、Ｍ′はＮｉ，Ｚｎ，Ｃｕ，Ｍｎ，Ｖ，Ｉｒ
，Ａｌ，Ｍｏ，Ｗ，Ｐｄ，Ｙ，Ｐｔ，Ｒｈ，Ｔｉ，Ｓｉ
又はＢであり、０＜ｘ≦０．５，０＜ｙ≦０．５である
。）で表わされかつペロブスカイト構造を持つことを特
徴とする新規なランタンクロマイト系複合酸化物を提供
する。[0007] Thus, in order to achieve the above object, the present invention provides the general formula La1-x Mx Cr1-y M'y
O3 (where M is an alkaline earth metal excluding magnesium, and M' is Ni, Zn, Cu, Mn, V, Ir
, Al, Mo, W, Pd, Y, Pt, Rh, Ti, Si
or B, and 0<x≦0.5, 0<y≦0.5. ) and is characterized by having a perovskite structure.
【０００８】同様に、本発明は、一般式（Ｌａ１−ｘ
Ｍｘ ）ａ （Ｃｒ１−ｙ Ｍ′ｙ ）ｂ Ｏ３ （式
中、Ｍはマグネシウムを除くアルカリ土類金属であり、
Ｍ′はＮｉ，Ｚｎ，Ｃｕ，Ｍｎ，Ｖ，Ｉｒ，Ａｌ，Ｍｏ
，Ｗ，Ｐｄ，Ｙ，Ｐｔ，Ｒｈ，Ｔｉ，Ｓｉ又はＢであり
、０＜ｘ≦０．５，０＜ｙ≦０．５、そして０．９５≦
ｂ／ａ＜１又は１＜ｂ／ａ≦１．０５である。）で表わ
される主としてペロブスカイト構造からなることを特徴
とする新規なランタンクロマイト系複合酸化物を提供す
る。Similarly, the present invention provides the general formula (La1-x
Mx )a (Cr1-y M'y)b O3 (where M is an alkaline earth metal other than magnesium,
M' is Ni, Zn, Cu, Mn, V, Ir, Al, Mo
, W, Pd, Y, Pt, Rh, Ti, Si or B, and 0<x≦0.5, 0<y≦0.5, and 0.95≦
b/a<1 or 1<b/a≦1.05. ) A novel lanthanum chromite-based composite oxide is provided which is characterized by mainly consisting of a perovskite structure.
【０００９】さらに、本発明によれば、上記のランタン
クロマイト系複合酸化物を用いた高温導電性材料及び高
温型燃料電池のセパレータを提供する。一般式Ｌａ１−
ｘ Ｍｘ Ｃｒ１−ｙ Ｍ′ｙ Ｏ３ で表わされるペ
ロブスカイト構造を持つランタンクロマイト系複合酸化
物は、最も理想的には、ペロブスカイト型（ＡＢＯ３
）構造のＡサイトにＬａ、ＢサイトにＣｒが配置したラ
ンタンクロマイトの基本構造において、Ｌａの一部がア
ルカリ土類金属で置換され、かつさらにＣｒの一部がＦ
ｅで置換された構造をなしていると考えられる。Furthermore, the present invention provides a high temperature conductive material and a separator for a high temperature fuel cell using the above lanthanum chromite complex oxide. General formula La1-
A lanthanum chromite-based composite oxide having a perovskite structure represented by
) In the basic structure of lanthanum chromite, in which La is placed at the A site and Cr is placed at the B site, a part of La is replaced with an alkaline earth metal, and a part of Cr is further replaced with F.
It is thought that it has a structure substituted with e.
【００１０】また、一般式（Ｌａ１−ｘ Ｍｘ ）ａ
（Ｃｒ１−ｙ Ｍ′ｙ ）ｂ Ｏ３ で表わされる主と
してペロブスカイト構造からなるランタンクロマイト系
複合酸化物は、上記のペロブスカイト構造（ｂ／ａ＝１
の場合）からＢサイトとＡサイトの比ｂ／ａが僅かにず
れた分だけ、ペロブスカイト構造以外の構造が含まれて
いると考えられる。[0010] Furthermore, the general formula (La1-x Mx)a
The lanthanum chromite-based composite oxide mainly consisting of a perovskite structure represented by (Cr1-y M′y )b O3 has the above-mentioned perovskite structure (b/a=1
It is considered that a structure other than the perovskite structure is included by a slight deviation in the ratio b/a of the B site and A site from the case of .
【００１１】Ｌａの一部をアルカリ土類金属で置換する
ことによって導電性が向上する。ただし、マグネシウム
はＡサイトのＬａではなくＢサイトのＣｒと置換するの
で、本発明では用いない。アルカリ土類金属の置換量は
、モル比で０．５まで、好ましくは０．０５〜０．３で
ある。これらのアルカリ土類金属による置換がこの範囲
内で多いほど導電性は高くなるが、この範囲を越えて増
加するともはやＬａと置換しきれなくなり、ペロブスカ
イト構造以外の複合酸化物（例えばＣａＣｒＯ４ ，Ｓ
ｒＣｒＯ４ など）を生じ、その特性を著しく低下させ
る。[0011] The conductivity is improved by substituting a part of La with an alkaline earth metal. However, since magnesium replaces La at the A site but Cr at the B site, it is not used in the present invention. The amount of alkaline earth metal substitution is up to 0.5 in molar ratio, preferably from 0.05 to 0.3. The more substitutions with these alkaline earth metals within this range, the higher the conductivity becomes; however, when the number increases beyond this range, it is no longer possible to replace La, and complex oxides other than perovskite structures (e.g. CaCrO4, S
rCrO4 etc.) and significantly deteriorate its properties.
【００１２】金属Ｍ′はランタンクロマイト格子のＢサ
イトのクロムの一部と置換して酸化クロムの蒸気圧を下
げ、その蒸発を抑制するために緻密な焼結体を得ること
を可能にする金属である。このような金属としては第一
に酸化クロムの蒸気圧を下げるもの、第二にクロムイオ
ンよりも体積拡散係数が大きいものが好ましい。この条
件を満たせばよいので、Ｎｉのほか、Ｚｎ，Ｃｕ，Ｍｎ
，Ｖ，Ｉｒ，Ａｌ，Ｍｏ，Ｗ，Ｐｄ，Ｙ，Ｐｔ，Ｐｈ，
Ｔｉ，Ｓｉ，Ｂが挙げられる。Metal M' is a metal that replaces a part of chromium at the B site of the lanthanum chromite lattice, lowers the vapor pressure of chromium oxide, and makes it possible to obtain a dense sintered body to suppress its evaporation. It is. As such a metal, firstly, it is preferable to use a metal that lowers the vapor pressure of chromium oxide, and secondly, it is preferable to use a metal that has a larger volume diffusion coefficient than chromium ions. As long as this condition is satisfied, in addition to Ni, Zn, Cu, Mn
, V, Ir, Al, Mo, W, Pd, Y, Pt, Ph,
Examples include Ti, Si, and B.
【００１３】また、金属Ｍ′の添加も焼結体の導電率を
向上させる効果があり、金属Ｍ′を添加しない場合の２
倍以上の導電率が得られる。金属Ｍ′の置換量はモル比
で０＜ｙ≦０．５、好ましくは０．０５≦ｙ≦０．３で
ある。Ｍ′の添加量が多くなると、ランタンクロマイト
格子中への固溶が困難になり、Ｍ′がＮｉの場合にはＬ
ａＮｉＯ３ が生成し、同様にＺｎ，Ｃｕ，Ｍｎ，Ｖ，
Ｉｒ，Ａｌ，Ｍｏ，Ｗ，Ｐｄ，Ｙ，Ｐｔ，Ｐｈ，Ｔｉ，
Ｓｉ，ＢではそれぞれＺｎＯ，ＣｕＯ，ＬａＭｎＯ３
，Ｖ２ Ｏ３ ，Ｉｒ２ Ｏ３ ，Ａｌ２ Ｏ３ ，Ｍ
ｏＯ２ ，ＷＯ３ ，ＰｄＯ，Ｙ２ Ｏ３ ，ＰｔＯ，
Ｐｈ２ Ｏ３ ，ＴｉＯ２ ，ＳｉＯ２ ，Ｂ２ Ｏ３
が生成するようになる。これらのうちＣｕＯ，ＬａＭ
ｎＯ３ ，Ｉｒ２ Ｏ３ 及びＹ２ Ｏ３ は電子導電
性のほかに酸素イオン導電性を有し、また、還元性雰囲
気下で不安定なのでランタンクロマイトとしての特性を
劣化させる。また、ＺｎＯ，Ｖ２ Ｏ３ ，Ａｌ２ Ｏ
３ ，ＭｎＯ２ ，ＷＯ３ ，ＰｄＯ，ＰｔＯ，Ｐｈ２
Ｏ３ ，ＴｉＯ２ ，ＳｉＯ２ ，Ｂ２ Ｏ３ は酸
化雰囲気で電気特性が悪く、電気導電材料としては使用
できない。従って、ランタンクロマイト格子中の固溶量
以上の金属Ｍ′の添加は好ましくない。[0013] Addition of metal M' also has the effect of improving the electrical conductivity of the sintered body.
More than double the conductivity can be obtained. The amount of metal M' substituted is 0<y≦0.5 in molar ratio, preferably 0.05≦y≦0.3. When the amount of M' added increases, it becomes difficult to form a solid solution in the lanthanum chromite lattice, and when M' is Ni, L
aNiO3 is generated, and similarly Zn, Cu, Mn, V,
Ir, Al, Mo, W, Pd, Y, Pt, Ph, Ti,
For Si and B, respectively, ZnO, CuO, and LaMnO3
,V2O3,Ir2O3,Al2O3,M
oO2, WO3, PdO, Y2 O3, PtO,
Ph2 O3 , TiO2 , SiO2 , B2 O3
will now be generated. Among these, CuO, LaM
nO3, Ir2O3, and Y2O3 have oxygen ion conductivity in addition to electronic conductivity, and are unstable in a reducing atmosphere, which deteriorates the properties of lanthanum chromite. Also, ZnO, V2 O3, Al2 O
3, MnO2, WO3, PdO, PtO, Ph2
O3, TiO2, SiO2, and B2 O3 have poor electrical properties in an oxidizing atmosphere and cannot be used as electrically conductive materials. Therefore, it is not preferable to add metal M' in an amount exceeding the amount of solid solution in the lanthanum chromite lattice.
【００１４】一般式（Ｌａ１−ｘ Ｍｘ ）ａ （Ｃｒ
１−ｙ Ｍ′ｙ ）ｂ Ｏ３ においてｂ／ａは必ずし
も１である必要はなく、その前後でも同様な効果を奏す
ることができるが、ｂ／ａを１から若干ずらした場合に
はセラミックスの強度を向上する効果を奏する。本発明
の材料は特にＦｅの添加により焼結性に優れ、緻密な焼
結体を得ることができるが、焼結体は多結晶より構成さ
れており、一般的に焼結性の向上は結晶粒径の拡大を促
し、結晶粒径が大きくなるにつれてセラミックス強度が
低下する。これはアルミナや安定化ジルコニアにおいて
もよく知られた現象である。そこで、ｂ／ａの比を１か
ら若干ずらすことによって、多結晶中にペロブスカイト
構造以外の構造を入れることで、粒径を抑制し、これに
よってセラミックス強度の向上を図ることができる。但
し、ｂ／ａが１からあまり大きくずれてしまうと、ペロ
ブスカイト構造以外のランタン酸化物やクロム酸化物な
どが増加し、これらは粒子界面にあって電気導電性を低
下させるので好ましくない。そこで、ｂ／ａは０．９５
〜１．０５の範囲内とする。General formula (La1-x Mx ) a (Cr
1-y M'y )b O3, b/a does not necessarily have to be 1, and the same effect can be achieved even before or after that, but if b/a is slightly shifted from 1, the strength of the ceramics will increase. It has the effect of improving The material of the present invention has excellent sinterability, especially due to the addition of Fe, and a dense sintered body can be obtained, but the sintered body is composed of polycrystals, and generally the improvement in sinterability is due to crystallization. It promotes grain size expansion, and as the crystal grain size increases, the ceramic strength decreases. This is a well-known phenomenon in alumina and stabilized zirconia. Therefore, by slightly shifting the b/a ratio from 1 and introducing a structure other than the perovskite structure into the polycrystal, the grain size can be suppressed, thereby improving the ceramic strength. However, if b/a deviates too much from 1, lanthanum oxides, chromium oxides, etc. other than the perovskite structure will increase, and these will be present at the particle interface and reduce electrical conductivity, which is not preferable. Therefore, b/a is 0.95
-1.05.
【００１５】本発明の新規なランタンクロマイト系複合
酸化物の製造手法自体は慣用法に従うことができる。す
なわち、ランタン源、アルカリ土類金属源、クロム源、
金属Ｍ′源を所定比に混合した粉末混合物を所定の温度
、一般的には、１０００〜１６００℃、好ましくは１０
００〜１２００℃で仮焼して得ることができる。仮焼時
間は一般に１〜数十時間、好ましくは１〜１０時間であ
る。仮焼雰囲気は大気中等の酸素含有雰囲気中で行なう
。仮焼時の圧力は大気圧でよい。The novel lanthanum chromite-based composite oxide of the present invention can be manufactured by any conventional method. Namely, lanthanum source, alkaline earth metal source, chromium source,
A powder mixture containing metal M' sources in a predetermined ratio is heated to a predetermined temperature, generally 1000 to 1600°C, preferably 10
It can be obtained by calcining at 00 to 1200°C. The calcination time is generally 1 to several tens of hours, preferably 1 to 10 hours. The calcination atmosphere is performed in an oxygen-containing atmosphere such as the air. The pressure during calcination may be atmospheric pressure.
【００１６】仮焼粉末の成形、焼成も慣用法に従うこと
ができるが、焼成温度は一般に１３００℃以上で、好ま
しくは１５００〜１６００℃、焼成時間は焼成体の形状
に依存するが一般に１〜１０時間、好ましくは１〜２時
間、焼成雰囲気は酸素含有雰囲気である。本発明のラン
タンクロマイト系複合酸化物は常圧焼結でも緻密な焼結
体が得られることを特徴としているが、加圧下で焼結す
ることを排斥するわけではない。[0016] Molding and firing of the calcined powder can also be carried out according to conventional methods, but the firing temperature is generally 1300°C or higher, preferably 1500 to 1600°C, and the firing time is generally 1 to 10°C, although it depends on the shape of the fired product. The firing atmosphere is an oxygen-containing atmosphere for a period of time, preferably 1 to 2 hours. Although the lanthanum chromite-based composite oxide of the present invention is characterized in that a dense sintered body can be obtained even by normal pressure sintering, sintering under pressure is not excluded.
【００１７】こうして得られる微量元素添加ランタンク
ロマイト焼結体は、常圧大気中における焼成によっても
９５％以上の相対密度を得ることができ、かつ導電率も
従来組成のものと比較して２倍以上の値を得ることがで
きる。しかも、この焼結体は耐酸化性、耐還元性に優れ
ているので、高温下で耐食性と導電性の両方が要求され
る高温導電性材料として有用である。とくに、導電性を
有しかつ耐食性と緻密性を有する点で、固体電解質型燃
料電池のセパレータ材料として有用である。The trace element-added lanthanum chromite sintered body obtained in this manner can have a relative density of 95% or more even when fired in the atmosphere at normal pressure, and has twice the electrical conductivity as compared to that of the conventional composition. It is possible to obtain the above values. Moreover, since this sintered body has excellent oxidation resistance and reduction resistance, it is useful as a high-temperature conductive material that requires both corrosion resistance and conductivity at high temperatures. In particular, it is useful as a separator material for solid oxide fuel cells because it has electrical conductivity, corrosion resistance, and denseness.
【００１８】図１にプラナー型固体電解質燃料電池の構
造の例を示す。同図中、１は固体電解質（例、Ｙ安定化
ジルコニア）のシートで上面にカソード（例、Ｌａ０．
９ Ｓｒ０．１ ＭｎＯ３ ）２、下面にアノード（例
、ＮｉＯ／ＺｒＯ２ サーメット）３が形成されている
。４がセパレータで本発明の新規なランタンクロマイト
系複合酸化物で作る。５は４と同じくランタンクロマイ
ト系複合酸化物で作るが、外部出力端子として使われる
。図１に見られる通り、セパレータ４はそれに形成され
た溝によって空気６及び燃料（例、水素）７の流路を構
成しかつ空気６と燃料７を分離するセパレータであると
共に、隣接する単位セルのアノード３とカソード２とを
電気的に接続する役割をも担うものである。外部出力端
子５は集積された単位セルの両端部において空気６と燃
料７の流路を形成すると共にアノード３又はカソード２
との電気的接続を行なう部材でもあり、これも本発明の
ランタンクロマイト系複合酸化物で構成する。また、図
１は２つの単位セルを集積した燃料電池を示したが、３
つ以上の単位セルを集積することも可能で、その場合に
は各単位セル間にセパレータ４を挿入する。FIG. 1 shows an example of the structure of a planar solid electrolyte fuel cell. In the figure, 1 is a sheet of solid electrolyte (eg, Y-stabilized zirconia) with a cathode (eg, La0.
9 Sr0.1 MnO3 ) 2, and an anode (eg, NiO/ZrO2 cermet) 3 is formed on the lower surface. 4 is a separator made of the novel lanthanum chromite complex oxide of the present invention. 5 is made of lanthanum chromite complex oxide like 4, but is used as an external output terminal. As seen in FIG. 1, the separator 4 is a separator that forms a flow path for air 6 and fuel (e.g. hydrogen) 7 by grooves formed therein, and separates the air 6 and fuel 7 from adjacent unit cells. It also plays the role of electrically connecting the anode 3 and cathode 2 of. The external output terminal 5 forms a flow path for air 6 and fuel 7 at both ends of the integrated unit cell, and also connects to the anode 3 or cathode 2.
It is also a member for electrical connection with the lanthanum chromite complex oxide of the present invention. In addition, although Fig. 1 shows a fuel cell in which two unit cells are integrated, three
It is also possible to integrate more than one unit cell, in which case a separator 4 is inserted between each unit cell.
【００１９】[0019]
【実施例】実施例１（ｂ／ａ＝１）酸化ランタン２６．
０６５ｇ、炭酸ストロンチウム５．９０５ｇ、酸化第二
クロム１３．６７９ｇ、酸化第二ニッケル１．６５４ｇ
を秤量し、メノウ乳鉢を用いて湿式混合した。この組成
はＬａ０．８ Ｓｒ０．２ Ｃｒ０．９ Ｎｉ０．１
Ｏ３ に相当する。
この混合粉末を１２００℃にて１時間仮焼した。昇温速
度は２０℃／ｍｉｎである。こうして得られたランタン
クロマイト粉末をＸ線回折法により分析した結果、第二
相の存在は確認できず、ニッケルはペロブスカイト構造
をもったランタンクロマイト格子中に固溶していること
がわかった。[Example] Example 1 (b/a=1) Lanthanum oxide 26.
065g, strontium carbonate 5.905g, chromic oxide 13.679g, nickel oxide 1.654g
were weighed and wet mixed using an agate mortar. This composition is La0.8 Sr0.2 Cr0.9 Ni0.1
Corresponds to O3. This mixed powder was calcined at 1200° C. for 1 hour. The temperature increase rate is 20°C/min. As a result of analyzing the lanthanum chromite powder thus obtained by X-ray diffraction, the presence of a second phase could not be confirmed, and it was found that nickel was dissolved in solid solution in the lanthanum chromite lattice having a perovskite structure.
【００２０】この粉末を３００ｋｇｆ／ｃｍ２ の荷重
でフローティング成形し、１６００℃にて２時間本焼成
した（昇温速度は５℃／ｍｉｎ）。こうして得られた焼
結体について、密度ならびに導電率を測定した。その結
果、密度にして６．２ｇ／ｃｍ３ （相対密度９５％以
上）、空気中１０００℃における導電率にして３９ｓ／
ｃｍを得た。また、この焼結体を走査型電子顕微鏡なら
びにＥＤＸ分光分析によって元素の分布を観察したが、
偏析等は見られず添加したニッケルは均一にクロムと置
換していることがわかった。[0020] This powder was float-molded under a load of 300 kgf/cm2, and main firing was performed at 1600°C for 2 hours (heating rate was 5°C/min). The density and conductivity of the sintered body thus obtained were measured. As a result, the density was 6.2g/cm3 (relative density 95% or more), and the conductivity at 1000℃ in air was 39s/cm3.
cm was obtained. In addition, the distribution of elements in this sintered body was observed using a scanning electron microscope and EDX spectroscopy.
No segregation was observed, and it was found that the added nickel was uniformly replaced by chromium.
【００２１】以上のものと同製法にて作製したＬａ０．
８ Ｓｒ０．２ ＣｒＯ３ 組成の焼結体（比較例）に
おいては密度５．０ｇ／ｃｍ３ （相対密度７６％）、
空気中１０００℃における導電率にして１８ｓ／ｃｍで
あった。このように、ニッケルを添加することによって
密度、導電率ともにかなり向上していることがわかる。
実施例２（ｂ／ａ＝０．９７）酸化ランタン２６．０６
５ｇ、炭酸ストロンチウム５．９０５ｇ、酸化第二クロ
ム１３．２６９ｇおよび酸化第二ニッケル１．６０４ｇ
を秤量し、メノウ乳鉢を用いて湿式混合した。この組成
はＬａ０．８ Ｓｒ０．２ Ｃｒ０．８７３ Ｎｉ０．
０９７Ｏ３ に相当する。この混合粉末を実施例１と同
様にして焼成した。[0021] La0.
8 Sr0.2 CrO3 composition sintered body (comparative example) has a density of 5.0 g/cm3 (relative density 76%),
The conductivity at 1000° C. in air was 18 s/cm. Thus, it can be seen that both density and conductivity are significantly improved by adding nickel. Example 2 (b/a=0.97) Lanthanum oxide 26.06
5g, strontium carbonate 5.905g, chromic oxide 13.269g and nickel oxide 1.604g
were weighed and wet mixed using an agate mortar. This composition is La0.8 Sr0.2 Cr0.873 Ni0.
Corresponds to 097O3. This mixed powder was fired in the same manner as in Example 1.
【００２２】得られた焼成生成物（粉末）はＸ線回折法
により分析すると、殆んどペロブスカイト構造であった
。この粉末を用いて実施例１と同様にして焼結体を調製
し、密度、導電率、曲げ強度、平均粒径を測定した。
結果を表１に示す。
実施例３（ｂ／ａ＝１．０２）酸化ランタン２６．０６
５ｇ、炭酸ストロンチウム５．９０５ｇ、酸化第二クロ
ム１３．９５２ｇおよび酸化第二ニッケル１．６８７ｇ
を秤量し、メノウ乳鉢を用いて湿式混合した。この組成
はＬａ０．８ Ｓｒ０．２ Ｃｒ０．９１８ Ｎｉ０．
１０２Ｏ３ に相当する。この混合粉末を実施例１と同
様にして焼成した。[0022] When the obtained fired product (powder) was analyzed by X-ray diffraction, it was found that most of it had a perovskite structure. A sintered body was prepared using this powder in the same manner as in Example 1, and the density, electrical conductivity, bending strength, and average particle size were measured. The results are shown in Table 1. Example 3 (b/a=1.02) Lanthanum oxide 26.06
5g, strontium carbonate 5.905g, chromic oxide 13.952g and nickel oxide 1.687g
were weighed and wet mixed using an agate mortar. This composition is La0.8 Sr0.2 Cr0.918 Ni0.
It corresponds to 102O3. This mixed powder was fired in the same manner as in Example 1.
【００２３】得られた焼成生成物（粉末）はＸ線回折法
により分析すると、殆んどペロブスカイト構造であった
。この粉末を用いて実施例１と同様にして焼結体を調製
し、密度、導電率、曲げ強度、平均粒径を測定した。
結果を表１に示す。[0023] When the obtained fired product (powder) was analyzed by X-ray diffraction, it was found that most of it had a perovskite structure. A sintered body was prepared using this powder in the same manner as in Example 1, and the density, electrical conductivity, bending strength, and average particle size were measured. The results are shown in Table 1.
【００２４】[0024]
【表１】[Table 1]
【００２５】表１の結果より、Ｓｒ及びＮｉの添加によ
り焼結体の密度（焼結性）、導電率ともに向上している
こと、またＡサイト、Ｂサイトの組成比ｂ／ａを１から
若干ずらすことにより機械的強度が向上し、かつ密度、
導電率は損なわれていないことが見られる。From the results in Table 1, it can be seen that the addition of Sr and Ni improves both the density (sinterability) and electrical conductivity of the sintered body, and that the composition ratio b/a of the A site and B site is changed from 1 to 1. By slightly shifting the mechanical strength and density,
It can be seen that the conductivity is intact.
【００２６】[0026]
【発明の効果】本発明により提供される新規ランタンク
ロマイト系複合酸化物は、常圧大気中で容易に緻密化し
、かつ導電率も優れているので、高温で使用する安定な
導体材料を提供することができ、とくに高温型燃料電池
のセパレータとして有用である。[Effects of the Invention] The novel lanthanum chromite-based composite oxide provided by the present invention is easily densified in normal pressure atmosphere and has excellent electrical conductivity, so it provides a stable conductive material that can be used at high temperatures. It is particularly useful as a separator for high-temperature fuel cells.
【図１】平板型固体電解質型燃料電池の模式図である。FIG. 1 is a schematic diagram of a flat plate solid electrolyte fuel cell.
１…固体電解質 ２…カソード ３…アノード ４…接合体 ５…外部出力端子 ６…空気 ７…燃料 1...Solid electrolyte 2...Cathode 3...Anode 4...Zygote 5...External output terminal 6...Air 7...Fuel
Claims (4)
Ｍ′ｙ Ｏ３ （式中、Ｍはマグネシウムを除くアル
カリ土類金属であり、Ｍ′はＮｉ，Ｚｎ，Ｃｕ，Ｍｎ，
Ｖ，Ｉｒ，Ａｌ，Ｍｏ，Ｗ，Ｐｄ，Ｙ，Ｐｔ，Ｒｈ，Ｔ
ｉ，Ｓｉ又はＢであり、０＜ｘ≦０．５であり、０＜ｙ
≦０．５である。）で表わされかつペロブスカイト構造
を持つことを特徴とするランタンクロマイト系複合酸化
物。Claim 1: General formula La1-x Mx Cr1-y
M′y O3 (wherein, M is an alkaline earth metal excluding magnesium, M′ is Ni, Zn, Cu, Mn,
V, Ir, Al, Mo, W, Pd, Y, Pt, Rh, T
i, Si or B, 0<x≦0.5, and 0<y
≦0.5. ) is a lanthanum chromite-based composite oxide characterized by having a perovskite structure.
Ｃｒ１−ｙ Ｍ′ｙ ）ｂ Ｏ３ （式中、Ｍはマグネ
シウムを除くアルカリ土類金属であり、Ｍ′はＮｉ，Ｚ
ｎ，Ｃｕ，Ｍｎ，Ｖ，Ｉｒ，Ａｌ，Ｍｏ，Ｗ，Ｐｄ，Ｙ
，Ｐｔ，Ｐｈ，Ｔｉ，Ｓｉ又はＢであり、０＜ｘ≦０．
５，０＜ｙ≦０．５、そして０．９５≦ｂ／ａ＜１又は
１＜ｂ／ａ≦１．０５である。）で表わされ主としてペ
ロブスカイト構造からなることを特徴とするランタンク
ロマイト系複合酸化物。Claim 2: General formula (La1-x Mx) a (
Cr1-y M'y )b O3 (wherein, M is an alkaline earth metal excluding magnesium, and M' is Ni, Z
n, Cu, Mn, V, Ir, Al, Mo, W, Pd, Y
, Pt, Ph, Ti, Si or B, and 0<x≦0.
5,0<y≦0.5, and 0.95≦b/a<1 or 1<b/a≦1.05. ) is a lanthanum chromite-based composite oxide characterized by mainly consisting of a perovskite structure.
イト系複合酸化物からなる高温導電性材料。3. A high temperature conductive material comprising the lanthanum chromite complex oxide according to claim 1 or 2.
イト系複合酸化物からなるセパレータを有する高温型燃
料電池。4. A high-temperature fuel cell comprising a separator made of the lanthanum chromite complex oxide according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03067464A JP3134883B2 (en) | 1990-03-30 | 1991-03-30 | Separator for solid oxide fuel cell |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-81259 | 1990-03-30 | ||
| JP8125990 | 1990-03-30 | ||
| JP03067464A JP3134883B2 (en) | 1990-03-30 | 1991-03-30 | Separator for solid oxide fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04219366A true JPH04219366A (en) | 1992-08-10 |
| JP3134883B2 JP3134883B2 (en) | 2001-02-13 |
Family
ID=26408681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03067464A Expired - Fee Related JP3134883B2 (en) | 1990-03-30 | 1991-03-30 | Separator for solid oxide fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3134883B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0616471A (en) * | 1991-06-28 | 1994-01-25 | Nitsukatoo:Kk | Heat resistant conductive sintered body |
| JP2017065991A (en) * | 2015-09-30 | 2017-04-06 | 大日精化工業株式会社 | Perovskite-based black powder, method for producing the same, and resin composition using the same |
-
1991
- 1991-03-30 JP JP03067464A patent/JP3134883B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0616471A (en) * | 1991-06-28 | 1994-01-25 | Nitsukatoo:Kk | Heat resistant conductive sintered body |
| JP2017065991A (en) * | 2015-09-30 | 2017-04-06 | 大日精化工業株式会社 | Perovskite-based black powder, method for producing the same, and resin composition using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3134883B2 (en) | 2001-02-13 |
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