CA2200160C - Lanthanide ceramic material - Google Patents
Lanthanide ceramic material Download PDFInfo
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- CA2200160C CA2200160C CA002200160A CA2200160A CA2200160C CA 2200160 C CA2200160 C CA 2200160C CA 002200160 A CA002200160 A CA 002200160A CA 2200160 A CA2200160 A CA 2200160A CA 2200160 C CA2200160 C CA 2200160C
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- ceramic material
- lanthanide
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- metal
- lanthanide oxide
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 51
- 229910052747 lanthanoid Inorganic materials 0.000 title claims description 26
- 150000002602 lanthanoids Chemical class 0.000 title claims description 26
- 229910000311 lanthanide oxide Inorganic materials 0.000 claims abstract description 23
- 239000011224 oxide ceramic Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 13
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 10
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 21
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 21
- 239000012141 concentrate Substances 0.000 claims description 13
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910002637 Pr6O11 Inorganic materials 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 3
- 239000000843 powder Substances 0.000 description 8
- 239000011572 manganese Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 2
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LEMJVPWNQLQFLW-UHFFFAOYSA-N [La+3].[La+3].[O-][Cr]([O-])=O.[O-][Cr]([O-])=O.[O-][Cr]([O-])=O Chemical class [La+3].[La+3].[O-][Cr]([O-])=O.[O-][Cr]([O-])=O.[O-][Cr]([O-])=O LEMJVPWNQLQFLW-UHFFFAOYSA-N 0.000 description 1
- ZJIYREZBRPWMMC-UHFFFAOYSA-N [Sr+2].[La+3].[O-][Cr]([O-])=O Chemical class [Sr+2].[La+3].[O-][Cr]([O-])=O ZJIYREZBRPWMMC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004814 ceramic processing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/016—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on manganites
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/42—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on chromites
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
- Ceramic Products (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
A lanthanide oxide ceramic material is provided herein having the general formula La a Ln b M'c M"d O3-.delta.. In such formula, Ln is a combination of Ce, Pr and Nd; M' is at least one alkaline earth metal; M" is at least one metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pd, Pt, Mg, Ru, Rh, Cr and Zr, and 0 <= a <= 1; 0.01 < b <= 1; 0 <= c <=
0.6; 0 <= d <= 1; and -1 < .delta. < +1.
Such material finds use as the ceramic material in a fuel cell.
0.6; 0 <= d <= 1; and -1 < .delta. < +1.
Such material finds use as the ceramic material in a fuel cell.
Description
(a) TITLE OF THE INVENTION
LANTHANIDE CERAMIC MATERIAL
(b) TECHNICAL. FIELD TO WHICH THE INVENTION RELATES
The present invention relates to a material based on a lanthanide-metal-containing, complex mixed oxide with functional electrical or catalytic properties exhibiting improved commercial and techncal performance.
(c) BACKGROUND ART
Classical ceramic materials for solid oxide components, a variety of catalysts, electrical heating elements and other electronic ceramics are based on mixed oxides containing lanthanide elements such as perovskites having the general formula AB03.
In this formula, the symbol A represents a single lanthanide element, and in some cases smaller amounts of alkaline earth metal elements. The symbol B represents a metal ion with an ionic radius smaller than the A cation. Changing the chemical composition makes it possible to control a variety of technologically important properties, e.g., 1 S electronic conductivity, ionic conductivity, heat conductivity, thermal expansion, catalytic properties, chemical stability and high temperature stability. However, the high prices for pure lanthanide lriaterials are prohibitive for a more widespread commercialization.
Furthermore, the pure mixed oxides typically used may be very refractory and very difficult to sinter into dense ceramic components.
(d) DESCRIPTION OF THE INVENTION
Broad aspects of this invention provide a novel lanthanide-based, complex oxide having an electrical conductivity at a high temperature, wherein a portion of the metal La in the general chemical formula is replaced by the metals Ce, Pr and Nd in amounts above 1 % . This new material makes it possible to use partly-refined lanthanum raw material, often named "lanthanum concentrates" instead of more expensive, highly refined lanthanum chemicals. The presence of the other lanthanides in the complex mixed oxide, in addition to traces of other impurities originating from the partly-refined lanthanum raw material, enhances the sinter activity of the mixed oxide, making densification easier. Furthermore, the lanthanum deficiency in the mixed oxide induced by partly or completely replacing lanthanum with other lanthanides reduces the detrimental reaction between lanthanum and other components adjacent to the mixed oxide material. This is a well known problem when using pure lanthanum ceramic materials as cell material in solid oxide fuel cells.
By a first broad aspect of this invention, a lanthanide oxide ceramic is provided having the general Formula LaaLnhM'~M"~03_~, wherein Ln is a combination of Ce, Pr and Nd; M' is at least one alkaline earth metal; M" is at least one metal selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, A1, V, Ir, Mo, W, Pd, Pt, Mg, Ru, Rh,CrandZr;O<a<_ 1;0.01 < b== 1;0<c _<0.6;0<d< l; and-1 < 8 < +1.
By a first variant thereof, the lanthanum oxide ceramic material has the formula Lao.54Ceo.osPro.o~Ndo.~ssro.~sMn03. By a second variant thereof, the lanthanide oxide ceramic material has the formula Lao 54Ceo.oSPr~.o,Ndo,,$Sro.lsCr03.
In accordance with a second broad aspect of the present invention, an improvement is provided in a process of preparing a lanthanide oxide ceramic material which includes combining a source of lanthanide elements, a source of an alkaline earth metal, and a source of a metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W., Pd, Pt, Mg, Ru, Rh, Cr and Zr, and forming the ceramic material from the sources, t:he improvement which comprises: employing lanthanum concentrate as the source of the lanthanide elements, the lanthanum concentrate containing 40 % La03, 4 % CeOz, 5 .5 % Pr6011 and 13 .5 % Nd203.
By a first variant thereof, the source of lanthanide elements contain 0.01 atomic percent to 50 atomic percent of each of Ce, Pr and Nd, based on the total amount of lanthanide elements. By a second variant thereof the lanthanide oxide ceramic material is formed from a lanthanum concentrate containing 40 % La03, 4 % Ce02, 5 .5 % Pr6011 and 13.5 %
Ndz03, an alkaline earth metal, and a metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pr, Pt, Mg, Ru, Rh, Cr and Zr. By a first variation of that second variant thereof, the lanthanide oxide ceramic material which is formed from a lanthanum concentrate containing 0.01 atomic percent to atomic percent of each of Ce, Pr, and Nd, based upon the total amount of lanthanide elements.
By a third aspect of this invention, an improvement is provided in a fuel cell having a ceramic material therein, wherein the ceramic material comprising a lanthanide oxide ceramic material having the general formula LaaLnbM'cM"d03_b, wherein Ln is a combination of Ce, Pr and Nd, M' is at least one alkaline earth metal, M" is at least one metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir,Mo,W,Pd,Pt,Mg,Ru,Rh,CrandZr;O<_a<_ 1;0.01 <b1,0<_c_<0.6;0_<d <_l;and-1 <8< +1.
By a first variant of this third aspect of the invention, the ceramic material comprises a lanthanide oxide ceramic material which has the formula Lao.saCeo.osPro.o~Ndo.~sSro.~sMn03. By a second variant of this third aspect of the invention, the ceramic material comprises a lanthanide oxide ceramic material, which has the formula Lao.54Ceo.oSPro o~Ndo , ~Sro.,sCr03.
By a third variant of this third aspect of this invention, the improved fuel cell includes a ceramic material which is a lanthanide oxide material which is prepared by a first procedure as described hereinabove and which is formed from a lanthanum concentrate containing 40 % La03, 4 ~~o Ce02, 5 .5 % Pr60" and 13 .5 % Na203, an alkaline earth metal, and a metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pr, Pt, Mg, Ru, Rh, Cr and Zr. By a fourth variant of this third aspect of the invention, the ceramic material comprises a lanthanide oxide ceramic material which is formed according to a second procedure as described hereinabove.
Changes in properties introduced by the other lanthanide elements when compared with mixed oxides without these other lanthanides may be compensated for by doping with other elements. For instance, in the case of lanthanum-based perovskites, the A-site may be doped with alkaline earth elements, e.g., Mg, Ca, Sr or Ba, and the B-site may be doped with metal elements or transition elements.
3a The lanthanide oxide ceramic material, according to an aspect of this invention, may be synthesized by mixing the partly-refined mixed lanthanide raw powder with strontium carbonate and manganese oxide, followed by calcination.
Another synthesis process, according to another aspect of this invention, is to dissolve the partly-refined mixed lanthanide raw powder in an acid, e.g., nitric acid, followed by the addition of salt solutions of strontium and manganese. This mixed salt solution may be pyrolysed to produce the desired lanthanide based material.
Lanthanum chromites represent state-of the-art materials for use as current interconnections in SOFC's. This material has an AB03-type perovskite structure and alkaline earth metal canons (e.g., Mg, Ca, Sr or Ba) are often substituted for a fraction of La on the A-lattice site, thereby greatly enhancing the electrical conductivity.
Lanthanum strontium chromites have become quite popular for SOFC
interconnections due to an excellent combination of properties.
According to aspects of this invention, lanthanide ceramic materials may be prepared as described above and in the following examples.
(e) AT LEAST ONE MODE FOR CARRYING OUT THE INVENTION
Example 1 Commercial Lanthanum Concentrate containing 40 % La203, 4 % Ce02, 5.5 Pr6011 and 13.5 % Nd203 plus 1 % other lanthanides is dissolved in 65 % HN03.
This solution is combined with a 1 M solution of Sr(N03)2 and Mn(N03)3 in quantities according to the chemical formula:
I-ao.saCeo.osl'ro.o~Ndo. isSro. isMn03 The resulting mixed salt solution is added glucose in a molar ratio of 1:1 with respect to the total metal cation ~ ' ~ 22 ~016U
LANTHANIDE CERAMIC MATERIAL
(b) TECHNICAL. FIELD TO WHICH THE INVENTION RELATES
The present invention relates to a material based on a lanthanide-metal-containing, complex mixed oxide with functional electrical or catalytic properties exhibiting improved commercial and techncal performance.
(c) BACKGROUND ART
Classical ceramic materials for solid oxide components, a variety of catalysts, electrical heating elements and other electronic ceramics are based on mixed oxides containing lanthanide elements such as perovskites having the general formula AB03.
In this formula, the symbol A represents a single lanthanide element, and in some cases smaller amounts of alkaline earth metal elements. The symbol B represents a metal ion with an ionic radius smaller than the A cation. Changing the chemical composition makes it possible to control a variety of technologically important properties, e.g., 1 S electronic conductivity, ionic conductivity, heat conductivity, thermal expansion, catalytic properties, chemical stability and high temperature stability. However, the high prices for pure lanthanide lriaterials are prohibitive for a more widespread commercialization.
Furthermore, the pure mixed oxides typically used may be very refractory and very difficult to sinter into dense ceramic components.
(d) DESCRIPTION OF THE INVENTION
Broad aspects of this invention provide a novel lanthanide-based, complex oxide having an electrical conductivity at a high temperature, wherein a portion of the metal La in the general chemical formula is replaced by the metals Ce, Pr and Nd in amounts above 1 % . This new material makes it possible to use partly-refined lanthanum raw material, often named "lanthanum concentrates" instead of more expensive, highly refined lanthanum chemicals. The presence of the other lanthanides in the complex mixed oxide, in addition to traces of other impurities originating from the partly-refined lanthanum raw material, enhances the sinter activity of the mixed oxide, making densification easier. Furthermore, the lanthanum deficiency in the mixed oxide induced by partly or completely replacing lanthanum with other lanthanides reduces the detrimental reaction between lanthanum and other components adjacent to the mixed oxide material. This is a well known problem when using pure lanthanum ceramic materials as cell material in solid oxide fuel cells.
By a first broad aspect of this invention, a lanthanide oxide ceramic is provided having the general Formula LaaLnhM'~M"~03_~, wherein Ln is a combination of Ce, Pr and Nd; M' is at least one alkaline earth metal; M" is at least one metal selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, A1, V, Ir, Mo, W, Pd, Pt, Mg, Ru, Rh,CrandZr;O<a<_ 1;0.01 < b== 1;0<c _<0.6;0<d< l; and-1 < 8 < +1.
By a first variant thereof, the lanthanum oxide ceramic material has the formula Lao.54Ceo.osPro.o~Ndo.~ssro.~sMn03. By a second variant thereof, the lanthanide oxide ceramic material has the formula Lao 54Ceo.oSPr~.o,Ndo,,$Sro.lsCr03.
In accordance with a second broad aspect of the present invention, an improvement is provided in a process of preparing a lanthanide oxide ceramic material which includes combining a source of lanthanide elements, a source of an alkaline earth metal, and a source of a metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W., Pd, Pt, Mg, Ru, Rh, Cr and Zr, and forming the ceramic material from the sources, t:he improvement which comprises: employing lanthanum concentrate as the source of the lanthanide elements, the lanthanum concentrate containing 40 % La03, 4 % CeOz, 5 .5 % Pr6011 and 13 .5 % Nd203.
By a first variant thereof, the source of lanthanide elements contain 0.01 atomic percent to 50 atomic percent of each of Ce, Pr and Nd, based on the total amount of lanthanide elements. By a second variant thereof the lanthanide oxide ceramic material is formed from a lanthanum concentrate containing 40 % La03, 4 % Ce02, 5 .5 % Pr6011 and 13.5 %
Ndz03, an alkaline earth metal, and a metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pr, Pt, Mg, Ru, Rh, Cr and Zr. By a first variation of that second variant thereof, the lanthanide oxide ceramic material which is formed from a lanthanum concentrate containing 0.01 atomic percent to atomic percent of each of Ce, Pr, and Nd, based upon the total amount of lanthanide elements.
By a third aspect of this invention, an improvement is provided in a fuel cell having a ceramic material therein, wherein the ceramic material comprising a lanthanide oxide ceramic material having the general formula LaaLnbM'cM"d03_b, wherein Ln is a combination of Ce, Pr and Nd, M' is at least one alkaline earth metal, M" is at least one metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir,Mo,W,Pd,Pt,Mg,Ru,Rh,CrandZr;O<_a<_ 1;0.01 <b1,0<_c_<0.6;0_<d <_l;and-1 <8< +1.
By a first variant of this third aspect of the invention, the ceramic material comprises a lanthanide oxide ceramic material which has the formula Lao.saCeo.osPro.o~Ndo.~sSro.~sMn03. By a second variant of this third aspect of the invention, the ceramic material comprises a lanthanide oxide ceramic material, which has the formula Lao.54Ceo.oSPro o~Ndo , ~Sro.,sCr03.
By a third variant of this third aspect of this invention, the improved fuel cell includes a ceramic material which is a lanthanide oxide material which is prepared by a first procedure as described hereinabove and which is formed from a lanthanum concentrate containing 40 % La03, 4 ~~o Ce02, 5 .5 % Pr60" and 13 .5 % Na203, an alkaline earth metal, and a metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pr, Pt, Mg, Ru, Rh, Cr and Zr. By a fourth variant of this third aspect of the invention, the ceramic material comprises a lanthanide oxide ceramic material which is formed according to a second procedure as described hereinabove.
Changes in properties introduced by the other lanthanide elements when compared with mixed oxides without these other lanthanides may be compensated for by doping with other elements. For instance, in the case of lanthanum-based perovskites, the A-site may be doped with alkaline earth elements, e.g., Mg, Ca, Sr or Ba, and the B-site may be doped with metal elements or transition elements.
3a The lanthanide oxide ceramic material, according to an aspect of this invention, may be synthesized by mixing the partly-refined mixed lanthanide raw powder with strontium carbonate and manganese oxide, followed by calcination.
Another synthesis process, according to another aspect of this invention, is to dissolve the partly-refined mixed lanthanide raw powder in an acid, e.g., nitric acid, followed by the addition of salt solutions of strontium and manganese. This mixed salt solution may be pyrolysed to produce the desired lanthanide based material.
Lanthanum chromites represent state-of the-art materials for use as current interconnections in SOFC's. This material has an AB03-type perovskite structure and alkaline earth metal canons (e.g., Mg, Ca, Sr or Ba) are often substituted for a fraction of La on the A-lattice site, thereby greatly enhancing the electrical conductivity.
Lanthanum strontium chromites have become quite popular for SOFC
interconnections due to an excellent combination of properties.
According to aspects of this invention, lanthanide ceramic materials may be prepared as described above and in the following examples.
(e) AT LEAST ONE MODE FOR CARRYING OUT THE INVENTION
Example 1 Commercial Lanthanum Concentrate containing 40 % La203, 4 % Ce02, 5.5 Pr6011 and 13.5 % Nd203 plus 1 % other lanthanides is dissolved in 65 % HN03.
This solution is combined with a 1 M solution of Sr(N03)2 and Mn(N03)3 in quantities according to the chemical formula:
I-ao.saCeo.osl'ro.o~Ndo. isSro. isMn03 The resulting mixed salt solution is added glucose in a molar ratio of 1:1 with respect to the total metal cation ~ ' ~ 22 ~016U
content and pyrolysed in a 600°C hot rotary furnace result-ing in a single phase complex perovskite_powder. After calcination at 900°C followed by ball milling the powder is suitable for traditional ceramic processing e.g. tape casting, screen printing or dry pressing. The X-ray dif-fraction spectrum of the calcined powder shows the charac-teristic lines for a single phase perovskite material.
Example 2 Commercial Lanthanum Concentrate containing 40%
La203, 4% Ce02, 5.5% Pr6O11 and 13.5% Nd203 plus 1_% other lanthanides is mixed with Sr(C03)Z and Cr203 in amounts according to the chemical formula:
Lao . 54Ceo . o5pro . o7Ndo . iBSro .15Cr03 The powder mixture is calcined at 900°C followed by spray-drying. The spray-dried powder is shaped by dry pressing followed by sintering in air, argon or nitrogen at tempera-tures between 1400°C and 1700°C. The X-ray diffraction spectrum of the calcined powder shows the characteristic lines for a single phase perovsite material.
Example 2 Commercial Lanthanum Concentrate containing 40%
La203, 4% Ce02, 5.5% Pr6O11 and 13.5% Nd203 plus 1_% other lanthanides is mixed with Sr(C03)Z and Cr203 in amounts according to the chemical formula:
Lao . 54Ceo . o5pro . o7Ndo . iBSro .15Cr03 The powder mixture is calcined at 900°C followed by spray-drying. The spray-dried powder is shaped by dry pressing followed by sintering in air, argon or nitrogen at tempera-tures between 1400°C and 1700°C. The X-ray diffraction spectrum of the calcined powder shows the characteristic lines for a single phase perovsite material.
Claims (12)
1. A lanthanide oxide ceramic material having the general formula:
La a Ln b M'c M" d O3-.delta., wherein Ln is a combination of Ce, Pr and Nd;
M' is at least one alkaline earth metal;
M" is at least one metal selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pd, Pt, Mg, Ru, Rh, Cr and Zr;
0 < a <= 1;
0.01 < b <= 1;
0 <= c <= 0.6;
0 <= d <= 1; and -1 < .delta. < +1.
La a Ln b M'c M" d O3-.delta., wherein Ln is a combination of Ce, Pr and Nd;
M' is at least one alkaline earth metal;
M" is at least one metal selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pd, Pt, Mg, Ru, Rh, Cr and Zr;
0 < a <= 1;
0.01 < b <= 1;
0 <= c <= 0.6;
0 <= d <= 1; and -1 < .delta. < +1.
2. The lanthanide oxide ceramic material as claimed in claim 1, having the formula La0.54Ce0.05Pr0.07Nd0.18Sr0.15MnO3.
3. The lanthanide oxide ceramic material as claimed in claim 1, having the formula La0.54Ce0.05Pr0.07Nd0.18Sr0.15CrO3.
4. An improvement in a process of preparing a lanthanide oxide ceramic material which includes combining a source of lanthanide elements, a source of an alkaline earth metal, and a source of a metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pd, Pt, Mg, Ru, Rh, Cr and Zr, and forming the ceramic material from said sources, the improvement which comprises: employing lanthanum concentrate as the source of the lanthanide elements, said lanthanum concentrate containing 40 % LaO3, 4% CeO2, 5.5% Pr6O11 and 13.5 % Nd2O3.
5. The improvement as claimed in claim 4, wherein the source of lanthanide elements contain 0.01 atomic percent to 50 atomic percent of each of Ce, Pr and Nd, based on the total amount of lanthanide elements.
6 6. The improvement as claimed in claim 4, wherein the lanthanide oxide ceramic material comprises the material as claimed in claim 3, which is formed from a lanthanum concentrate containing 40% LaO3, 4% CeO2, 5.5% Pr6O11, and 13.5%
Nd2O3, an alkaline earth metal, and a metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pr, Pt, Mg, Ru, Rh, Cr and Zr.
Nd2O3, an alkaline earth metal, and a metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pr, Pt, Mg, Ru, Rh, Cr and Zr.
7. The lanthanide oxide ceramic material as claimed in claim 6, which is formed from a lanthanum concentrate containing 0.01 atomic percent to 50 atomic percent of each of Ce, Pr, and Nd, based upon the total amount of lanthanide elements.
8. In a fuel cell having a ceramic material therein, the improvement which comprises providing, as said ceramic material, a ceramic material comprising a lanthanide oxide ceramic material having the general formula of:
La a Ln b M' c M" d O3-.delta., wherein Ln is a combination of Ce, Pr and Nd;
M' is at least one alkaline earth metal;
M" is at least one metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pd, Pt, Mg, Ru, Rh, Cr and Zr; and 0 < a <= 1;
0.01 < b <= 1;
0 <= c <= 0.6;
0 <= d <= 1; and -1 < .delta. < +1.
La a Ln b M' c M" d O3-.delta., wherein Ln is a combination of Ce, Pr and Nd;
M' is at least one alkaline earth metal;
M" is at least one metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pd, Pt, Mg, Ru, Rh, Cr and Zr; and 0 < a <= 1;
0.01 < b <= 1;
0 <= c <= 0.6;
0 <= d <= 1; and -1 < .delta. < +1.
9. In a fuel cell having a ceramic material therein as claimed in claim 8, the improvement which comprises providing, as said ceramic material, a ceramic material comprising a lanthanide oxide ceramic material, having the formula La0.54Ce0.05Pr0.07Nd0.18Sr0.15MnO3.
10. In a fuel cell having a ceramic material therein, as claimed in claim 8, the improvement which comprises providing, as said ceramic material, a ceramic material comprising a lanthanide oxide ceramic material, having the formula La0.54Ce0.05Pr0.07Nd0.18Sr0.15CrO3.
11. In a fuel cell having a ceramic material therein, as claimed in claim 8, the improvement which comprises providing, as said ceramic material, a ceramic material comprising the lanthanide oxide ceramic material as claimed in claim 6, which is formed from a lanthanum concentrate containing 40%; LaO3, 4% CeO2, 5.5 % Pr6O11 and 13.5 %
Nd2O3, an alkaline earth metal, and a metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pr, Pt, Mg, Ru, Rh, Cr and Zr.
Nd2O3, an alkaline earth metal, and a metal which is selected from the group consisting of Co, Fe, Ni, Zn, Cu, Mn, Al, V, Ir, Mo, W, Pr, Pt, Mg, Ru, Rh, Cr and Zr.
12. In a fuel cell having a ceramic material therein, as claimed in claim 8, the improvement which comprises providing, as said ceramic material, a ceramic material comprising a lanthanide oxide ceramic material which is formed according to the improvement as claimed in claim 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1379396P | 1996-03-21 | 1996-03-21 | |
| US60/013,793 | 1996-03-21 | ||
| US08/794,317 US5759936A (en) | 1996-03-21 | 1997-02-03 | Lanthanide ceramic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2200160A1 CA2200160A1 (en) | 1997-09-21 |
| CA2200160C true CA2200160C (en) | 2004-06-15 |
Family
ID=26685259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002200160A Expired - Fee Related CA2200160C (en) | 1996-03-21 | 1997-03-17 | Lanthanide ceramic material |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5759936A (en) |
| EP (1) | EP0796827B1 (en) |
| JP (1) | JPH1053463A (en) |
| KR (1) | KR100253493B1 (en) |
| CN (1) | CN1195703C (en) |
| AT (1) | ATE198877T1 (en) |
| AU (1) | AU710795B2 (en) |
| CA (1) | CA2200160C (en) |
| DE (1) | DE69703943T2 (en) |
| DK (1) | DK0796827T3 (en) |
| ES (1) | ES2155638T3 (en) |
| NO (1) | NO312627B1 (en) |
| RU (1) | RU2201905C2 (en) |
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|---|---|---|---|---|
| US5932146A (en) * | 1996-02-29 | 1999-08-03 | Siemens Westinghouse Power Corporation | Air electrode composition for solid oxide fuel cell |
| US5916700A (en) * | 1998-01-23 | 1999-06-29 | Siemens Westinghouse Power Corporation | Lanthanum manganite-based air electrode for solid oxide fuel cells |
| EP0947484A1 (en) * | 1998-04-01 | 1999-10-06 | Haldor Topsoe A/S | Ceramic material for use in the separation of oxygen from gas mixture |
| JPH11322412A (en) * | 1998-05-13 | 1999-11-24 | Murata Mfg Co Ltd | Multiple oxide ceramic material and solid electrolyte fuel cell |
| US6653519B2 (en) * | 1998-09-15 | 2003-11-25 | Nanoscale Materials, Inc. | Reactive nanoparticles as destructive adsorbents for biological and chemical contamination |
| US6521202B1 (en) * | 1999-06-28 | 2003-02-18 | University Of Chicago | Oxygen ion conducting materials |
| EP1304164A1 (en) * | 2001-10-15 | 2003-04-23 | Haldor Topsoe A/S | Process for the production of mixed metal oxide containing catalysts |
| US6800204B2 (en) * | 2002-02-15 | 2004-10-05 | Clear Water Filtration Systems | Composition and process for removing arsenic and selenium from aqueous solution |
| US7670711B2 (en) * | 2002-05-03 | 2010-03-02 | Battelle Memorial Institute | Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices |
| DE10223746A1 (en) * | 2002-05-28 | 2003-12-18 | Honeywell Specialty Chemicals | Process for the production of mixed oxides containing lanthanum, strontium and manganese for electrodes in fuel cells |
| CN1314620C (en) * | 2003-04-25 | 2007-05-09 | 中国科学技术大学 | Perovskite Oxide Reinforced Dense Ceramic Oxygen Permeable Membrane Material and Its Oxygen Separator |
| DE10351955A1 (en) * | 2003-11-07 | 2005-06-16 | Forschungszentrum Jülich GmbH | Cathode material for a high-temperature fuel cell (SOFC) and a cathode producible therefrom |
| CN1294670C (en) * | 2004-03-03 | 2007-01-10 | 哈尔滨工业大学 | Method for preparing positive electrode material for lanthanum gallate solid electrolyte fuel cell |
| JP4876373B2 (en) | 2004-04-23 | 2012-02-15 | トヨタ自動車株式会社 | Cathode for fuel cell and method for producing the same |
| US7468218B2 (en) * | 2004-05-07 | 2008-12-23 | Battelle Memorial Institute | Composite solid oxide fuel cell anode based on ceria and strontium titanate |
| WO2010003926A1 (en) * | 2008-07-08 | 2010-01-14 | Technical University Of Denmark | Magnetocaloric refrigerators |
| CN102089912A (en) * | 2008-07-14 | 2011-06-08 | 株式会社村田制作所 | Materials for interconnectors, cell separation structures, and solid electrolyte fuel cells |
| US8139597B2 (en) * | 2008-10-03 | 2012-03-20 | Motorola Solutions, Inc. | Method for trunking radio frequency resources |
| US8279991B2 (en) | 2008-10-03 | 2012-10-02 | Motorola Solutions, Inc. | Method of efficiently synchronizing to a desired timeslot in a time division multiple access communication system |
| US8503409B2 (en) | 2010-04-15 | 2013-08-06 | Motorola Solutions, Inc. | Method for direct mode channel access |
| US8599826B2 (en) | 2010-04-15 | 2013-12-03 | Motorola Solutions, Inc. | Method for synchronizing direct mode time division multiple access (TDMA) transmissions |
| US8462766B2 (en) | 2011-03-07 | 2013-06-11 | Motorola Solutions, Inc. | Methods and apparatus for diffusing channel timing among subscriber units in TDMA direct mode |
| CN103319179B (en) * | 2013-05-14 | 2015-04-22 | 内蒙古工业大学 | A zirconium-doped modified La2NiMnO6 ceramic dielectric adjustable material and its preparation method |
| TWI594488B (en) * | 2014-07-08 | 2017-08-01 | Univ Nat Taipei Technology | Ceramic cathode material for solid oxide fuel cell and its preparation method |
| EP3829265A4 (en) * | 2018-07-23 | 2022-03-02 | China Tabacco Hubei Industrial Corporation Limited | CERAMIC HEATER AND METHOD OF PREPARING AND USING CERAMIC HEATER |
| RU2749746C1 (en) * | 2020-12-18 | 2021-06-16 | Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук | Electrode material for electrochemical devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4562124A (en) * | 1985-01-22 | 1985-12-31 | Westinghouse Electric Corp. | Air electrode material for high temperature electrochemical cells |
| US4851303A (en) * | 1986-11-26 | 1989-07-25 | Sri-International | Solid compositions for fuel cells, sensors and catalysts |
| SU1726443A1 (en) * | 1989-10-18 | 1992-04-15 | Уральский Научно-Исследовательский Химический Институт Научно-Производственного Объединения "Кристалл" | Method for preparation of rare-earth and alkali-earth element manganates |
| US5001021A (en) * | 1989-12-14 | 1991-03-19 | International Fuel Cells Corporation | Ceria electrolyte composition |
| US5407618A (en) * | 1990-08-13 | 1995-04-18 | The Boeing Company | Method for producing ceramic oxide compounds |
| JPH0644991A (en) * | 1992-07-27 | 1994-02-18 | Ngk Insulators Ltd | Manufacture of interconnector for solid electrolyte type fuel cell |
| US5604048A (en) * | 1993-02-26 | 1997-02-18 | Kyocera Corporation | Electrically conducting ceramic and fuel cell using the same |
| DE69403294T2 (en) * | 1993-08-16 | 1997-12-11 | Westinghouse Electric Corp | Stable air electrode for high-temperature electrochemical cells with solid oxide electrolyte |
| JP2846567B2 (en) * | 1993-09-03 | 1999-01-13 | 日本碍子株式会社 | Porous sintered body and solid oxide fuel cell |
| JP3011387B2 (en) * | 1993-11-10 | 2000-02-21 | 財団法人電力中央研究所 | Ceramics, cylindrical solid electrolyte fuel cells using the same, and flat solid electrolyte fuel cells |
| JP3358884B2 (en) * | 1994-08-12 | 2002-12-24 | 三菱重工業株式会社 | Interconnector material |
-
1997
- 1997-02-03 US US08/794,317 patent/US5759936A/en not_active Expired - Lifetime
- 1997-02-04 DE DE69703943T patent/DE69703943T2/en not_active Expired - Lifetime
- 1997-02-04 AT AT97101658T patent/ATE198877T1/en active
- 1997-02-04 ES ES97101658T patent/ES2155638T3/en not_active Expired - Lifetime
- 1997-02-04 EP EP97101658A patent/EP0796827B1/en not_active Expired - Lifetime
- 1997-02-04 DK DK97101658T patent/DK0796827T3/en active
- 1997-02-26 NO NO19970863A patent/NO312627B1/en not_active IP Right Cessation
- 1997-03-17 CA CA002200160A patent/CA2200160C/en not_active Expired - Fee Related
- 1997-03-18 AU AU16379/97A patent/AU710795B2/en not_active Ceased
- 1997-03-19 KR KR1019970009261A patent/KR100253493B1/en not_active Expired - Fee Related
- 1997-03-19 JP JP9066754A patent/JPH1053463A/en active Pending
- 1997-03-20 RU RU97104538/03A patent/RU2201905C2/en not_active IP Right Cessation
- 1997-03-20 CN CNB971030987A patent/CN1195703C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR100253493B1 (en) | 2000-04-15 |
| EP0796827A1 (en) | 1997-09-24 |
| KR970065473A (en) | 1997-10-13 |
| RU2201905C2 (en) | 2003-04-10 |
| AU710795B2 (en) | 1999-09-30 |
| CA2200160A1 (en) | 1997-09-21 |
| ES2155638T3 (en) | 2001-05-16 |
| CN1195703C (en) | 2005-04-06 |
| NO312627B1 (en) | 2002-06-10 |
| JPH1053463A (en) | 1998-02-24 |
| NO970863D0 (en) | 1997-02-26 |
| ATE198877T1 (en) | 2001-02-15 |
| NO970863L (en) | 1997-09-22 |
| CN1163244A (en) | 1997-10-29 |
| DE69703943D1 (en) | 2001-03-01 |
| DE69703943T2 (en) | 2001-05-23 |
| DK0796827T3 (en) | 2001-04-09 |
| EP0796827B1 (en) | 2001-01-24 |
| US5759936A (en) | 1998-06-02 |
| AU1637997A (en) | 1997-09-25 |
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