DE2858801C2 - Zirconia ceramic for use as solid electrolyte - Google Patents
Zirconia ceramic for use as solid electrolyteInfo
- Publication number
- DE2858801C2 DE2858801C2 DE2858801A DE2858801A DE2858801C2 DE 2858801 C2 DE2858801 C2 DE 2858801C2 DE 2858801 A DE2858801 A DE 2858801A DE 2858801 A DE2858801 A DE 2858801A DE 2858801 C2 DE2858801 C2 DE 2858801C2
- Authority
- DE
- Germany
- Prior art keywords
- al2o3
- ceramic
- zro2
- yb2o3
- mol
- 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.)
- Expired - Lifetime
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000000919 ceramic Substances 0.000 title claims abstract description 25
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 22
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 22
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012141 concentrate Substances 0.000 claims abstract 3
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 8
- 238000003825 pressing Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000003801 milling Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 230000003019 stabilising effect Effects 0.000 abstract 1
- 238000005382 thermal cycling Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000035939 shock Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4073—Composition or fabrication of the solid electrolyte
-
- 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
- C04B35/10—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 aluminium oxide
- C04B35/111—Fine ceramics
- C04B35/117—Composites
- C04B35/119—Composites with zirconium oxide
-
- 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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
- C04B35/488—Composites
- C04B35/4885—Composites with aluminium oxide
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
Die Erfindung geht aus von einem Formkörper für die Verwendung als Festelektrolyt nach der Gattung des Hauptanspruchs. Zirkoniumoxid, ZrO₂, tritt in drei verschiedenen Modifikationen auf, einer kubischen Hochtemperaturmodifikation, einer ebenfalls bei hohen Temperaturen stabilen tetragonalen Modifikation sowie einer bei niedrigen Temperaturen stabilen monoklinen Modifikation. Da die bei Temperaturänderungen auftretenden Modifikationswechsel mit Volumenänderungen verbunden sind, können in Formteilen ZrO₂ bei solchen Temperatur änderungen Risse und Brüche auftreten. Es ist daher notwendig und auch allgemein üblich, die kubische Hochtemperaturmodifikation teilweise oder vollständig zu stabilisieren, indem man ein oder mehrere Stabilisatoroxide, wie z. B. CaO, Y₂O₃ oder Yb₂O₃, zugibt. Durch diese Maßnahmen werden die unter Volumenänderungen ablaufenden Phasenumwandlungen bei Temperaturänderungen weitgehend oder vollständig unterbunden, so daß die daraus hergestellten Fremdkörper wesentlich thermostabiler sind. The invention relates to a shaped body for use as Solid electrolyte according to the genus of the main claim. Zirconium oxide, ZrO₂ occurs in three different modifications, one cubic High temperature modification, also at high temperatures stable tetragonal modification and one at low Temperatures stable monoclinic modification. Because of temperature changes occurring modification changes with volume changes are connected, in moldings ZrO₂ at such temperature Changes cracks and breaks occur. It is therefore necessary and also common, the cubic high temperature modification partially or fully stabilize by using an or several stabilizer oxides, such as. B. CaO, Y₂O₃ or Yb₂O₃, admits. Through these measures, those taking place under volume changes Phase changes with temperature changes largely or completely prevented, so that the foreign bodies produced from it are much more thermostable.
Ein solcher vollständig stabilisierter Zirkoniumoxid muß bei hohen Temperaturen gesintert werden, weil die Diffusion der Reaktionspartner im kubischen ZrO₂ stark gehemmt ist. Dies führt zu einem grobkörnigen Gefüge mit unzureichenden mechanischen Eigenschaften. - Durch Zusatz von geringen Mengen (<5 Mol-%) an Sinterhilfsmitteln kann die Sintertemperatur gesenkt werden; das Gefüge dieser Zirkoniumoxid- Keramik ist aber immer noch relativ grob und die mechanischen Eigenschaften sind daher noch nicht ausreichend. Als Sinterhilfsmittel kommen Al₂O₃, SiO₂ und Silicate in Frage. Mit SiO₂-haltigen Zusätzen wird allerdings auch besonders die Hochtemperaturfestigkeit der Keramik verschlechtert.Such a fully stabilized zirconium oxide must be sintered at high temperatures because of the diffusion the reaction partner in the cubic ZrO₂ is strongly inhibited. This leads to a coarse-grained structure with insufficient mechanical properties. - By adding minor The sintering temperature can affect amounts (<5 mol%) of sintering aids be lowered; the structure of this zirconium oxide Ceramics are still relatively coarse and the mechanical ones Properties are therefore not yet sufficient. As Sintering aids are Al₂O₃, SiO₂ and silicates in question. With SiO₂-containing additives, however, is also special the high temperature strength of the ceramic deteriorates.
Feinkörnige Gefüge lassen sich bei sogenannter teilstabilisierter ZrO₂-Keramik erzeugen, die schon bei niedrigen Temperaturen dicht sintert, z. B. bei Zugabe von 5 Mol-% Y₂O₃. Formteile aus solcher teilstabilisierter ZrO₂-Keramik haben nun hervorragende mechanische Eigenschaften. Sie können aber durch irreversible Phasenumwandlungen von meta stabilem tetragonalem ZrO₂ in monoklines ZrO₂ Gefügeschäden erleiden, insbesondere bei wiederholter Temperaturwechsel beanspruchung, die schließlich zum Bruch der Formteile führen können.Fine-grained structures can be found in so-called partially stabilized Generate ZrO₂ ceramics, even at low Temperatures densely sintered, e.g. B. with the addition of 5 mol% Y₂O₃. Molded parts made from such partially stabilized ZrO₂ ceramics now have excellent mechanical properties. they but can be caused by irreversible phase transformations of meta stable tetragonal ZrO₂ in monoclinic ZrO₂ structural damage suffer, especially with repeated temperature changes stress that eventually leads to breakage of the molded parts being able to lead.
Aus der DE-AS 17 71 273 ist ein Verfahren zur Herstellung von Keramikteilen aus stabilisiertem Zirkoniumoxid bekannt, das Al₂O₃ enthält. Dieses Verfahren setzt hohe Sintertemperaturen von 1600°C bis 1900°C voraus, damit sich die im Vorprodukt bei 1100 bis 1300°C gebildeten Ca-Verbindungen mit Al₂O₃, Fe₂O₃ und/oder SiO₂ wieder auflösen/zersetzen und somit CaO zur Stabilisierung des ZrO₂ liefern können.DE-AS 17 71 273 describes a process for the production known from ceramic parts made of stabilized zirconium oxide, that contains Al₂O₃. This process sets high sintering temperatures from 1600 ° C to 1900 ° C ahead, so that the in the pre-product Ca compounds formed at 1100 to 1300 ° C. Dissolve / decompose Al₂O₃, Fe₂O₃ and / or SiO₂ and thus can provide CaO to stabilize the ZrO₂.
Aus der DE-PS 27 54 522 ist ein weiteres Verfahren zur Herstellung eines festen Mischelektrolytmaterials bekannt, das aus mindestens einer nicht-elektrolytischen Komponente bzw. Phase und mindestens einer Komponente bzw. Phase, die ein guter Sauerstoffionenleiter ist, besteht, wobei die Körnchen der Sauerstoffionen leitenden Komp ponente 25 bis 72 Vol.-% des Gemisches ausmachen. Dabei geht es in der Hauptsache darum, die Wärmeausdehnungskoeffizienten zweier unterschiedlicher Materialien anzupassen, wobei die beste Anpassung an Aluminiumoxid durch ein Mischelektrolytmaterial mit einem Gehalt an Aluminiumoxid als nicht-elektrolytischer Komponente von 50% erreicht wird.From DE-PS 27 54 522 is another method of manufacture a solid mixed electrolyte material known from at least a non-electrolytic component or phase and at least a component or phase that is a good oxygen ion conductor is, with the granules of the oxygen ion conductive comp Component 25 to 72 vol .-% of the mixture. It goes in the main thing is the thermal expansion coefficient of two different ones Adapt materials, being the best adaptation to Alumina through a mixed electrolyte material containing Alumina achieved as a non-electrolytic component of 50% becomes.
Es ist Aufgabe der Erfindung, die Eigenschaften der Formkörper für die Verwendung als Festelektrolyt in Meßfühlern bezüglich Ansprechzeit und Beständigkeit zu verbessern. Diese Aufgabe wird durch die kennzeichnenden Merkmale des Hauptanspruchs gelöst.It is an object of the invention to determine the properties of the shaped body the use as a solid electrolyte in sensors with regard to response time and improve durability. This task is accomplished by the characteristic features of the main claim solved.
Wesentliches Merkmal der ZrO₂-Keramikwerkstoffe gemäß Hauptpatent 28 10 134 ist, daß ihr Gefüge durch Zusatz von feinteiligem Al₂O₃ bzw. Al₂O₃-Verbindungen, die das Kornwachstum bremsen, sehr feinkörnig gehalten wird. Die ZrO₂-Werkstoffe haben damit hohe Werte der mechanischen Festigkeit und der Temperaturschockbeständigkeit. Al₂O₃-Zusätze erhöhen außerdem die Wärmeleitfähigkeit der Keramik und verringern ihre thermische Ausdehnung, womit die Thermoschockbeständigkeit weiter gesteigert wird.Essential feature of the ZrO₂ ceramic materials according to the main patent 28 10 134 is that their structure by adding finely divided Al₂O₃ or Al₂O₃ compounds that slow down grain growth, is kept very fine-grained. The ZrO₂ materials therefore have high Mechanical strength and thermal shock resistance values. Al₂O₃ additives also increase the thermal conductivity of the ceramic and reduce its thermal expansion, with which the Thermal shock resistance is further increased.
Wenn die O₂-Ionenleitfähigkeit der ZrO₂-Keramik bei ihrer Anwendung von Bedeutung ist, muß der Al₂O₃-Zusatz in bestimmten Grenzen gehalten werden. Bei einer vollstabilisierten ZrO₂-Keramik mit 7,5 Mol.-% Y₂O₃ und 92,5 Mol.-% ZrO₂ verringert ein Al₂O₃-Zusatz von 40 Vol.-% die Leitfähigkeit gerade so stark, daß sie die von teilstabilisierter Keramik mit 5 Mol.-% Y₂O₃ und 95 Mol.-% ZrO₂ ohne Al₂O₃-Zusatz eben erreicht. Mit mehr als 50 Vol.-% Al₂O₃ fällt die Leitfähigkeit der genannten vollstabi lisierten Keramik beschleunigt ab. Der Abfall der elektrischen Leitfähigkeit, der durch Al₂O₃-Zusätze zu mit Y₂O₃ stabilisierter Keramik enststeht, kann durch Substitution des Y₂O₃ durch Yb₂O₃ teilweise kompensiert werden.If the O₂ ion conductivity of ZrO₂ ceramics in their application is of importance, the Al₂O₃ addition must be within certain limits being held. With a fully stabilized ZrO₂ ceramic 7.5 mol .-% Y₂O₃ and 92.5 mol .-% ZrO₂ reduced one Al₂O₃ addition of 40 vol .-% just as strong conductivity that they are the partially stabilized ceramic with 5 mol .-% Y₂O₃ and 95 mol .-% ZrO₂ without Al₂O₃ addition just reached. With more than 50 vol .-% Al₂O₃ falls the conductivity of the full stabilization accelerated ceramic. The drop in electrical conductivity, the stabilized by Al₂O₃ additives with Y₂O₃ Ceramic arises, can by substitution of Y₂O₃ by Yb₂O₃ are partially compensated.
Es ist aber auch möglich, Formkörper aus zwei oder mehr Massen mit unterschiedlich hohen Al₂O₃-Gehalten zusammenzusintern. Voraussetzung hierfür ist, daß die Massen annähernd gleich stark schwinden. Dies kann mit der Mahlfeinheit und mit einer Variation von organischen Preßhilfsmitteln bzw. Bindern abgestimmt werden.However, it is also possible to use moldings made from two or more materials to sinter different levels of Al₂O₃. requirement the reason for this is that the masses shrink almost equally. This can be done with the fineness and with a variation of organic Pressing aids or binders are matched.
Durch die Ausbildung des Formkörpers gemäß Anspruch 1 aus zwei oder mehr Teilen mit unterschiedlich hohem Aluminiumoxid-Gehalt wird einerseits, durch den Teil oder die Teile mit relativ geringerem Aluminiumoxid- Gehalt, eine schnellere Ansprechzeit beim Aufheizen des als Meßfühler zur Bestimmung des Sauerstoffgehaltes in Abgasen ver wendeten Formkörpers gewährleistet und andererseits, durch den Teil oder die Teile mit relativ höherem Aluminiumoxid-Gehalt und somit schlechterer Leitfähigkeit, das Auftreten eines inneren Kurzschlusses zwischen den Elektroden verhindert.By forming the shaped body according to claim 1 from two or more parts with different levels of aluminum oxide are through the part or parts with relatively less alumina Salary, a faster response time when heating the ver as a sensor for determining the oxygen content in exhaust gases guaranteed molded body and on the other hand, by the part or the parts with a relatively higher alumina content and thus poor conductivity, the occurrence of an internal short circuit prevented between the electrodes.
In vorteilhafter Weise kann dabei die Kuppe des geschlossenen Rohrendes eines fingerförmigen Formkörpers aus Al₂O₃-armer oder Al₂O₃-freier stabilisierter ZrO₂ bestehen, die eine hohe O₂-Ionenleitfähigkeit hat, und der restliche Körper aus einer Al₂O₃-reichen derartigen Keramik, die eine hohe Temperaturbeständigkeit aufweist.In an advantageous manner, the top of the closed pipe end can a finger-shaped body made of poor Al₂O₃ or Al₂O₃-free stabilized ZrO₂ consist of a high Has O₂ ion conductivity, and the rest of the body from one Al₂O₃-rich ceramics that have a high temperature resistance having.
Die Erfindung wird anhand des folgenden Ausführungsbeispiels näher erläutert.The invention is based on the following embodiment explained in more detail.
Vormischen im Mischaggregat;
Mahlen der Vormischung in Kugelmühle auf Kornfeinheit <1 µm;
Granulieren mit Zusatz von organischen Bindemitteln (<3 Gew.-%);
Verpressen zu Formkörpern;
Sintern in oxidierender Sinteratmosphäre bei Temperaturen zwischen 1400°C und 1650°C.Premixing in the mixing unit;
Grinding the premix in a ball mill to a particle size of <1 µm;
Granulation with the addition of organic binders (<3% by weight);
Pressing to shaped bodies;
Sintering in an oxidizing sintering atmosphere at temperatures between 1400 ° C and 1650 ° C.
Die nach dem Beispiel hergestellten Formkörper wurden verschiedenen Prüfverfahren unterworfen, von denen hier insbesondere die Biegebruchfestigkeit sowie die Temperaturschockbeständigkeit interessieren. Die Biegebruchfestigkeit wurde durch radiale Belastung von Ringproben ermittelt, während die Temperaturschockbeständigkeit durch eine Schallemissionsanalyse bei einseitiger Abschreckung von Probekörpern mit einem Kühlluftstrahl geprüft wurde, wobei das Aufheizen der Probekörper mit linearem Temperaturanstieg und periodischen Abkühlen erfolgte. Vergleiche mit entsprechenden Probekörpern aus teilstabilisierter Keramik, wie sie oben im Stand der Technik genannt sind, ergaben, daß die Formkörper aus der erfindungsgemäßen ZrO₂-Keramik die gleiche Biegebruchfestigkeit aufweisen wie die aus der teilstabilisierten Keramik. Während die mechanische Festigkeit der vollstabilisierten Keramik schon mit Zusätzen von 8 Vol.-% Al₂O₃ der der teilstabilisierten annähernd gleichkommt, erreicht die Thermoschockbeständigkeit der vollstabilisierten Keramik die der teilstabilisierten erst bei Al₂O₃-Zusätzen <15 Vol.-% Al₂O₃. Dagegen ist die Gefügestabilität der erfindungsgemäßen Keramik derjenigen der teilstabilisierten Keramik weit überlegen.The moldings produced according to the example were different Subject to test procedures, of which here in particular the flexural strength and the temperature shock resistance interested. The flexural strength was determined by radial loading of ring samples is determined while the Resistance to temperature shock through a sound emission analysis with one-sided deterrence of test specimens with a Cooling air jet was checked, heating the test specimen with linear temperature rise and periodic cooling took place. Compare with corresponding test specimens partially stabilized ceramics, as described above in the prior art are mentioned, showed that the moldings from the invention ZrO₂ ceramic has the same flexural strength have like the partially stabilized ceramic. While the mechanical strength of the fully stabilized ceramic already with the addition of 8 vol .-% Al₂O₃ of the partially stabilized is almost the same as the thermal shock resistance of fully stabilized ceramics that of partially stabilized ceramics with Al₂O₃ additives <15 vol .-% Al₂O₃. In contrast, the structural stability the ceramics according to the invention that of the partially stabilized Ceramics far superior.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2858801A DE2858801C2 (en) | 1978-03-09 | 1978-03-09 | Zirconia ceramic for use as solid electrolyte |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2858801A DE2858801C2 (en) | 1978-03-09 | 1978-03-09 | Zirconia ceramic for use as solid electrolyte |
| DE19782810134 DE2810134A1 (en) | 1978-03-09 | 1978-03-09 | ZIRCONIUM OXIDE CERAMICS WITH A FINE-GRAY AND THERMALLY STABLE STRUCTURE AND HIGH THERMAL SHOCK RESISTANCE, MOLDED BODIES MANUFACTURED FROM THEM, METHOD FOR MANUFACTURING THE MOLDED BODIES AND THEIR USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2858801C2 true DE2858801C2 (en) | 1991-08-01 |
Family
ID=25774018
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2858801A Expired - Lifetime DE2858801C2 (en) | 1978-03-09 | 1978-03-09 | Zirconia ceramic for use as solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2858801C2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1771273B2 (en) * | 1968-04-27 | 1976-05-06 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | PROCESS FOR MANUFACTURING PARTS FROM ZIRCONIA CERAMICS |
| DE2754522A1 (en) * | 1976-12-07 | 1978-06-08 | Commw Scient Ind Res Org | SOLID MIXED ELECTROLYTE MATERIAL AS WELL AS OXYGEN SENSORS THEREOF AND PROCESS FOR THE PRODUCTION OF IT |
-
1978
- 1978-03-09 DE DE2858801A patent/DE2858801C2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1771273B2 (en) * | 1968-04-27 | 1976-05-06 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | PROCESS FOR MANUFACTURING PARTS FROM ZIRCONIA CERAMICS |
| DE2754522A1 (en) * | 1976-12-07 | 1978-06-08 | Commw Scient Ind Res Org | SOLID MIXED ELECTROLYTE MATERIAL AS WELL AS OXYGEN SENSORS THEREOF AND PROCESS FOR THE PRODUCTION OF IT |
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