WO2004106262A1 - Ceramique oxydee a base d'oxyde d'aluminium - Google Patents

Ceramique oxydee a base d'oxyde d'aluminium Download PDF

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Publication number
WO2004106262A1
WO2004106262A1 PCT/EP2004/005571 EP2004005571W WO2004106262A1 WO 2004106262 A1 WO2004106262 A1 WO 2004106262A1 EP 2004005571 W EP2004005571 W EP 2004005571W WO 2004106262 A1 WO2004106262 A1 WO 2004106262A1
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Prior art keywords
phase
ceramic material
oxide ceramic
wear
mixture
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PCT/EP2004/005571
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German (de)
English (en)
Inventor
Wolfgang Burger
Volker Sommer
Aude Muller
Carmen Hesch
Ana HERRÁN FUERTES
Dietmar Klotz
Simon Heinzmann
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Ceramtec GmbH
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Ceramtec GmbH
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Priority claimed from DE102004023765A external-priority patent/DE102004023765A1/de
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Publication of WO2004106262A1 publication Critical patent/WO2004106262A1/fr
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Definitions

  • the invention relates to an oxide-ceramic material based on aluminum oxide (Al 2 O 3 ), its production and molded articles made from this material.
  • ZPTA materials Zirconia-Platelet-Toughened Alumina
  • GGV cast materials
  • the wear is not yet satisfactory.
  • the size and number of pores in the material is an important factor.
  • pores in the surface of foils have a negative impact on the life of the screens, especially when calcium carbonate is used as a filler.
  • the object is achieved according to the invention by an oxide ceramic material with the following structure:
  • the material consists of two main components.
  • the one main component, the wear phase consists of a polycrystalline ⁇ -Al 2 ⁇ 3 -based oxide ceramic with a very small grain size, such as the so-called sol-gel grain known from the abrasive industry, for example Cubitron 321® from 3M, or a single-crystalline corundum , oxidic fibers or whiskers.
  • the size of these particles is in the range from 2 ⁇ m to 40 ⁇ m, which is why the wear phase can also be referred to as microceramic.
  • the listed components of the wear phase are embedded individually or as a mixture of two or more of these components in any quantity ratio in a second main component, a binding phase for the wear phase.
  • This binding phase is brought into a liquid state compared to the first phase and encloses the first, non-liquefied wear phase after it has solidified.
  • the binding phase which should not react with the wear phase, can be: a eutectic mixture, for example Al 2 ⁇ 3 -Zr ⁇ 2 or Al 2 ⁇ 3 -Zr ⁇ 2 -Ti ⁇ 2 , or other low-melting eutectics such as alkaline earth metal or rare earth titanate, inorganic glass or a mixture of the materials suitable as the binding phase.
  • the binding phase has the same meaning in the composition of the overall material as, for example, cobalt in hard metal materials.
  • Nanoscale powders are preferably used for the inorganic binding phase which is formed from the eutectic mixture.
  • Components Al 2 ⁇ 3 -Zr ⁇ 2 or Al 2 ⁇ 3 -Zr ⁇ 2 -Ti ⁇ 2 is preferably between 50 nm and 250 nm.
  • the eutectic mixture has a volume fraction of 5% to 40% in
  • the eutectic composition according to the phase diagram, see FIG. 1 is 57.4 wt% aluminum oxide and 42.6 wt% zirconium oxide.
  • Cerium oxide is added in a concentration of 3 wt% to 25 wt%.
  • Aluminum oxide is preferably made from an aluminum salt or a
  • the nanoscale zirconium oxide is preferably obtained from a gas phase process, for example by a reaction of
  • the nanoscale eutectic mixture of the individual components Al 2 O 3 and ZrO 2 or Al O 3 , ZrO and TiO 2 as the binding phase is produced by mixed grinding, preferably in a continuous attritor mill.
  • An alumina-zirconia mixture in the eutectic range in a composition of Al 2 O 3 from 54 wt% to 61 wt% and Z D2 from 39 wt% to 46 is used as the binding phase wt% used.
  • the eutectic composition itself is preferably chosen: Al 2 O 3 with 57.4 wt% and ZrO 2 with 42.6 wt%.
  • Glass and the low-melting eutectics for example the alkaline earth metals or rare earth titanates, have a similar behavior.
  • these materials have the advantage that a change in the microstructure of the microceramic used in the wear phase, in particular the grain growth in the sol-gel grain or reactions of the sol-gel grain with the binding phase, can be almost excluded.
  • Materials with a low eutectic temperature include, for example, alkaline earth metal or rare earth titanates of the following compositions with their melting temperature in the eutectic: MgNb 2 O 6 -Nb 2 O 5 (1430 ° C), CaNb 2 O 6 - Nb 2 O 5 (1370 ° C), Sr 2 Nb 10 O 27 -Nb 2 ⁇ 5 (1290 ° C), La 4 Ti 9 O 24 (1445 ° C), Nd 4 Ti 9 O 24 (1440 ° C).
  • the composition of the glass binding phase is chosen so that its components or the glass powder melt during sintering, but the components of the wear phase do not. It is also possible to use glass powders of the appropriate composition in nanoscale particle size.
  • the temperatures range from about 500 ° C (soda-potash-lime glasses) to about 1250 ° C (boron-alumina glasses).
  • the proportion of the glass phase or the low melting eutectics with 5% to 40% by volume corresponds to the proportion of the binding phase from the eutectic mixture. Due to the sintering temperatures, which correspond to the processing temperatures in the glass industry, their processes are also suitable for shaping. The shaping can take place, for example, in the viscous state of the binding phase by pressing in conventional glass molds. This enables the production of shaped bodies with complex geometries.
  • composition of a glass suitable for the binding phase is listed below: 0.06 wt% MgO, 0.01 wt% Fe 2 O 3 , 0.02 wt% Na 2 O, 0.09 wt% ZrO 2 , 0.01 wt % SrO, 0.02 wt% CeO 2 , 6 wt% AI 2 O 3 , 64 wt% SiO 2 , ⁇ 0.01 wt% TiO 2 , 25 to 30 wt% CaO, 0.01 wt% K 2 O, 0.1 wt% Ba 2 O.
  • the binding phase can also be formed from a mixture of eutectic mixture and glass in the form of its components or glass powder or materials with a low eutectic temperature.
  • the softening and melting temperatures of the glass or the materials with a low eutectic temperature and the eutectic mixture should correspond within narrow limits.
  • sol-gel grain as the wear phase is particularly advantageous. It is extremely tough and very wear-resistant. These properties are based on the one hand on the microstructure and on the other hand on the chemical composition.
  • the grain With regard to the microstructure, the grain consists of extremely fine primary particles that are sintered into the corresponding agglomerates of different sizes. The extremely fine primary particles are generated by the sol-gel technology and justify the high wear resistance.
  • the sol-gel grains In their chemical composition, the sol-gel grains have other accompanying elements in addition to aluminum oxide. The accompanying elements form ternary phases with the aluminum oxide, which make them tough.
  • the chemical composition of these so-called microceramics is very complex, for example from:
  • the grain has a complex polycrystalline microstructure, composed of crystallites of alpha alumina, spinel (MgA ⁇ O ⁇ and hexagonal rare earth aluminates.
  • the material according to the invention is produced in the following steps: in the binding phase from a eutectic mixture or from components of a glass or from glass powder or materials with a low eutectic temperature, so-called low-melting eutectics, or a mixture of eutectic mixture and glass or glass powder or low-melting Eutectics are added to the wear phase an amount of commercially available sol-gel grain or corundum, fibers, or whiskers or a mixture of two or more of these components, which is tailored to the intended use.
  • the binding phase is usually in the form of slip.
  • the binder phase and the added components of the wear phase are homogenized by mechanical mixing, preferably by means of rotary grinding, but can also be carried out in a vibratory mill. Furthermore, the mixture can also be produced in so-called microreactors.
  • Fibers or whiskers or a mixture of two or more of these If wear components are present in a homogeneous state, this mixture is constantly stirred to avoid sedimentation. It may also be necessary to add dispersing agents to the suspension in order to avoid sedimentation of the microceramics.
  • binders are added to the suspension, for example polyacrylate or polyvinyl alcohol. This suspension is then dried in a spray drying process. The spray grain is then pressed into a shaped body. Alternatively, the slip can also be processed further using other shaping processes, for example the slip casting process.
  • a particularly advantageous method is the so-called DCC method.
  • the slurry being coagulated by an enzyme-catalyzed chemical reaction, it is possible in particular to produce components close to the final shape.
  • the gel casting process is also suitable for shaping close to the final shape.
  • monomeric chemical compounds are added to the slip, which are polymerized by thermal or catalytic reactions.
  • Sintering is understood here to mean any suitable heat treatment at a temperature at which the binding phase is converted into a liquid state. After cooling, it is in the status di .
  • the eutectic temperature is decisive. If an over- or under-eutectic binding phase is used, the sintering temperature must be adjusted accordingly in order to achieve a liquid binding phase for the already sintered microceramics.
  • the temperature to be set depends on the Melting temperature of the glass-forming components or the melting temperature of the glass powder. If necessary, chemical solid-state reactions are initiated deliberately during sintering between the glass phase and microceramic. The softening and melting temperatures of the glass or the eutectic mixture should correspond within narrow limits. The same procedure should be followed if other materials with a low eutectic temperature are used.
  • Pore-free surfaces of wear parts are particularly advantageous in the paper industry, for example, because added pores in the components used there have a negative impact on paper quality and accelerate component wear.
  • the pore-free nature of foil segments prevents the fillers from getting stuck in the pores and thus significantly reduces screen wear.
  • Hot isostatic post-compression is a possible option for further compression.
  • the shaped body obtained after sintering can be given its predetermined contour and surface by hard machining with diamond tools, by grinding or lapping. Such processing takes place when the molded body is to be designed as a high-precision component.
  • Typical applications for such shaped sintered bodies are, in particular, indexable inserts for the machining of cast and steel materials. Furthermore, these materials can also be used in a wide variety of wear applications, for example as thread guiding devices, texturing disks or thread brakes in the textile industry, as welding rollers or as wear parts in the Paper industry such as foils and drainage technology components.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

Dans l'état de la technique, les matières ZPTA (Ziconia-Platelet-Toughened Alumina) constituent les céramiques oxydées les plus dures, les plus tenaces et les plus résistantes. Ces matières sont utilisées pour le travail du métal, de préférence pour l'usinage avec enlèvement de copeaux, ou bien pour constituer des pièces d'usure. Le comportement à l'usure et la porosité de ces pièces ne sont toutefois pas encore satisfaisants. L'invention concerne donc une céramique oxydée à base d'une phase d'usure constituée de grains sol-gel frittés de façon dense ou de corindon,ou de fibres ou de Whisker, ou bien d'un mélange d'au moins deux de ces composants. Cette céramique oxydée se caractérise en ce que la phase d'usure est incorporée dans une phase de liaison inorganique et que la température de fusion de la phase de liaison est inférieure à la température de fusion de la phase d'usure.
PCT/EP2004/005571 2003-05-28 2004-05-24 Ceramique oxydee a base d'oxyde d'aluminium Ceased WO2004106262A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10324233 2003-05-28
DE10324233.3 2003-05-28
DE102004023765.4 2004-05-11
DE102004023765A DE102004023765A1 (de) 2003-05-28 2004-05-11 Oxidkeramischer Werkstoff auf der Basis von Aluminiumoxid

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WO2004106262A1 true WO2004106262A1 (fr) 2004-12-09

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4543107A (en) * 1984-08-08 1985-09-24 Norton Company Vitrified bonded grinding wheels containing sintered gel aluminous abrasive grits
US5143522A (en) * 1979-11-09 1992-09-01 Washington Mills Electro Minerals Corporation Abrasive products containing fused alumina zirconia and reduced titania
WO2001056947A1 (fr) * 2000-02-02 2001-08-09 3M Innovative Properties Company PARTICULES ABRASIVES EUTECTIQUES Al2O3-Y2O3 FUSIONNEES, ARTICLES ABRASIFS ET LEURS PROCEDES DE PRODUCTION ET D'UTILISATION

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5143522A (en) * 1979-11-09 1992-09-01 Washington Mills Electro Minerals Corporation Abrasive products containing fused alumina zirconia and reduced titania
US5143522B1 (en) * 1979-11-09 1998-01-06 Washington Mills Electro Miner Abrasive products containing fused alumina zirconia and reduced titania
US4543107A (en) * 1984-08-08 1985-09-24 Norton Company Vitrified bonded grinding wheels containing sintered gel aluminous abrasive grits
WO2001056947A1 (fr) * 2000-02-02 2001-08-09 3M Innovative Properties Company PARTICULES ABRASIVES EUTECTIQUES Al2O3-Y2O3 FUSIONNEES, ARTICLES ABRASIFS ET LEURS PROCEDES DE PRODUCTION ET D'UTILISATION

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