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WO2013004637A2 - Procédé de fabrication d'une céramique poreuse - Google Patents

Procédé de fabrication d'une céramique poreuse Download PDF

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Publication number
WO2013004637A2
WO2013004637A2 PCT/EP2012/062761 EP2012062761W WO2013004637A2 WO 2013004637 A2 WO2013004637 A2 WO 2013004637A2 EP 2012062761 W EP2012062761 W EP 2012062761W WO 2013004637 A2 WO2013004637 A2 WO 2013004637A2
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Prior art keywords
zirconium
porous ceramic
cerium
ceramic
hafnium
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WO2013004637A3 (fr
Inventor
Uwe Glatzel
Christian Konrad
Rainer VÖLKL
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Universitaet Bayreuth
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Universitaet Bayreuth
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    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/04—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by dissolving-out added substances
    • 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
    • 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
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/401—Alkaline earth metals
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/404—Refractory metals
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/405—Iron group metals
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/407—Copper

Definitions

  • the invention relates to a novel process for producing a porous ceramic comprising zirconium, cerium and / or hafnium oxide.
  • a porous ceramic has special properties, such as a high temperature and thermal shock resistance, a large micro-crack stability and biostability and compatibility - which they prefer for special applications.
  • a porous ceramic is used, for example, as technical ceramics for components and components, in medicine as a prosthesis, as a support framework for the ingrowth of bone material or as a dental implant, in environmental and process engineering as a catalyst support, as a filter material and as an electrical and thermal insulation material.
  • Soc, 85; 2002 known to use an oxide powder as a pore former, which is reduced after the sintering process and dissolved out of the component.
  • a multimodal pore size distribution is achieved in these methods in which pore formers of different sizes are used.
  • porous zirconia ceramics Another way of making a porous zirconia ceramics is from C.R. Rambo, J. Cao and H. Sieber; Preparation and properties of highly porous, biomorphic YSZ ceramics; Materials Chemistry and Physics; 2004 known.
  • a preform z As wood is impregnated with a zirconium-containing solution, pyrolyzed and fired at a temperature up to 1550 ° C, the preform burns out and only the oxide skeleton remains.
  • US Pat. No. 4,203,772 describes the production of a porous zirconium oxide ceramic, the porosity being achieved by the use of zirconium hydroxide.
  • the described methods require relatively high temperatures for sintering the zirconia. Furthermore, the achievement of a defined porosity can not be adequately controlled with the described methods. Thus, it may undesirably lead to a partially closed porosity, as may be the distribution of the oxide particles is not homogeneous. This is disadvantageous for the infiltration in the preparation of catalysts and in particular for use as a filter material.
  • the object of the invention is to find an alternative method for producing a porous ceramic comprising zirconium, cerium and / or hafnium oxide, which avoids in particular the disadvantages of a sintering process.
  • This object is achieved in that zirconium, cerium and / or hafnium is melted together with at least one noble metal and at least one oxygen affinity element to a melt, the melt is cooled under solidification, the solidified melt is subjected to internal oxidation in which zirconium, cerium and / or hafnium and the at least one oxygen-affine element oxidize, and finally the more noble metal is dissolved out so that the porous ceramic remains.
  • the invention is based on the consideration of omitting, as far as possible, a sintering process for producing a porous ceramic on account of the disadvantages mentioned.
  • the invention recognizes that this can be achieved by no longer using ceramic starting materials for the production. Rather, the production is now carried out by fusion metallurgy, whereby metallic starting materials including the oxygen-affine additive are melted. The melt is then cooled while solidification.
  • the invention then resorts to the principle of internal oxidation.
  • the internal oxidation basically occurs when two or more elements are present within an alloy, which have very different inclinations for the oxidation.
  • Each of these elements can be assigned a temperature-dependent oxygen partial pressure (or oxygen activity) at which the element oxidizes. If the oxygen partial pressure in a gaseous environment is lower than the equilibrium partial pressure, or if the oxygen activity in a solid solution is below the equilibrium activity, the element considered is not oxidized.
  • the achievement of the invention is to use the principle of the internal oxidation now for the production of a porous ceramics.
  • the invention overcomes the problem that the internal oxidation is a process dependent on the rate of diffusion of the oxygen. Internal areas of a metal or alloy are oxidized so far only slowly and usually incomplete, since oxygen must penetrate from the outside into the volume. For this reason, thin material layers, such as sheets or the like, are primarily treated to produce dispersion-strengthened materials.
  • the invention makes use of the knowledge found in connection with dispersion-strengthened materials that oxygen-affine additives are able to accelerate the process of internal oxidation, as described in B. Kloss et. al., Fast internal oxidation of Ni-Zr-Y alloys at low oxygen pressure, Oxide Met, Vol. 61, Nos. 3/4, April 2004.
  • oxygen-affine additive is added to the melt in addition to a base metal such as zirconium, cerium or hafnium and a noble metal, this not only accelerates the internal oxidation of the solidified melt, so that a complete oxidation of the less noble metal can be achieved, but leads also to a porous coherent oxide ceramic within the remaining matrix of the more noble metal. When finally the nobler metal is dissolved out, this coherent structure remains as the produced porous oxide ceramic.
  • the oxygen-affine additive is also oxidized in the internal oxidation. The oxygen-affine additive is thus usually part of the finished ceramic.
  • oxygen-affine is to be understood as referring to the nobler metal. according to characterized in that its reaction with oxygen must be possible, while the noble metal does not oxidize at the same time.
  • the oxygen partial pressure during the internal oxidation is chosen to be greater in particular than the equilibrium oxygen partial pressure of the two base elements. If it is also smaller than the equilibrium oxygen partial pressure of the noble element, no external oxidation of the noble element occurs. If it is higher, the noble element is also oxidized. In this case, this oxide layer is preferably mechanically removed before dissolving the metallic matrix.
  • the times for the internal oxidation are roughly between 1 and 100 hours for a material thickness of one millimeter.
  • Oxidation in solution is possible in principle. However, it is not technically preferred because the rate of diffusion of oxygen at the temperatures achievable in solution is not sufficient to penetrate quickly enough into the material interior.
  • the base metals zirconium, cerium and hafnium. Compared to zirconium, cerium or hafnium, more noble metals can be selected according to the electrochemical stress series.
  • the pore size of the ceramic structure can be easily and definedly influenced by the composition of the starting melt and by the process control during solidification of the melt in the described method.
  • Starting with a melt of zirconium, cerium and / or hafnium with the other nobler metal solidifies the cooling of low-alloyed metals primarily the nobler metal.
  • the residual melt solidifies in a mostly elektica reaction and forms secondarily particles of noble metal and intermetallic phases.
  • the solidified melt there is thus an inhomogeneous distribution of the nobler and less noble metals. Due to the structure of the failed pure noble metal coarse pores are given. There is no internal oxidation. The coarse pores become smaller, the faster the cooling process takes place.
  • the pore size moves here in a range between 2 ⁇ and 50 ⁇ .
  • the secondary particles of noble metal fine pores are caused whose pore size is in the range between 1 and 2 ⁇ .
  • the cooling rate the size of these first two types of pores can be adjusted.
  • tertiary noble metal is precipitated, whereby micro pores are defined whose pore size is in a range below 1 ⁇ m.
  • a porous ceramic can thus be achieved by process control, which has coarse, fine and very small pores, and in particular has a multimodal pore distribution.
  • process control which has coarse, fine and very small pores, and in particular has a multimodal pore distribution.
  • a porous ceramic can be produced substantially only with one or two of these types of pores.
  • the starting materials are melted under vacuum or under inert gas so as to minimize the oxidation of the oxygen-affine elements during the melting process.
  • the more noble metal to zirconium, cerium or hafnium is selected from the group consisting of nickel, iron, cobalt and copper. These metals are available at relatively low cost and can also be dissolved out of the inner-oxidized workpiece chemically, for example by acid treatment.
  • the oxygen-affine element is selected from the group consisting of magnesium, calcium, scandium, titanium, thorium, yttrium or lanthanides. From the lanthanides, preference is given to choosing cerium, gadolinium or ytterbium. Cerium acts as an oxygen-affine element with regard to the nobler metal. It can also remain as an oxide in the finished ceramic. It has been found that these high oxygen affinity elements are capable of substantially accelerating the internal oxidation of a zirconium, cerium and / or hafnium-containing alloy. For the dissolution of the noble metal this example, can be solved galvanically. The nobler metal is preferably dissolved out chemically, in particular by means of an acid treatment.
  • hydrochloric, hydrofluoric or nitric acid is suitable for this purpose.
  • acid treatment is preferably carried out at a temperature between 20 ° C and 70 ° C and can be assisted by pressure.
  • the oxygen-affinity additive oxide may or may not remain in the ceramic as mentioned.
  • the porous ceramic is advantageously produced with a content of zirconium, cerium and / or hafnium between 2% by weight and 50% by weight.
  • the proportion of zirconium, cerium and / or hafnium is chosen here in accordance with the desired pore volume content of the porous ceramic. The larger the total content of zirconium, cerium and / or hafnium, the lower the pore volume fraction in the finished ceramic, since the matrix of the remaining nobler metal is dissolved out.
  • the porous ceramic is prepared with a total content of the oxygen affinity element between 0.1 wt .-% and 10 wt .-%.
  • the porous ceramic is prepared with a weight ratio of zirconium, cerium and / or hafnium to the sum of the oxygen-affine elements between 40: 1 and 1: 1, in particular between 5: 1 and 10: 1. It has been found that the rate of internal oxidation at such a weight ratio of zirconium, cerium and / or hafnium is greatly increased over the oxygen affinity element. In the range between 5: 1 and 10: 1, a maximum of the oxidation rate is achieved.
  • the range data mentioned above for the production of the ceramic refer in each case to the starting alloy.
  • the melt produced is preferably poured off.
  • the melt can this both in metallic molds, especially by continuous casting, as well as in ceramic shell molds, z. B. after the investment casting process, are poured.
  • investment casting even complicated geometries can be realized already during prototyping, which later also has the finished ceramic component.
  • casting conditions of the finished alloy material can also be influenced by casting conditions. In addition to the alloy composition and the process control during cooling, the process control during casting thus represents another possibility for adjusting the size and the distribution of the pores in the finished ceramic.
  • the melt is atomized while cooling to form a powder.
  • metallic particles with a diameter between 1 ⁇ m and 100 ⁇ m can be produced.
  • the subsequent internal oxidation and dissolution of the noble metal porous ceramic powder particles are created.
  • the internal oxidation is carried out at a temperature between 400 ° C and 1400 ° C, wherein the melting temperature is not exceeded.
  • the heat treatment of the solidified melt for internal oxidation is preferably carried out in an oxidizing atmosphere, in particular in air or in oxygen.
  • the temperature control sets the size of the oxide particles and thus the size of the smallest pores.
  • the heat treatment time required for the internal oxidation depends on the oxidation temperature and composition of the alloy. The parameters should be set as far as possible so that complete internal oxidation is achieved. Our own investigations have shown that oxidation rates of up to 1 mm / h can be achieved.
  • the strength of the porous structure can be increased by a final sintering.
  • a sintering process for the invention as such is not necessary.
  • the invention does not exclude additionally sintering the finished porous ceramic.
  • a porous ceramic of zirconium, cerium and / or hafnium oxide which is produced in particular according to the abovementioned process.
  • a porous ceramic is characterized in particular by the fact that the ceramic particles, that is to say the oxides of zirconium, cerium and / or hafnium, are of threadlike form. This thread-like structure of the ceramic particles results from the diffusion-controlled process of internal oxidation. It has been found that the ratio of the length of the ceramic particles to their width in the porous ceramic is greater than 1:10.
  • the produced porous ceramic is further characterized in an advantageous embodiment in that a dendritic structure of the pores is included.
  • a dendritic structure ie a tree-like structure with continuous branching, is caused by the solidification behavior of the alloy.
  • first nuclei of the solidified metal or of the solidified alloy form, on which the further solidification proceeds.
  • the nobler metal is dissolved out, the pores form the negative structure of the solidified noble metal. This structure has the distinctive dendritic shape.
  • the invention is characterized overall by comparatively low process temperatures (if the solidified melt is assumed), by the possibility of a simple influencing of the pore sizes by the process control during solidification, pouring and oxidizing heat treatment, by a direct geometrical influence of the workpiece by casting the melt in the desired final contour and by the possibility a machining of the component. The latter is possible even after the internal oxidation.
  • the porous ceramic is further characterized by a homogeneous open porosity, since the metallic matrix that is dissolved out, previously was consistent.
  • the stretched ceramic particles promote the cohesion of the ceramic and possibly lead to a higher damage tolerance.
  • the higher specific surface area of the stretched ceramic particles improves the catalytic properties when the ceramic is used as catalyst support.
  • the fusible alloy can also be used as a coating.
  • FIG. 1 a micrograph of the surface of a zirconium-yttrium oxide ceramic produced by the present process
  • FIG. 2 Micrographs of zirconium-yttrium oxide ceramics made of a Ni-2Zr-0.2Y alloy at different solidification rates.
  • FIG. 1 shows the surface of a porous zirconium-yttrium oxide ceramic 1 produced according to the method described above.
  • a melt of a Ni-8Zr-0.2Y alloy (the values denote in the nickel alloy 8 atomic percent zirconium and 0.2 atomic percent yttrium) was prepared by melting pieces at a temperature of 1500 ° C. The melt was then poured into a preheated to 1300 ° C ceramic shell mold into rods with a length of 150 mm and a diameter of about 15 mm and passively cooled to room temperature under vacuum. From the frozen bodies ben discs were separated with a thickness of a few mm.
  • the disks were subjected to internal oxidation for 8 to 12 hours under air and normal pressure at a temperature of 1100 ° C. Thereafter, the outer oxide layer was mechanically removed and finally chemically dissolved out of the disks to form the porous ceramic nickel. For this, the slices were placed in a 65% nitric acid at a temperature of 70 ° C for about 8 to 12 hours.
  • the structure of the porous zirconium-yttrium oxide ceramics 1 is clearly apparent.
  • the resulting overall structure of these filamentary ceramic particles 3 is penetrated by pores 5 in all directions.
  • the coarse pores which have a dendritic structure 6.
  • Such a dendritic structure 6 is characterized by a stem 7, from which several branches 8 branch off.
  • the diameter of the coarse pores is greater than 10 ⁇ .
  • Example 3 By melting a Ni-7,7Zr-1, 1Y alloy at a temperature of about 1500 ° C, a porous zirconium-yttrium oxide ceramic was prepared. The
  • the oxidation temperature directly affects the specific surface of the resulting ceramic.
  • the specific surface area drops from about 28 m 2 / g to about 1 m 2 / g via about 17 m 2 / g. With low oxidation temperatures below 800 ° C even higher specific surface areas can be generated.
  • FIG. 2 shows four micrographs of a porous zirconium-yttrium ceramic produced from a Ni-2Zr-0.2Y alloy. Except for the pouring and cooling parameters, the process parameters correspond to Example 4. The internal oxidation was carried out at a temperature of 1000 ° C according to Example 3. The metallic nickel particles as well as the oxides formed between them become recognizable. The micrographs each show samples which were produced at different solidification rates, namely at 18 K / s, at 38 K / s, at 170 K / s and at 10 4 K s (Kelvin per second) with otherwise identical process parameters.
  • the solidification rates were by casting in a pre-heated to 1000 ° C ceramic shell and final passive cooling (18 K / s) by casting in a pre-heated to 300 ° C ceramic shell and passive cooling (38 K / s), by casting in a room temperature present copper mold and realized by casting into a gossip mold (10 4 K / s).
  • the effects on the porous ceramic essentially relate to the size of the pore fractions of the largest and middle pores. The faster it is cooled, the smaller these pore fractions become. In the final microsection, to a certain extent, only one pore fraction of the smallest pores (in the form of the later-removed metallic nickel particles) can be seen.
  • the examples show a multimodal pore size distribution.
  • the size of all fractions of the pores can be influenced by the process control.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une céramique poreuse (1) comprenant de l'oxyde de zirconium, de cérium et/ou d'hafnium, ainsi qu'une céramique (1) fabriquée selon ledit procédé. Selon le procédé, le zirconium, le cérium et/ou l'hafnium sont fondus avec au moins un métal plus noble et au moins un élément ayant une affinité pour l'oxygène jusqu'à l'obtention d'une masse fondue; la masse fondue est refroidie jusqu'à solidification; la masse fondue solidifiée est soumise à une oxydation interne, le zirconium, le cérium et/ou l'hafnium ainsi que ledit au moins un élément ayant une affinité pour l'oxygène s'oxydant, et, pour finir, le métal plus noble est éliminé de sorte qu'il reste la céramique poreuse.
PCT/EP2012/062761 2011-07-01 2012-06-29 Procédé de fabrication d'une céramique poreuse Ceased WO2013004637A2 (fr)

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DE102011107827.8 2011-07-01
DE102011107827A DE102011107827A1 (de) 2011-07-01 2011-07-01 Verfahren zur Herstellung einer porösen Keramik

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CN116283278A (zh) * 2023-02-20 2023-06-23 深圳市翔通光电技术有限公司 一种锆氧化物及其制备方法
CN117092090A (zh) * 2023-07-12 2023-11-21 重庆材料研究院有限公司 一种弥散强化铂基材料中氧化锆含量的测定方法

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JP5176198B2 (ja) * 2007-02-21 2013-04-03 独立行政法人産業技術総合研究所 マクロポーラスな連通孔を持つセラミック多孔体の製造方法
US7892660B2 (en) * 2007-12-18 2011-02-22 General Electric Company Wetting resistant materials and articles made therewith
FR2937320B1 (fr) * 2008-10-17 2011-07-29 Saint Gobain Ct Recherches Procede de fabrication d'un produit en matiere ceramique fondue, produit obtenu et utilisations de ce produit
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CN116283278A (zh) * 2023-02-20 2023-06-23 深圳市翔通光电技术有限公司 一种锆氧化物及其制备方法
CN117092090A (zh) * 2023-07-12 2023-11-21 重庆材料研究院有限公司 一种弥散强化铂基材料中氧化锆含量的测定方法

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