EP2234935A2 - Produit en matiere ceramique fondue, procede de fabrication et utilisations - Google Patents

Produit en matiere ceramique fondue, procede de fabrication et utilisations

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Publication number
EP2234935A2
EP2234935A2 EP08865039A EP08865039A EP2234935A2 EP 2234935 A2 EP2234935 A2 EP 2234935A2 EP 08865039 A EP08865039 A EP 08865039A EP 08865039 A EP08865039 A EP 08865039A EP 2234935 A2 EP2234935 A2 EP 2234935A2
Authority
EP
European Patent Office
Prior art keywords
equal
product according
less
oxides
zro
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.)
Withdrawn
Application number
EP08865039A
Other languages
German (de)
English (en)
French (fr)
Inventor
Emmanuel Nonnet
Yves Boussant-Roux
Eric Hanus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Centre de Recherche et dEtudes Europeen SAS
Original Assignee
Saint Gobain Centre de Recherche et dEtudes Europeen SAS
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Filing date
Publication date
Application filed by Saint Gobain Centre de Recherche et dEtudes Europeen SAS filed Critical Saint Gobain Centre de Recherche et dEtudes Europeen SAS
Publication of EP2234935A2 publication Critical patent/EP2234935A2/fr
Withdrawn legal-status Critical Current

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    • 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
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    • 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
    • C04B35/481—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 containing silicon, e.g. zircon
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Definitions

  • the present invention relates to products of ceramic material obtained by melting, or "molten products", and in particular melted particles that can be used in particular in apparatus and processes for micromilling, wet microdispersion and surface treatment.
  • Apparatuses and processes for micromilling, wet microdispersion and surface treatment are well known, and are particularly developed in industries such as:
  • the surface treatment industry which uses particles in particular for cleaning metal molds (for the manufacture of bottles, for example), deburring parts, descaling, preparing a support for for a coating, surface finishing (for example satin finishing of steel), shot blasting of pre-strains (called “shot peening” in English), or even forming of parts (called “peen-forming”) in the English language).
  • the particles conventionally used for these markets are generally substantially spherical in shape and between 0.005 and 4 mm in size. Depending on the target markets, they may have one or more of the following properties:
  • Rounded grain sand such as OTTAWA sand for example, is a natural and inexpensive product, but unsuitable for modern, pressurized and high flow mills. Indeed, the sand is not very resistant, of low density, variable in quality and abrasive for the material.
  • Glass beads widely used, have better strength, lower abrasiveness and availability in a wider range of sizes.
  • the glass-ceramic glass beads such as those described in JP-S61 -168552 or JP-S59-174540, are more resistant than glass beads.
  • Metal balls, in particular made of steel, have also been known for a long time for the abovementioned applications, but their use remains marginal because they often have insufficient chemical inertia with respect to the products treated, notably resulting in pollution of the mineral charges. and a graying of the paints, and too high a density requiring special grinders involving in particular a high energy consumption, a significant heating and a high mechanical stress of the equipment.
  • sintered ceramic particles obtained by cold forming of a ceramic powder followed by consolidation by baking at high temperature
  • the melted ceramic particles generally obtained by melting a feed of raw materials, converting the molten material into particles, and solidifying them.
  • the vast majority of the melted ceramic particles used in the aforementioned applications have a zirconia-silica (ZrO 2 - SiO 2 ) composition in which the zirconia is crystallized in monoclinic and / or partially stabilized form (by suitable additions), and where the silica, as well as some of the optional additives, form a matrix binding the zirconia crystals.
  • ZrO 2 - SiO 2 zirconia-silica
  • the document EP 0 662 461 describes melted particles whose mechanical strength increases with the amount of Y 2 ⁇ 3 and whose density, and therefore the grinding efficiency, increases with the amount of CeO 2.
  • An object of the invention is to satisfy this need.
  • the invention proposes a molten product having the following chemical composition, in percentages by weight on the basis of the oxides and for a total of 100%: (ZrO 2 + HfO 2 ): 100% complement , 6% ⁇ CeO 2 ⁇ 31%,
  • the inventors have discovered that, in the presence of yttrium oxide, the addition of cerium oxide beyond a threshold content leads to a decrease in the wear resistance. They then discovered that the ratio Y modifies this threshold content and determined the above conditions in order to optimize the compromise between density and wear resistance.
  • a melted ceramic product according to the invention thus has both a satisfactory density and good wear resistance.
  • the product may still have one or more of the optional features of the following list of product characteristics:
  • the mass ratio C is greater than or equal to 0.15, greater than or equal to 0.18, or greater than or equal to 0.20, or greater than or equal to 0.22, or greater than or equal to
  • C may especially be greater than or equal to 0.2, preferably greater than or equal to 0.3 and preferably less than or equal to 0.50;
  • the mass ratio Y is greater than or equal to 0.025, or greater than or equal to 0.030, or greater than or equal to 0.035, or greater than or equal to 0.040, or even greater than or equal to 0.045 or 0.050, and / or less than or equal to at 0.090, or less than or equal to 0.085, or less than or equal to 0.080, or less than or equal to 0.070, or even less than or equal to 0.060; Y may in particular be greater than or equal to 0.030, preferably greater than or equal to 0.040, preferably greater than or equal to 0.045 and less than or equal to 0.090, preferably less than or equal to 0.080, preferably less than or equal to 0.060;
  • C is greater than or equal to 0.2 and less than or equal to 0.5 if Y is greater than or equal to 0.030 and less than or equal to 0.060;
  • the ratio by mass (Zr ⁇ 2 + Hf ⁇ 2 ) / Si ⁇ 2 is greater than or equal to 1, or greater than or equal to 1, 5, or greater than or equal to 2, or greater than or equal to 4, or greater than or equal to 6, or greater than or equal to 8, or greater than or equal to 10, even greater than or equal to 14 and / or less than or equal to 30, or less than or equal to 25, or even less than or equal to 20, or even lower or equal to 15; preferably, the mass ratio (ZrO 2 + HfO 2 ) / SiO 2 is greater than or equal to 1.5, preferably greater than or equal to 4, more preferably greater than or equal to 10 and less than or equal to 25, preferably less than or equal to 20, more preferably less than or equal to 15;
  • the mass ratio AI 2 CVSiO 2 is greater than or equal to 0.1, or greater than or equal to 0.2, or greater than or equal to 0.5 and / or less than or equal to 3.2, or lower or equal to 2, or less than or equal to 1, 5.
  • the mass ratio AI 2 CVSiOa is greater than or equal to 0.2, preferably greater than or equal to 0.5 and less than or equal to 3.2, preferably less than or equal to 2;
  • the MgO / SiO 2 ratio is greater than 0 and preferably less than 1, preferably less than 0.77;
  • the content of CeO 2 is greater than or equal to 8%, or greater than or equal to 10%, or greater than or equal to 10.5%, or greater than or equal to 12% , or greater than or equal to 15%, or greater than or equal to
  • the CeO 2 content may also be greater than or equal to 20%; -
  • the CeO 2 content is greater than or equal to 10% and the CeO 2 and Y 2 O 3 contents are in accordance with formulas (III) and (IV), and preferably (V) and (VI);
  • the content of Y 2 O 3 is greater than or equal to 1%, or greater than or equal to 1, 65%, or greater than or equal to 2%, or greater than or equal to 2.5%, or greater than or equal to 3%, or greater than or equal to 3.4%, greater than or equal to 3.5% and / or less than or equal to 9%, or less than or equal to 8% , or less than or equal to 6.5%, or less than or equal to 5.5%, or even less than or equal to 5%, or less than or equal to 4.5%, or less than or equal to 3.7%, even less than or equal to 3.6%;
  • the Y 2 O 3 content is greater than or equal to 1.65% and less than or equal to 6.5%, preferably less than or equal to 4.5%, and the CeO 2 and
  • Y 2 O 3 comply with formulas (III) and (IV), and preferably (V) and (VI);
  • the content of Al 2 O 3 , in weight percent on the oxide basis is greater than or equal to 0.5%, or greater than or equal to 1%, or greater than or equal to 2%, or greater or equal to 4% and / or less than or equal to 25%, or less than or equal to 20%, or less than or equal to 15%, or less than or equal to 12%, or less than or equal to 10%, or less or equal to 8%.
  • the content of SiO 2 is greater than or equal to 0.5%, greater than or equal to 1%, or greater than or equal to 2.5%, or greater or equal to 3%, or greater than or equal to 4%, and / or less than or equal to 30%, or less than or equal to 20%, or less than or equal to 17
  • % or less than or equal to 16%, or less than or equal to 14%, or less than or equal to 12%, or less than or equal to 10%, or less than or equal to 8%;
  • the content of TiO 2 is greater than or equal to 0.5%, or greater than or equal to 1%, or even greater or equal to 1, 25%, even greater than or equal to 1, 5%, and / or less than or equal to 5%, even less than or equal to 3%, or even less than or equal to 2%;
  • the MgO content may be greater than or equal to 0.5%, even greater than or equal to 1%, or greater than or equal to 1.6%, and preferably lower or equal to 4%, preferably less than or equal to
  • the ZrO 2 content, in mass percentage on the basis of the oxides, is greater than or equal to 45%, or greater than or equal to 50%, or greater than or equal to 55%, or greater than or equal to 60% and or less than or equal to 85%, or less than or equal to 80% or less than or equal to 75%, or less than or equal to 70%.
  • the content of ZrO 2 , as a weight percentage based on the oxides is greater than or equal to 55%, preferably greater than or equal to 60% and less than or equal to 75%, preferably less than or equal to 70% .
  • Oxygen oxides are present only in the form of impurities; - The oxide content may represent more than 99.5% or more than 99.9%, and even substantially 100% of the total mass of the product;
  • the product is in the form of a particle or a ball, or a set of particles or beads. These beads and particles may have a size less than or equal to 4 mm and / or greater than or equal to 5 ⁇ m; - Preferably, the product is in the form of a ball having a sphericity greater than or equal to 0.7, preferably greater than or equal to 0.8, more preferably greater than or equal to 0.9;
  • the product has a density greater than or equal to 4, greater than or equal to 4.5, greater than or equal to 4.7, or greater than or equal to 5, greater than or equal to 5.2, or greater or equal to 5.4;
  • the product has a planetary wear less than or equal to 3.5%, or less than or equal to 2.9%, or less than or equal to 2.5%, or less than or equal to 2.3%, or less than or equal to at 2.1%, or even less than or equal to 1, 9%.
  • the invention provides a molten product having the following chemical composition, in percentages by weight on the basis of the oxides and for a total of 100%: (ZrO 2 + HfO 2 ): 100% complement , 1, 5% -S CeO 2 -S 31%,
  • ⁇ SiO 2 0.5% ⁇ SiO 2 , preferably 2.5% ⁇ SiO 2 , or even 4% ⁇ SiO 2 and SiO 2 ⁇ 17.4%, or even SiO 2 ⁇ 17%, SiO 2 ⁇ 15%, SiO 2 ⁇ 10 %, or SiO 2 ⁇ 8%, 0 ⁇ TiO 2 ⁇ 8.5%,
  • the content of SiO 2 is greater than or equal to 2.5%, preferably greater than or equal to 4% and less than or equal to 17%, preferably less than or equal to 8%. %.
  • the CeO 2 content may be greater than 6%.
  • the optional features of the product characteristics list defined above may optionally be applied to this product.
  • a product according to the invention of this type also has a good compromise between density and wear resistance.
  • the invention provides a molten product having the following chemical composition, in percentages by mass on the basis of the oxides and for a total of 100%:
  • the content of Al 2 O 3 is greater than or equal to 1%, preferably greater than or equal to 4% and less than or equal to 10%, preferably less than or equal to at 8 %.
  • the CeO 2 content may be greater than 6%. Furthermore, to the extent that they are not inconsistent with 0.5% ⁇ AI 2 O 3 , the optional features of the product characteristics list defined above may optionally be applied to this product. As will be seen in more detail in the following description, a product according to the invention of this type also has a good compromise between density and wear resistance.
  • the invention provides a molten product having the following chemical composition, in percentages by weight on the basis of the oxides and for a total of 100%: (ZrO 2 + HfO 2 ): 100% complement, 1, 5% ⁇ CeO 2 ⁇ 31%, 0.8% ⁇ Y 2 O 3 ⁇ 8.5%, 0% ⁇ AI 2 O 3 ⁇ 30%, or even 0.5% ⁇ AI 2 O 3 , 0% ⁇ SiO 2 ⁇ 37%,
  • the TiO 2 content is greater than or equal to 1% and less than or equal to 8.5%, preferably less than or equal to 5%.
  • the CeO 2 content may be greater than 6%.
  • the optional features of the product characteristics list defined above may optionally be applied to this product.
  • a product according to the invention of this type also has a good compromise between density and wear resistance.
  • the invention provides a molten product having the following chemical composition, in percentages by mass on the basis of the oxides and for a total of 100%: (ZrO 2 + HfO 2 ): 100% complement,
  • a product according to the invention of this type also has a good compromise between density and wear resistance.
  • the invention also relates to a powder comprising more than 80%, more than
  • the invention also relates to a powder obtained by grinding particles, in particular beads, according to the invention.
  • the invention also relates to a method of manufacturing a product, comprising the following successive steps: a) mixing raw materials to form a feedstock, b) melting the feedstock so as to form a melt, and c) solidifying the melt to obtain a melt.
  • the feedstock is determined so that the melt is in accordance with any one of the five main embodiments of the invention described above.
  • the invention also relates to the use of a product according to the invention, for example obtained according to a process according to the invention, as a grinding agent, a dispersion agent in a humid medium or for the treatment of surfaces, in particular in the applications mentioned in the preamble of the present description.
  • the products according to the invention, and in particular the fused beads according to the invention are used without having previously undergone a heat treatment capable of having crystallized them, even partially, and preferably are used under conditions that do not lead to such crystallization.
  • Min (x; y) is equal to the smallest of x and y values.
  • Powder means a solid product individualized in a powder.
  • Bit means a particle having a sphericity, that is to say a ratio between its smallest and largest diameter, greater than or equal to 0.6, whatever the way in which this sphericity was obtained.
  • the "size" of a ball (or particle) is the average of its largest dimension dM and its smallest dimension dm: (dM + dm) / 2.
  • Melted product means a product obtained by solidification by cooling of a molten material.
  • molten material is a mass which, to maintain its shape, must be contained in a container.
  • a molten material is usually liquid. However, it may contain solid particles, but in insufficient quantity so that they can structure said mass.
  • impurities means the inevitable constituents necessarily introduced with the raw materials.
  • the compounds forming part of the group of oxides, nitrides, oxynitrides, carbides, oxycarbides, carbonitrides and metallic species of sodium and other alkalis, iron, vanadium and chromium are impurities.
  • the residual carbon is one of the impurities of the composition of the products according to the invention.
  • Hafnium oxide is not considered an impurity.
  • precursor of an oxide is meant a component capable of supplying said oxide during the manufacture of a product according to the invention.
  • “Surface treatment” means an operation consisting in modifying the state of a surface by the mechanical action of particles projected onto this surface. The projected particles are solid and do not adhere to the surface. In other words, the term “surface treatment” does not cover applications in which the product would be fixed in the form of a layer on a surface.
  • the feedstock is formed of the desired oxides in the product or precursors thereof.
  • ZrSiO 4 natural zircon sand containing about 66% ZrO 2 and 33% SiO 2 , plus impurities is used.
  • the contribution of ZrO 2 through zircon is indeed much more economical than an addition of ZrO 2 .
  • the compositions can be adjusted by addition of pure oxides, mixtures of oxides or mixtures of precursors of these oxides, especially ZrO 2 , SiO 2 , CeO 2 , Y 2 O 3 , TiO 2 , Al 2 O 3 .
  • the chemical analysis of a molten ceramic product is generally substantially identical to that of the feedstock.
  • the skilled person knows how to adapt the composition the starting charge accordingly.
  • no oxide other than ZrO 2 + HfO 2 , SiO 2 , Y 2 O 3 , CeO 2 , TiO 2 and Al 2 O 3 is introduced voluntarily, in the form of oxide or oxide precursor, in the starting charge, the other oxides present being thus impurities.
  • step b) the feedstock is melted, preferably in an electric arc furnace. Electrofusion makes it possible to manufacture large quantities of particles with interesting yields. But all known furnaces are conceivable, such as an induction furnace or a plasma furnace, provided they allow to melt the feedstock to form a bath of molten material.
  • step c) a stream of the molten liquid is dispersed in small liquid droplets which, as a result of the surface tension, take, for the majority of them, a substantially spherical shape.
  • This dispersion can be performed by blowing, in particular with air and / or steam, or by any other method of atomizing a melt, known to those skilled in the art.
  • a melted ceramic particle with a size of 5 ⁇ m to 4 mm can thus be produced.
  • the cooling resulting from the dispersion leads to the solidification of the liquid droplets. Particles, in particular beads, are then melted.
  • Any conventional method for producing melted particles, especially melted beads, can be implemented. For example, it is possible to manufacture a melted and cast block, then to grind it and, if necessary, to make a granulometric selection.
  • Conditions (III) and (IV) may in particular be satisfied by a product of the invention comprising from 55% to 75% by weight of (ZrO 2 + HfO 2 ), as a percentage by weight on the basis of the oxides, and a mass ratio Y 2 ⁇ 3 / (ZrO 2 + HfO 2 ) of between 0.03 and 0.09, preferably between 0.03 and 0.06.
  • the mass ratio Y is greater than or equal to 0.02.
  • Y is preferably greater than or equal to 0.03, preferably 0.04, more preferably 0.045.
  • the wear resistance may be unsatisfactory in certain applications.
  • a product according to the invention for example obtained by a process according to the invention, may have a mass ratio C advantageously between 0.2 and 0.5, and a mass ratio Y of between 0.03 and 0, 06.
  • the compromise between density and wear resistance is then considered optimal.
  • the mass ratio C is less than or equal to 0.6.
  • harmful phases can be formed, such as zirconia in the cubic crystallographic form.
  • the mass ratio C may be greater than or equal to 0.30, or greater than or equal to 0.40 and / or less than or equal to 0.55, or less than or equal to 0.50, or less than or equal to 0.45 or less than or equal to 0.40, or even less than or equal to 0.35.
  • the mass ratio Y is preferably less than or equal to 0.09, preferably less than or equal to 0.06. Indeed, with a Y ratio> 0.09, CeO 2 content maximizing the density of the product leads to unsatisfactory wear resistance in some applications.
  • the mass ratio Y may be greater than or equal to 0.025, or greater than or equal to 0.030, greater than or equal to 0.035, or greater than or equal to 0.040 and / or less than or equal to 0.085, or less or equal to 0.080, or even lower than or equal to 0.070, or even less than or equal to 0.060.
  • the product may have one or more of the features of the above product feature list, since these features are not inconsistent with these embodiments.
  • the CeO 2 content is greater than or equal to 6%, preferably 10%, by weight based on the oxides. These contents make it possible to obtain particularly high densities.
  • the content of CeO 2 is greater than or equal to 10% and the contents of ZrO 2 , CeO 2 and Y 2 O 3 comply with the conditions (III) and (IV), and preferably the conditions (V) and ( VI).
  • the CeO 2 content is also less than or equal to 31% by weight based on the oxides. The inventors have indeed found that beyond this content, the resulting products were no longer satisfactory especially in terms of resistance to wear.
  • the content of CeO 2 may be greater than or equal to 8%, or greater than or equal to 10%, or greater than or equal to 10.5%, or greater or equal to 12%, or greater than or equal to 15%, or greater than or equal to 17% and / or less than or equal to 30%, or less than or equal to 28%, less than or equal to 26%, or less than or equal to at 25%, or even less than or equal to 20%.
  • silica improves the creation of solid product particles, that is to say with few internal porosities, or even without internal porosity.
  • the silica content is greater than 2.5%.
  • the best performances have been obtained with silica contents of between 2.5% and 17%, and even more so between 4% and 8%.
  • this favorable effect is reduced if the MgO content is too high.
  • the MgO content is less than or equal to 6%.
  • the presence of alumina and / or titanium oxide improves the wear resistance of the product. This is why the alumina content is preferably greater than 0.5%, preferably greater than or equal to 1%, preferably greater than or equal to 4%.
  • the alumina content remains below 30% in order to favor the introduction of the elements CeO 2 and Y 2 O 3 , the positive influence of which is particularly remarkable. In addition, higher levels of alumina no longer improve the wear resistance.
  • the TiO 2 content is greater than 1%. Preferably, the TiO 2 content is less than 8.5%. The inventors have indeed found that beyond this value, harmful secondary phases based on TiO 2 and ZrO 2 appear, resulting in a reduction in the wear resistance.
  • a product according to the invention may advantageously have a density greater than or equal to 4, or greater than or equal to 4.5, greater than or equal to 4.7, or greater than or equal to 5, or even greater than or equal to 5.2, or greater than or equal to 5.4.
  • a product according to the invention may also advantageously have a planetary wear less than or equal to 3.5%, or less than or equal to 2.9%, or less than or equal to 2.5%, or less than or equal to 2%. , 3%, or less than or equal to 2.1%, or even less than or equal to 1, 9%, the planetary wear being measured according to the protocol described hereinafter in the tests.
  • the chemical composition of a product according to the invention can make it suitable for other applications than those described in the present description, especially as a dry grinding agent, retaining and heat exchange.
  • the density of the particles according to the invention is measured by a method using a helium pycnometer (AccuPyc 1330 from Micromeritics®), according to a method based on the measurement of the volume of gas (in this case Helium) displaced.
  • the following methods provide excellent simulation of actual service behavior in grinding applications.
  • the contents of the bowl are then washed on a 100 ⁇ m sieve so as to remove the residual silicon carbide as well as the tearing of material due to wear during grinding. After sieving through a 100 .mu.m sieve, the particles are then oven-dried at 100.degree. C. for 3 hours and then weighed (mass m).
  • Planetary wear expressed as a percentage, is given by the following formula: 100 (m 0 -m) / m 0
  • a zircon composition is used for the feedstock, and yttrium oxide, cerium oxide, aluminum oxide, silicon oxide and optionally polyisocyanate are added. zirconium oxide (zirconia) and titanium oxide.
  • a pulverulent composition consisting of zircon sand and the other oxides mentioned above is introduced into a Héroult-type electric arc furnace so as to melt it.
  • the molten material is cast in the form of a net and then dispersed into balls by blowing compressed air. Several melting / casting cycles are carried out by adjusting in the composition the oxides of yttrium, cerium, aluminum, silicon and optionally zirconium and titanium.
  • the products are particularly effective when they exhibit both a planetary wear of less than or equal to 2.7 and a density greater than 4.5 (these are in particular products 8 to 10, 12, 13, 16 to 24, 25 to 28, 31, 35, 36 and 38) or when they exhibit both planetary wear less than 3.4 and density greater than 5 (these are in particular products 8 to 10 , 12, 13, 18, 20 to 24, 26 to 28, 30, 31, 35, 36, 38 and 39).
  • Examples 2, 3, 5, 6, 11, 15, 34 or 37 illustrate in particular that an insufficient CeO 2 content does not make it possible to produce particles having a good density.
  • the density of the resulting particles varies from 3.9 (Examples 6, 15 and 34) to 4.6 (Example 11).
  • Reference examples 32 and 33 illustrate that particles having a CeO 2 content of greater than 31% exhibit poor wear resistance (respectively 7.9 and 7.4 in planetary wear).
EP08865039A 2007-12-20 2008-12-22 Produit en matiere ceramique fondue, procede de fabrication et utilisations Withdrawn EP2234935A2 (fr)

Applications Claiming Priority (2)

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FR0760155A FR2925485B1 (fr) 2007-12-20 2007-12-20 Produit en matiere ceramique fondue, procede de fabrication et utilisations.
PCT/FR2008/052394 WO2009081074A2 (fr) 2007-12-20 2008-12-22 Produit en matiere ceramique fondue, procede de fabrication et utilisations

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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
FR2966824B1 (fr) * 2010-10-29 2013-04-05 Saint Gobain Ct Recherches Particule en matiere ceramique fondue.
FR2973368B1 (fr) * 2011-03-31 2013-11-08 Saint Gobain Ct Recherches Grains fondus atz
FR2973793A1 (fr) * 2011-04-08 2012-10-12 Rhodia Operations Composition a base d'oxydes de zirconium, de cerium, d'au moins une terre rare autre que le cerium et de silicium, procedes de preparation et utilisation en catalyse
FR3042792A1 (fr) * 2015-10-21 2017-04-28 Saint-Gobain Centre De Rech Et D'Etudes Europeen Bille en un produit fondu
JP6697910B2 (ja) * 2016-03-17 2020-05-27 第一稀元素化学工業株式会社 ジルコニウム質組成物及びその製造方法
FR3072092B1 (fr) * 2017-10-11 2021-11-12 Saint Gobain Ct Recherches Procede de fabrication d'un bloc fondu a haute teneur en zircone

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JPS59152266A (ja) * 1983-02-18 1984-08-30 東芝モノフラツクス株式会社 ジルコニア質耐火物
US4599270A (en) * 1984-05-02 1986-07-08 The Perkin-Elmer Corporation Zirconium oxide powder containing cerium oxide and yttrium oxide
US5059095A (en) * 1989-10-30 1991-10-22 The Perkin-Elmer Corporation Turbine rotor blade tip coated with alumina-zirconia ceramic
FR2714905B1 (fr) * 1994-01-11 1996-03-01 Produits Refractaires Billes en matière céramique fondue.
GB2305430B (en) * 1995-09-21 1997-08-27 Matsushita Electric Works Ltd Zirconia based ceramic material and process of making the same
FR2836682B1 (fr) * 2002-03-01 2005-01-28 Saint Gobain Ct Recherches Produit refractaire fondu et coule a forte teneur en zircone

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TW200938513A (en) 2009-09-16
CA2709339A1 (fr) 2009-07-02
EA201000838A1 (ru) 2010-12-30
WO2009081074A3 (fr) 2010-04-08
WO2009081074A2 (fr) 2009-07-02
CN101903307A (zh) 2010-12-01
JP2011506263A (ja) 2011-03-03
FR2925485B1 (fr) 2011-07-15
AU2008339733A1 (en) 2009-07-02
FR2925485A1 (fr) 2009-06-26
KR20100098644A (ko) 2010-09-08

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