WO2024079356A1 - Alumina-zirconia-silica refractory product - Google Patents

Alumina-zirconia-silica refractory product Download PDF

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Publication number
WO2024079356A1
WO2024079356A1 PCT/EP2023/078573 EP2023078573W WO2024079356A1 WO 2024079356 A1 WO2024079356 A1 WO 2024079356A1 EP 2023078573 W EP2023078573 W EP 2023078573W WO 2024079356 A1 WO2024079356 A1 WO 2024079356A1
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Prior art keywords
product according
less
mass content
na2û
ratio
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PCT/EP2023/078573
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French (fr)
Inventor
Isabelle Cabodi
Olivier Citti
Isabell GROSS
Pierrick VESPA
Michel Gaubil
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Saint-Gobain Centre De Recherches Et D'etudes Europeen
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Publication of WO2024079356A1 publication Critical patent/WO2024079356A1/en

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    • 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
    • C04B35/107—Refractories by fusion casting
    • C04B35/109—Refractories by fusion casting containing zirconium oxide or zircon (ZrSiO4)
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Definitions

  • the invention relates to a fused AZS (Alumina-Zircona-Silica) refractory product as well as a glass melting furnace comprising such a product.
  • AZS Allumina-Zircona-Silica
  • Glass melting furnaces generally include a very large number of refractory products, arranged in different locations depending on their properties. For each part of the oven, the product chosen will be one that does not cause defects rendering the glass unusable (which would reduce production yields) and is resistant long enough to give the oven a satisfactory lifespan.
  • molten blocks most often include an intergranular vitreous phase connecting crystallized grains.
  • the problems posed by sintered blocks and molten blocks, and the technical solutions adopted to solve them, are therefore generally different.
  • a composition developed to manufacture a sintered block is therefore not a priori usable as is to manufacture a molten block, and vice versa.
  • Molten blocks are obtained by melting a mixture of suitable raw materials in an electric arc furnace or by any other suitable technique. The molten material is then conventionally poured into a mold, then solidified. Generally, the product obtained then undergoes a controlled cooling cycle to bring it to room temperature without fracturing. This operation is called “annealing” by those skilled in the art.
  • AZS molten Alumina-Zircona-Silica products
  • AZS products typically contain less than 80% by mass of zirconia.
  • AZS products also contain corundum (free, or in the form of a corundum/zirconia eutectic) in a quantity generally greater than 10%, or even greater than 30%.
  • AZS products conventionally contain sodium oxide Na2 ⁇ to give the glassy phase suitable physical and chemical properties. Generally, K2O and Na2 ⁇ are believed to have equivalent effects.
  • US 2,438,552 recommends the addition of sodium oxide (1.0 to 2.2%) and a total MgO + CaO content of between 0.2% and 0.8%, to respond to feasibility problems concerning AZS products containing 9% to 12% SiC>2 and 0.4% to 1.7% iron oxide.
  • EP939065 proposes to reduce the exudation rate of AZS products containing 20% to 59% of ZrC>2 and 5% to 12% of SiC>2 by adding B2O3, P2O5 and at least one of the oxides of the group SnC>2, ZnO , CuO and MnC
  • WO2011161588 offers AZS products resistant to exudation having, in addition to AI2O3, from 30% to 50% ZrC>2, from 8% to 16% SiC>2, Y2O3 and more than 0.2% Na2O+K2O +B 2 O3.
  • Block control or “monitoring” methods have been developed. We know in particular the methods using electromagnetic waves, in particular radar waves (“Radar based sensors” (TOF)). The applications of these methods, however, remain limited to cases where the residual thickness is low.
  • the invention proposes a melted and cast refractory product comprising, in mass percentages on the basis of oxides and for a total of 100%:
  • Fe2Os + Ti ⁇ 2 ⁇ 0.60% other species: ⁇ 1.0% - the ratio (K 2 O/1.52) /(Na 2 0 + K 2 O/1.52) being greater than 0.30 with Na 2 O ⁇ 0.60%, or
  • Na 2 O and K 2 O had a different effect on the penetration capacity of radar waves in a block in a product according to the invention.
  • Na 2 O and K 2 O not only improve the penetration ability of radar waves into the block, but also preserve the feasibility.
  • the control can therefore be carried out up to a greater depth, preferably over the entire thickness of the block.
  • a product according to the invention is therefore perfectly suited to controlling its residual thickness.
  • a product according to the invention may also include one or more of the following optional characteristics, including when it conforms to the particular embodiments described below and these optional characteristics are not incompatible with said particular embodiments:
  • the total porosity of the product is less than 10%, or even less than 5%;
  • the oxides represent more than 90%, more than 95%, more than 99%, or even substantially 100% of the mass of the product;
  • the mass content of ZrO 2 + HfO 2 is less than 54.0%, or even less than 53.0%, or even less than 52.5%, or even less than 52.0%, or even less than 51.0%, or even less than 50.5%, or even less than 50.0%, or even less than 49.5%, or even less than 49.0%, or even less than 48.5%, or even less than 48.0%, or even less at 47.0%, or even less than 46.0%, and/or greater than 40.0%, or even greater than 41.0%, or even greater than 42.0%, or even greater than 42.5%, or even greater at 43.0%, or even greater than 43.5%, or even greater than 44.0%, or even greater than 44.5%, or even greater than 45.0%, or even greater than 45.5%;
  • the SiO 2 mass content is less than 13.8%, or even less than 13.6%, or even less than 13.5%, or even less than 13.4%, or even less than 13.3%, or even less than 13.2%, or even less than 13.0%, or even less than 12.7%, or even less than 12.5% and/or preferably greater than 10.6%, or even greater than 10.7%, or even greater at 10.8%, or even higher than
  • the mass content of AI2O3 is less than 46.0%, or even less than 45.5%, or even less than 45.0%, or even less than 44.0%, or even less than 43.5%, or even less than 43 .0%, or even less than 42.0% and/or greater than 29.0%, or even greater than 30.0%, or even greater than 32.0%, or even greater than 34.0%, or even greater than 36, 0%;
  • the sum of the mass contents of sodium oxide Na2 ⁇ and potassium oxide K 2 O is preferably greater than 0.85%, greater than 0.90%, greater than 0.95%, greater than
  • the mass content of Na2 ⁇ is preferably less than 1.50%, or even less than 1.40%, or even less than 1.30%, or even less than 1.20%, or even less than 1.00%, or even less at 0.80%, even less than 0.75%, even less than 0.60%, even less than 0.55%, even less than 0.50%, even less than 0.40%, less than 0, 30%, less than 0.20%, or less than 0.10%; in one embodiment, Na2 ⁇ is present as an impurity;
  • the K 2 O mass content is preferably less than 2.50%, or even less than 2.00%, or even less than 1.90%, or even less than 1.80%, or even less than 1.70%, or even less than
  • the ratio (K2O/1.52)/(Na2O + K2O/1.52) is greater than 0.40, or even greater than 0.45, or even greater than 0.50, or even greater than 0.60, or even greater at 0.62, or even greater than 0.65, or even greater than 0.70, or even greater than 0.75, or even greater than 0.80 and/or less than 0.95, or even less than 0.90;
  • - B2O3 is present as an impurity and/or the mass content of boron oxide B2O3 is less than 0.90%, preferably less than 0.80%, preferably less than 0.70%, preferably less than 0.60%, preferably less than 0.50%, less than 0.40%, % or even less than 0.30%, even less than 0.20%, or even less than 0.10%;
  • the Y2O3 mass content is less than 0.80%, or even less than 0.60%, or even less than 0.50%, or even less than 0.40%, or even less than 0.30%, or even less than 0 .20%;
  • the total mass content of “other species” is less than 0.9%, or even less than 0.8%, or even less than 0.6%, or even less than 0.5%, or even less than 0.4%;
  • the mass content of any “other species”, in particular Ta2Ü5 and/or Nb2Ü5, is less than 0.4%, or even less than 0.3%, or even less than 0.2%, or less than 0, 1%;
  • the sum of the mass contents of calcium oxide CaO, barium oxide BaO, strontium oxide SrO and magnesium oxide MgO is less than 0.6%, less than 0.5%, less than 0.4% , or even less than 0.3%;
  • the CaO mass content is less than 0.4%, or even less than 0.3%;
  • the SrO mass content is less than 0.4%, or even less than 0.3%;
  • the MgO mass content is less than 0.4%, or even less than 0.3%;
  • the product comes in the form of a block.
  • the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
  • Na2 ⁇ + K 2 O 0.80% to 2.50%, or even 0.80% to 2.00%
  • Fe2Ü3 + TiÜ2 ⁇ 0.60% other species: ⁇ 1.0% with a ratio (K 2 O/1.52) / (Na2O + K 2 O/1.52) greater than 0.60, or even greater than 0.65.
  • the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
  • AI2O3 100% supplement, preferably ⁇ 44.0%
  • K2O 1.00% to 2.00%, preferably 1.10% to 1.80%
  • Na2 ⁇ ⁇ 0.50%, preferably ⁇ 0.40%, preferably ⁇ 0.30%
  • B2O3 ⁇ 1.0% Fe2Ü3 + TiÜ2: ⁇ 0.60% other species: ⁇ 1.0% with a ratio (K 2 O/1.52) / (Na2O + K 2 O/1.52) greater than 0.65, or even greater than 0.70.
  • the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
  • K2O 0.70% to 1.80%, preferably 0.80% to 1.60%
  • Na2 ⁇ ⁇ 0.60%, preferably ⁇ 0.50%, preferably ⁇ 0.40%
  • Fe2Ü3 + TiÜ2 ⁇ 0.60% other species: ⁇ 1.0% with a ratio (K 2 O/1.52) / (Na2O + K 2 O/1.52) greater than 0.62, preferably greater at 0.65, preferably greater than 0.70.
  • the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
  • SiO 2 10.5% to 14.0%, or even 10.5% to 13.0%
  • AI2O3 100% supplement, preferably ⁇ 44.0%
  • K 2 O ⁇ 2.00%, or even 0.60% to 1.80%
  • B2O3 ⁇ 1.0%, even ⁇ 0.5% with a ratio (K 2 O/1.52) / (Na2O + K 2 O/1.52) greater than 0.60, even greater than 0.65 .
  • the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
  • AI2O3 100% supplement, preferably ⁇ 44.0%
  • K 2 O ⁇ 2.00% B 2 O 3 : ⁇ 0.5% with a ratio (K 2 O/1.52) / (Na 2 O + K 2 O/1.52) greater than 0.50.
  • the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
  • AI 2 O 3 100% complement, preferably ⁇ 44.0%
  • B 2 O 3 ⁇ 0.5% with a ratio (K 2 O/1.52) / (Na 2 O + K 2 O/1.52) greater than 0.60.
  • the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
  • SiO 2 10.5% to 14.0%, preferably 10.5% to 13.5%
  • K 2 O ⁇ 2.00%, preferably 0.30% to 1.80% with a ratio (K 2 O/1.52)/(Na 2 O + K 2 O/1.52) preferably higher at 0.60, preferably greater than 0.62, or even greater than 0.65, 0.70, or 0.75.
  • the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
  • K 2 O ⁇ 2.00% with a ratio (K 2 O/1.52) /(Na 2 O + K 2 O/1.52) greater than 0.65.
  • the invention also relates to a process for manufacturing a refractory product according to the invention, comprising the following successive steps: a) mixing of raw materials so as to form a starting charge, b) melting of said starting charge until obtaining a molten material, c) casting and solidifying said molten material, by cooling, so as to obtain a refractory product, this process being remarkable in that said raw materials are chosen so that said refractory product is in accordance with the invention.
  • the oxides for which a minimum content is necessary, or precursors of these oxides are added systematically and methodically.
  • the contents of these oxides are taken into account in the sources of other oxides where they are present as impurities.
  • the cooling is controlled, preferably so as to be carried out at a rate of less than 20°C per hour, preferably at a rate of approximately 10°C per hour.
  • the invention also relates to a glass melting furnace comprising a refractory product according to the invention, or a refractory product manufactured or likely to have been manufactured according to a process according to the invention, in particular in a region intended to be in contact with molten glass, in particular in a glass melting furnace tank, in particular to constitute an electrode holder block, for example in a floor of such a tank.
  • the invention thus relates to a glass melting furnace comprising a tank intended to contain or containing molten glass, the tank comprising a block of a product according to the invention.
  • the invention finally relates to a method for controlling a glass melting furnace according to the invention, said method comprising the following operations:
  • an electromagnetic wave to a block of a refractory product according to the invention preferably a radar type wave, with a frequency preferably between 1 and 10 gigahertz, or even between 1 and 6 gigahertz;
  • the application of the electromagnetic wave is carried out while the furnace is in service, the block optionally being in contact with molten glass.
  • the application of the electromagnetic wave and the analysis can be carried out by all known techniques, for example using the SmartMelter® device offered by PaneraTech.
  • a product is conventionally said to be “molten” when it is obtained by a process involving melting a charge until a molten material is obtained, then solidifying this material by cooling.
  • a block is an object with all dimensions greater than 10 mm. All dimensions of a block according to the invention are preferably greater than 50 mm, preferably greater than 100 mm.
  • a block according to the invention can for example have a general parallelepiped shape or a specific shape adapted to its use. Unlike a layer, a block of a melted and cast refractory product is conventionally obtained by a process comprising molding and demolding operations.
  • the block in one product according to the invention before or after dismantling/machining, can have one, or even two or three overall dimensions (thickness, length, or width) of at least 150 mm, preferably at least 250 mm, or even at least 400 mm, or even at least 500 mm, or even at least 600 mm, or even at least 800 mm or even at least 1000 mm, and/or less than 2000mm,
  • oxide contents in a product according to the invention are mass percentages based on the oxides.
  • a mass content of an oxide of a metallic element refers to the total content of this element expressed in the form of the most stable oxide, according to the usual industry convention.
  • HfO 2 is not chemically dissociable from ZrO 2 .
  • HfO 2 is not added voluntarily to the feed.
  • HfO 2 therefore only designates traces of hafnium oxide, this oxide always being naturally present in sources of zirconium oxide at contents generally less than 5%, generally less than 2%.
  • the mass content of HfO 2 is less than 5%, preferably less than 3%, preferably less than 2%.
  • the total content of zirconium oxide and traces of hafnium oxide can be designated either as “ZrO 2 ” or as “ZrO 2 + HfO 2 ”. HfO 2 is therefore not included in the “other species”.
  • impurities we mean the inevitable constituents, introduced with the raw materials or resulting from reactions with these constituents. Impurities are not constituents necessary, but only tolerated. For example, compounds belonging to the group of oxides, nitrides, oxynitrides, carbides, oxycarbides, carbonitrides and metallic species of iron, titanium, vanadium and chromium are impurities.
  • Total porosity is typically equal to 100 x (1 - the ratio of geometric density divided by absolute density).
  • Geometric density is measured according to standard ISO 5016:1997 or EN 1094-4 and expressed in g/cm 3 . It is conventionally equal to the ratio of the mass of the sample divided by the apparent volume.
  • the absolute density value expressed in g/cm 3 , can be measured by dividing the mass of a sample by the volume of that sample ground so as to substantially eliminate porosity.
  • the Zr ⁇ 2 + HfO2 content makes it possible to meet the requirements of high corrosion resistance. On the other hand, too high contents are harmful for the industrial feasibility of blocks.
  • the hafnium oxide, HfC>2, present in the product according to the invention is preferably the hafnium oxide naturally present in ZrO 2 sources. Its content in a product according to the invention is therefore less than 4%, generally less than 2%, or even less than 1%.
  • SiC>2 allows in particular the formation of an intergranular vitreous phase contributing to the feasibility of the products because it is able to effectively accommodate temperature deformations.
  • the mass content of SiC>2 is preferably limited in order to limit the quantity of glassy phase.
  • the presence of Na2O+K 2 O contributes to the feasibility of the products.
  • the mass content of Na2O+K 2 O is preferably limited in order to limit the quantity of vitreous phase and in particular to maintain good resistance to corrosion by molten glass as well as good wave propagation.
  • K 2 O The presence of K 2 O is necessary to have a ratio (K 2 O/1.52) / (Na2 ⁇ + K 2 O/1.52) greater than 0.30, or even greater than 0.40, or even greater than 0, 50, or even greater than 0.60, or even greater than 0.62, or even greater than 0.65, and allow good penetration of the waves into the block.
  • Na2 ⁇ has an unfavorable effect on the good penetration of waves into the block.
  • the mass content of sodium oxide Na2O must therefore remain limited.
  • B2O3 may have an adverse effect on feasibility.
  • the mass content of boron oxide B 2 O3 must therefore remain limited.
  • Y2O3 may have an adverse effect on feasibility.
  • the mass content of Y2O3 must therefore remain limited.
  • the mass content of Fe20s + TiO2 is less than 0.60%, preferably less than 0.50%, preferably less than 0.30%.
  • the mass content of P2O5 is less than 0.05%.
  • these oxides are harmful, particularly for the exudation of refractory products or the coloring of glass and their content must be limited to traces introduced as impurities with the raw materials.
  • the “other species” are the oxide species which are not listed above, namely species other than ZrC>2, HfC>2, SiC>2, Al2O3, Na2 ⁇ , K 2 O, B2O3, Y2O3, TiC> 2 and Fe20s.
  • the "other species” are limited to species whose presence is not particularly desired and which are generally present as impurities in the raw materials.
  • the product according to the invention is in the form of a block, preferably a block of which at least one, preferably at least two, or even all of the overall dimensions are greater than 150 mm.
  • the total porosity of the product according to the invention is less than 15%, or even less than 10%, or even less than 5%, or even less than 2%, or even less than 1%.
  • a product according to the invention can be conventionally manufactured following steps a) to c) described below: a) mixing of raw materials so as to form a starting charge, b) melting of said starting charge until obtaining of a molten material, c) solidification of said molten material, by cooling, so as to obtain a refractory product according to the invention.
  • step a) the raw materials are chosen so as to guarantee the oxide contents in the finished product obtained at the end of step c).
  • the fusion is preferably carried out thanks to the combined action of a fairly long electric arc, not producing reduction, and stirring promoting the reoxidation of the products.
  • This process consists of using an electric arc furnace whose arc flashes between the load and at least one electrode spaced from this load and in adjusting the length of the arc so that its reducing action is reduced to a minimum, while maintaining a oxidizing atmosphere above the molten bath and by stirring said bath, for example by the action of the arc itself.
  • step c) the cooling is preferably carried out at a speed of less than 20°C per hour, preferably at a speed of approximately 10°C per hour, preferably in a mold of the desired dimensions, taking into account the weighting and possible machining after step c).
  • any conventional process for manufacturing zirconia-based melted products intended for applications in glass melting furnaces can be implemented, provided that the composition of the starting charge makes it possible to obtain products having a composition conforming to that of a product according to the invention.
  • the products were prepared using the classic arc furnace melting process, then poured into a mold to obtain blocks with a minimum size of 150 mm x 250 mm x 500 mm after unblocking.
  • the average chemical analysis of the products obtained is given in Table 1; this is a chemical analysis of the liquid filler poured into the mold, given in mass percentages.
  • Species other than ZrO2, HfO2, SiO2, AI2O3, B2O3, Na2O and K 2 O, in particular Fe2Os, TiO2 and Y2O3 (if present) are impurities, with Y2O3 ⁇ 0.2% and Fe2Os + TO2 ⁇ 0.3 %.
  • the external state of the products obtained is observed. Their size, with the three dimensions greater than 150 mm and at least one dimension of at least 400 mm, makes it possible to estimate industrial feasibility. If a through slot is present, the feasibility is considered unsatisfactory. The products are then cut in half to observe the filling. In case of incorrect filling, the feasibility is considered unsatisfactory. Otherwise, the feasibility is considered satisfactory. All examples of the invention present satisfactory feasibility.
  • cylindrical bars of product of approximately 4 mm in diameter and 13 mm in height were penetrated by a wave of 2.4 gigahertz at 1000°C (corresponding to a temperature close to that of the external face of the tank blocks).
  • a wave of 2.4 gigahertz at 1000°C corresponding to a temperature close to that of the external face of the tank blocks.
  • the invention therefore provides a product which exhibits remarkable performance in the environment of a glass melting furnace tank.

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Abstract

The present invention relates to a molten cast refractory product comprising, in mass percent on the basis of oxides, and for a total of 100%: ZrO2 + HfO2: 39.0% to 55.0% with HfO2 < 5%, SiO2: 10.5% to 14.0%, Al2O3: complement to 100%, Na2O + K2O: 0.80% to 3.00%, B2O3: < 1.0 %, Fe2O3 + TiO2: < 0.60%, other types: < 1.0% - the ratio (K2O/1.52)/(Na2O + K2O/1.52) being greater than 0.30 with Na2O < 0.60%, or - the ratio (K2O/1.52)/(Na2O + K2O/1.52) being greater than 0.60.

Description

Description Description
Titre : PRODUIT REFRACTAIRE ALUMINE-ZIRCONE-SILICE Title: ALUMINA-ZIRCONIA-SILICA REFRACTORY PRODUCT
Domaine Domain
L'invention concerne un produit réfractaire fondu AZS (Alumine-Zircone-Silice) ainsi qu'un four de fusion de verre comportant un tel produit. The invention relates to a fused AZS (Alumina-Zircona-Silica) refractory product as well as a glass melting furnace comprising such a product.
Technique antérieure Prior art
Les fours de fusion de verre comprennent généralement un très grand nombre de produits réfractaires, disposés à différents endroits selon leurs propriétés. Pour chaque partie du four, le produit choisi sera celui ne provoquant pas de défauts rendant le verre inutilisable (ce qui réduirait les rendements de production) et résistant suffisamment longtemps pour apporter au four une durée de vie satisfaisante. Glass melting furnaces generally include a very large number of refractory products, arranged in different locations depending on their properties. For each part of the oven, the product chosen will be one that does not cause defects rendering the glass unusable (which would reduce production yields) and is resistant long enough to give the oven a satisfactory lifespan.
Parmi les blocs réfractaires, on distingue les blocs fondus et les blocs frittés. Among the refractory blocks, we distinguish molten blocks and sintered blocks.
A la différence des blocs frittés, les blocs fondus comportent le plus souvent une phase vitreuse intergranulaire reliant des grains cristallisés. Les problèmes posés par les blocs frittés et par les blocs fondus, et les solutions techniques adoptées pour les résoudre, sont donc généralement différents. Une composition mise au point pour fabriquer un bloc fritté n'est donc pas a priori utilisable telle quelle pour fabriquer un bloc fondu, et réciproquement. Unlike sintered blocks, molten blocks most often include an intergranular vitreous phase connecting crystallized grains. The problems posed by sintered blocks and molten blocks, and the technical solutions adopted to solve them, are therefore generally different. A composition developed to manufacture a sintered block is therefore not a priori usable as is to manufacture a molten block, and vice versa.
Les blocs fondus, souvent appelés « électrofondus » ou « fondus et coulés », sont obtenus par fusion d'un mélange de matières premières appropriées dans un four à arc électrique ou par toute autre technique adaptée. La matière en fusion est ensuite classiquement coulée dans un moule, puis solidifiée. Généralement, le produit obtenu subit alors un cycle de refroidissement contrôlé pour être amené à température ambiante sans fracturation. Cette opération est appelée « recuisson » par l'homme de l'art. Molten blocks, often called "electrocast" or "melt and cast", are obtained by melting a mixture of suitable raw materials in an electric arc furnace or by any other suitable technique. The molten material is then conventionally poured into a mold, then solidified. Generally, the product obtained then undergoes a controlled cooling cycle to bring it to room temperature without fracturing. This operation is called “annealing” by those skilled in the art.
On connaît des produits fondus Alumine-Zircone-Silice, dits « AZS », comportant majoritairement de l'alumine (AI2O3), de la zircone (ZrÛ2) et de la silice (SiO2). En particulier, les produits AZS comportent classiquement moins de 80% en masse de zircone. Les produits AZS présentent également du corindon (libre, ou sous la forme d’un eutectique corindon/zircone) en une quantité généralement supérieure à 10%, voire supérieure à 30%. Les produits AZS comportent classiquement de l’oxyde de sodium Na2Û pour conférer à la phase vitreuse des propriétés physiques et chimiques adaptées. Généralement, K2O et Na2Û sont réputés avoir des effets équivalents. We know of molten Alumina-Zircona-Silica products, called “AZS”, mainly comprising alumina (Al2O3), zirconia (ZrO2) and silica (SiO2). In particular, AZS products typically contain less than 80% by mass of zirconia. AZS products also contain corundum (free, or in the form of a corundum/zirconia eutectic) in a quantity generally greater than 10%, or even greater than 30%. AZS products conventionally contain sodium oxide Na2Û to give the glassy phase suitable physical and chemical properties. Generally, K2O and Na2Û are believed to have equivalent effects.
US 2 438 552 préconise l'ajout d’oxyde de sodium (1 ,0 à 2,2%) et une teneur totale MgO+CaO comprise entre 0,2% et 0,8%, pour répondre à des problèmes de faisabilité concernant des produits AZS comportant de 9% à 12% de SiC>2 et de 0,4% à 1 ,7% d’oxyde de fer. US 2,438,552 recommends the addition of sodium oxide (1.0 to 2.2%) and a total MgO + CaO content of between 0.2% and 0.8%, to respond to feasibility problems concerning AZS products containing 9% to 12% SiC>2 and 0.4% to 1.7% iron oxide.
EP939065 propose de réduire le taux d'exsudation des produits AZS contenant 20% à 59% de ZrC>2 et 5% à 12% de SiC>2 en ajoutant B2O3, P2O5 et au moins un des oxydes du groupe SnC>2, ZnO, CuO et MnC EP939065 proposes to reduce the exudation rate of AZS products containing 20% to 59% of ZrC>2 and 5% to 12% of SiC>2 by adding B2O3, P2O5 and at least one of the oxides of the group SnC>2, ZnO , CuO and MnC
WO2011161588 propose des produits AZS résistant à l’exsudation présentant, outre AI2O3, de 30% à 50 % de ZrC>2, de 8% à 16 % de SiC>2, du Y2O3 et plus de 0,2% de Na2O+K2O+B2O3.WO2011161588 offers AZS products resistant to exudation having, in addition to AI2O3, from 30% to 50% ZrC>2, from 8% to 16% SiC>2, Y2O3 and more than 0.2% Na2O+K2O +B 2 O3.
Un des facteurs limitant la durée de vie des fours de verrerie est l’usure des blocs, en particulier des blocs constituant les parois latérales de la cuve. Le contrôle de l’épaisseur résiduelle des blocs fondus dans un four en service est difficile, notamment du fait de la température de leur environnement. Des méthodes de contrôle (ou « monitoring ») des blocs ont été développées. On connaît en particulier les méthodes utilisant des ondes électromagnétiques, en en particulier des ondes radar (« Radar based sensors » (TOF)). Les applications de ces méthodes restent cependant limitées aux cas où l’épaisseur résiduelle est faible. One of the factors limiting the lifespan of glassmaking furnaces is the wear of the blocks, in particular the blocks constituting the side walls of the tank. Controlling the residual thickness of blocks melted in an operating furnace is difficult, particularly due to the temperature of their environment. Block control (or “monitoring”) methods have been developed. We know in particular the methods using electromagnetic waves, in particular radar waves (“Radar based sensors” (TOF)). The applications of these methods, however, remain limited to cases where the residual thickness is low.
Il existe donc un besoin permanent pour améliorer ces méthodes. There is therefore a continuing need to improve these methods.
Exposé de l’invention Presentation of the invention
Résumé de l’invention Summary of the invention
L’invention propose un produit réfractaire fondu et coulé comportant, en pourcentages massiques sur la base des oxydes et pour un total de 100% : The invention proposes a melted and cast refractory product comprising, in mass percentages on the basis of oxides and for a total of 100%:
ZrO2 + HfO2 : 39,0% à 55,0%, avec HfC>2 < 5% ZrO 2 + HfO 2 : 39.0% to 55.0%, with HfC>2 < 5%
SiO2 : 10,5% à 14,0% SiO 2 : 10.5% to 14.0%
AI2O3 : complément à 100% AI2O3: 100% supplement
Na2Û + K2O : 0,80% à 3,00% Na2Û + K2O: 0.80% to 3.00%
B2O3 : < 1 ,0 % B2O3: <1.0%
Fe2Os + TiÛ2 : < 0,60% autres espèces : < 1 ,0% - le rapport (K2O/1 ,52) /(Na20 + K2O/1 ,52) étant supérieur à 0,30 avec Na2O < 0,60%, ouFe2Os + TiÛ2: < 0.60% other species: < 1.0% - the ratio (K 2 O/1.52) /(Na 2 0 + K 2 O/1.52) being greater than 0.30 with Na 2 O < 0.60%, or
- le rapport (K2O/1 ,52) /(Na2O + K2O/1 ,52) étant supérieur à 0,60. - the ratio (K 2 O/1.52) / (Na 2 O + K 2 O/1.52) being greater than 0.60.
Comme on le verra plus en détail dans la suite de la description, plutôt que de chercher à améliorer l’appareillage utilisé pour le contrôle, les inventeurs ont cherché à améliorer la qualité de la réponse des blocs sollicités par un tel contrôle. De manière surprenante, ils ont découvert que Na2O et K2O avaient un effet différent sur la capacité de pénétration des ondes radar dans un bloc en un produit selon l’invention. En outre, ils ont découvert que, dans une plage de teneurs déterminée par plusieurs critères, et en particulier par le rapport (K2O/1 ,52) / (Na2O + K2O/1 ,52), Na2O et K2O non seulement améliorent la capacité de pénétration des ondes radar dans le bloc, mais aussi préservent la faisabilité. As will be seen in more detail later in the description, rather than seeking to improve the equipment used for control, the inventors sought to improve the quality of the response of the blocks requested by such control. Surprisingly, they discovered that Na 2 O and K 2 O had a different effect on the penetration capacity of radar waves in a block in a product according to the invention. In addition, they discovered that, in a range of contents determined by several criteria, and in particular by the ratio (K 2 O/1.52) / (Na 2 O + K 2 O/1.52), Na 2 O and K 2 O not only improve the penetration ability of radar waves into the block, but also preserve the feasibility.
Le contrôle peut donc être réalisé jusqu’à une profondeur supérieure, de préférence sur toute l’épaisseur du bloc. The control can therefore be carried out up to a greater depth, preferably over the entire thickness of the block.
Un produit selon l’invention est donc parfaitement adapté pour un contrôle de son épaisseur résiduelle. A product according to the invention is therefore perfectly suited to controlling its residual thickness.
Un produit selon l’invention peut encore comporter une ou plusieurs des caractéristiques optionnelles suivantes, y compris lorsqu’il est conforme aux modes de réalisation particuliers décrits ci-après et que ces caractéristiques optionnelles ne sont pas incompatibles avec lesdits modes de réalisation particuliers : A product according to the invention may also include one or more of the following optional characteristics, including when it conforms to the particular embodiments described below and these optional characteristics are not incompatible with said particular embodiments:
- la porosité totale du produit est inférieure à 10%, voire inférieure à 5% ; - the total porosity of the product is less than 10%, or even less than 5%;
- de préférence, les oxydes représentent plus de 90%, plus de 95%, plus de 99%, voire sensiblement 100% de la masse du produit ; - preferably, the oxides represent more than 90%, more than 95%, more than 99%, or even substantially 100% of the mass of the product;
- la teneur massique en ZrO2 + HfO2 est inférieure à 54,0%, voire inférieure à 53,0%, voire inférieure à 52,5%, voire inférieure à 52,0%, voire inférieure à 51 ,0%, voire inférieure à 50,5%, voire inférieure à 50,0%, voire inférieure à 49,5%, voire inférieure à 49,0%, voire inférieure à 48,5%, voire inférieure à 48,0%, voire inférieure à 47,0%, voire inférieure à 46,0%, et/ou supérieure à 40,0%, voire supérieure à 41 ,0%, voire supérieure à 42,0%, voire supérieure à 42,5%, voire supérieure à 43,0%, voire supérieure à 43,5%, voire supérieure à 44,0%, voire supérieure à 44,5%, voire supérieure à 45,0%, voire supérieure à 45,5% ; - the mass content of ZrO 2 + HfO 2 is less than 54.0%, or even less than 53.0%, or even less than 52.5%, or even less than 52.0%, or even less than 51.0%, or even less than 50.5%, or even less than 50.0%, or even less than 49.5%, or even less than 49.0%, or even less than 48.5%, or even less than 48.0%, or even less at 47.0%, or even less than 46.0%, and/or greater than 40.0%, or even greater than 41.0%, or even greater than 42.0%, or even greater than 42.5%, or even greater at 43.0%, or even greater than 43.5%, or even greater than 44.0%, or even greater than 44.5%, or even greater than 45.0%, or even greater than 45.5%;
- la teneur massique en SiO2 est inférieure à 13,8%, voire inférieure à 13,6%, voire inférieure à 13,5%, voire inférieure à 13,4%, voire inférieure à 13,3%, voire inférieure à 13,2%, voire inférieure à 13,0%, voire inférieure à 12,7%, voire inférieure à 12,5% et/ou de préférence supérieure à 10,6%, voire supérieure à 10,7%, voire supérieure à 10,8%, voire supérieure à- the SiO 2 mass content is less than 13.8%, or even less than 13.6%, or even less than 13.5%, or even less than 13.4%, or even less than 13.3%, or even less than 13.2%, or even less than 13.0%, or even less than 12.7%, or even less than 12.5% and/or preferably greater than 10.6%, or even greater than 10.7%, or even greater at 10.8%, or even higher than
10,9%, voire supérieure à 11 ,0%, voire supérieure à 11 ,3%, voire supérieure à 11 ,5% ; - la teneur massique en AI2O3 est inférieure à 46,0%, voire inférieure à 45,5%, voire inférieure à 45,0%, voire inférieure à 44,0%, voire inférieure à 43,5%, voire inférieure à 43,0%, voire inférieure à 42,0% et/ou supérieure à 29,0%, voire supérieure à 30,0%, voire supérieure à 32,0%, voire supérieure à 34,0%, voire supérieure à 36,0% ; 10.9%, or even greater than 11.0%, or even greater than 11.3%, or even greater than 11.5%; - the mass content of AI2O3 is less than 46.0%, or even less than 45.5%, or even less than 45.0%, or even less than 44.0%, or even less than 43.5%, or even less than 43 .0%, or even less than 42.0% and/or greater than 29.0%, or even greater than 30.0%, or even greater than 32.0%, or even greater than 34.0%, or even greater than 36, 0%;
- la somme des teneurs massiques en oxyde de sodium Na2Û et en oxyde de potassium K2O est de préférence supérieure à 0,85%, supérieure à 0,90%, supérieure à 0,95%, supérieure à- the sum of the mass contents of sodium oxide Na2Û and potassium oxide K 2 O is preferably greater than 0.85%, greater than 0.90%, greater than 0.95%, greater than
1 ,00% et/ou de préférence inférieure à 2,90%, de préférence inférieure à 2,80%, de préférence inférieure à 2,70%, de préférence inférieure à 2,60%, inférieure à 2,50%, voire inférieure à 2,30%, voire inférieure à 2,20%, voire inférieure à 2,10%, voire inférieure à 2,00%, voire inférieure à 1 ,90% ; 1.00% and/or preferably less than 2.90%, preferably less than 2.80%, preferably less than 2.70%, preferably less than 2.60%, less than 2.50%, or even less than 2.30%, or even less than 2.20%, or even less than 2.10%, or even less than 2.00%, or even less than 1.90%;
- la teneur massique en Na2Û est de préférence inférieure à 1 ,50%, voire inférieure à 1 ,40%, voire inférieure à 1 ,30%, voire inférieure à 1 ,20%, voire inférieure à 1 ,00%, voire inférieure à 0,80%, voire inférieure à 0,75%, voire inférieure à 0,60%, voire inférieure à 0,55%, voire inférieure à 0,50%, voire inférieure à 0,40%, inférieure à 0,30%, inférieure à 0,20%, ou inférieure à 0,10% ; dans un mode de réalisation, Na2Û est présent à titre d’impureté ; - the mass content of Na2Û is preferably less than 1.50%, or even less than 1.40%, or even less than 1.30%, or even less than 1.20%, or even less than 1.00%, or even less at 0.80%, even less than 0.75%, even less than 0.60%, even less than 0.55%, even less than 0.50%, even less than 0.40%, less than 0, 30%, less than 0.20%, or less than 0.10%; in one embodiment, Na2Û is present as an impurity;
- la teneur massique en K2O est de préférence inférieure à 2,50%, voire inférieure à 2,00%, voire inférieure à 1 ,90%, voire inférieure à 1 ,80%, voire inférieure à 1 ,70%, voire inférieure à- the K 2 O mass content is preferably less than 2.50%, or even less than 2.00%, or even less than 1.90%, or even less than 1.80%, or even less than 1.70%, or even less than
1 ,60%, voire inférieure à 1 ,50% et/ou supérieure à 0,60%, supérieure à 0,65%, voire supérieure à 0,70%, voire supérieure à 0,75%, voire supérieure à 0,80%, voire supérieure à 1 ,00% ; 1.60%, or even less than 1.50% and/or greater than 0.60%, greater than 0.65%, or even greater than 0.70%, or even greater than 0.75%, or even greater than 0, 80%, or even greater than 1.00%;
- le rapport (K2O/1 ,52) /(Na2O + K2O/1 ,52) est supérieur à 0,40, voire supérieur à 0,45, voire supérieur à 0,50, voire supérieur à 0,60, voire supérieur à 0,62, voire supérieur à 0,65, voire supérieur à 0,70, voire supérieur à 0,75, voire supérieur à 0,80 et/ou inférieur à 0,95, voire inférieur à 0,90 ; - the ratio (K2O/1.52)/(Na2O + K2O/1.52) is greater than 0.40, or even greater than 0.45, or even greater than 0.50, or even greater than 0.60, or even greater at 0.62, or even greater than 0.65, or even greater than 0.70, or even greater than 0.75, or even greater than 0.80 and/or less than 0.95, or even less than 0.90;
- B2O3 est présent à titre d’impureté et/ou la teneur massique en oxyde de bore B2O3 est inférieure à 0,90%, de préférence inférieure à 0,80%, de préférence inférieure à 0,70%, de préférence inférieure à 0,60%, de préférence inférieure à 0,50%, inférieure à 0,40%, %, voire inférieure à 0,30%, voire inférieure à 0,20%, voire inférieure à 0,10% ; - B2O3 is present as an impurity and/or the mass content of boron oxide B2O3 is less than 0.90%, preferably less than 0.80%, preferably less than 0.70%, preferably less than 0.60%, preferably less than 0.50%, less than 0.40%, % or even less than 0.30%, even less than 0.20%, or even less than 0.10%;
- la teneur massique en Y2O3 est inférieure à 0,80%, voire inférieure à 0,60%, voire inférieure à 0,50%, voire inférieure à 0,40%, voire inférieure à 0,30%, voire inférieure à 0,20% ; - the Y2O3 mass content is less than 0.80%, or even less than 0.60%, or even less than 0.50%, or even less than 0.40%, or even less than 0.30%, or even less than 0 .20%;
- la somme des teneurs massiques en oxyde de fer et en oxyde de titane, Fe20s + TiÛ2, est inférieure à 0,40%, de préférence inférieure à 0,30%, de préférence inférieure à 0,20% ; - the sum of the mass contents of iron oxide and titanium oxide, Fe20s + TiO2, is less than 0.40%, preferably less than 0.30%, preferably less than 0.20%;
- la teneur massique totale des « autres espèces » est inférieure à 0,9%, voire inférieure à 0,8%, voire inférieure à 0,6%, voire inférieure à 0,5%, voire inférieure à 0,4% ; - the total mass content of “other species” is less than 0.9%, or even less than 0.8%, or even less than 0.6%, or even less than 0.5%, or even less than 0.4%;
- les « autres espèces », c'est-à-dire autres que ZrO2,HfO2, SiC>2, AI2O3, Na2Û, K2O, B2O3, Fe2C>3 et TO2, ne sont constituées que par des impuretés ; - “other species”, that is to say other than ZrO2, HfO2, SiC>2, AI2O3, Na2Û, K 2 O, B2O3, Fe2C>3 and TO2, are only made up of impurities;
- la teneur massique d'une « autre espèce » quelconque, notamment de Ta2Ü5 et/ou en Nb2Ü5, est inférieure à 0,4%, voire inférieure à 0,3%, voire inférieure à 0,2%, inférieure à 0,1% ; - the mass content of any “other species”, in particular Ta2Ü5 and/or Nb2Ü5, is less than 0.4%, or even less than 0.3%, or even less than 0.2%, or less than 0, 1%;
- la somme des teneurs massiques en oxyde de calcium CaO, en oxyde de baryum BaO, en oxyde de strontium SrO et en oxyde de magnésium MgO est inférieure à 0,6%, inférieure à 0,5%, inférieure à 0,4%, voire inférieure à 0,3% ; - the sum of the mass contents of calcium oxide CaO, barium oxide BaO, strontium oxide SrO and magnesium oxide MgO is less than 0.6%, less than 0.5%, less than 0.4% , or even less than 0.3%;
- la teneur massique en CaO est inférieure à 0,4%, voire inférieure à 0,3% ; - the CaO mass content is less than 0.4%, or even less than 0.3%;
- la teneur massique en BaO est inférieure à 0,4%, voire inférieure à 0,3% ; - the mass content of BaO is less than 0.4%, or even less than 0.3%;
- la teneur massique en SrO est inférieure à 0,4%, voire inférieure à 0,3% ; - the SrO mass content is less than 0.4%, or even less than 0.3%;
- la teneur massique en MgO est inférieure à 0,4%, voire inférieure à 0,3% ; - the MgO mass content is less than 0.4%, or even less than 0.3%;
- le produit se présente sous la forme d’un bloc. - the product comes in the form of a block.
Suivant un mode de réalisation particulièrement avantageux, le produit réfractaire fondu et coulé selon l’invention comprend, en pourcentages massiques sur la base des oxydes : According to a particularly advantageous embodiment, the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
ZrC>2 + HfC>2 : 39,0% à 51 ,0%, de préférence 39,0% à 49,5%, de préférenceZrC>2 + HfC>2: 39.0% to 51.0%, preferably 39.0% to 49.5%, preferably
42,5% à 49,5% 42.5% to 49.5%
SiO2 : 10,5% à 14,0% SiO 2 : 10.5% to 14.0%
AI2O3 : complément à 100% AI2O3: 100% supplement
Na2Û + K2O : 0,80% à 2,50%, voire 0,80% à 2,00% Na2Û + K 2 O: 0.80% to 2.50%, or even 0.80% to 2.00%
Na2O : < 0,60% Na 2 O: < 0.60%
K2O : < 2,00% K 2 O: < 2.00%
B2O3 : < 1 ,0%, voire < 0,5% B2O3: < 1.0%, even < 0.5%
Fe2Ü3 + TiÜ2 : < 0,60% autres espèces : < 1 ,0% avec un rapport (K2O/1 ,52) /(Na2O + K2O/1 ,52) supérieur à 0,60, voire supérieur à 0,65. Fe2Ü3 + TiÜ2: < 0.60% other species: < 1.0% with a ratio (K 2 O/1.52) / (Na2O + K 2 O/1.52) greater than 0.60, or even greater than 0.65.
Suivant un mode de réalisation particulièrement avantageux, le produit réfractaire fondu et coulé selon l’invention comprend, en pourcentages massiques sur la base des oxydes : According to a particularly advantageous embodiment, the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
ZrC>2 + HfC>2 : 39,0% à 51 ,0%, de préférence 39,0% à 49,5%, de préférenceZrC>2 + HfC>2: 39.0% to 51.0%, preferably 39.0% to 49.5%, preferably
42,5% à 49,5% 42.5% to 49.5%
SiO2 : 10,5% à 13,0% SiO 2 : 10.5% to 13.0%
AI2O3 : complément à 100%, de préférence < 44,0% AI2O3: 100% supplement, preferably < 44.0%
K2O : 1 ,00% à 2,00%, de préférence 1 ,10% à 1 ,80% K2O: 1.00% to 2.00%, preferably 1.10% to 1.80%
Na2Û : < 0,50%, de préférence < 0,40%, de préférence < 0,30%Na2Û: <0.50%, preferably <0.40%, preferably <0.30%
B2O3 : < 1 ,0% Fe2Ü3 + TiÜ2 : < 0,60% autres espèces : < 1 ,0% avec un rapport (K2O/1 ,52) /(Na2O + K2O/1 ,52) supérieur à 0,65, voire supérieur à 0,70.B2O3: < 1.0% Fe2Ü3 + TiÜ2: < 0.60% other species: < 1.0% with a ratio (K 2 O/1.52) / (Na2O + K 2 O/1.52) greater than 0.65, or even greater than 0.70.
Suivant un mode de réalisation particulièrement avantageux, le produit réfractaire fondu et coulé selon l’invention comprend, en pourcentages massiques sur la base des oxydes : According to a particularly advantageous embodiment, the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
ZrC>2 + HfC>2 : 42,5% à 49,5%, de préférence 42,5% à 48,0% ZrC>2 + HfC>2: 42.5% to 49.5%, preferably 42.5% to 48.0%
SiC>2 : 10,5% à 13,0%, de préférence 11 ,0% à 13,0% SiC>2: 10.5% to 13.0%, preferably 11.0% to 13.0%
AI2O3 : complément à 100% AI2O3: 100% supplement
K2O : 0,70% à 1 ,80%, de préférence 0,80% à 1 ,60%, K2O: 0.70% to 1.80%, preferably 0.80% to 1.60%,
Na2Û : < 0,60%, de préférence < 0,50%, de préférence < 0,40%,Na2Û: <0.60%, preferably <0.50%, preferably <0.40%,
B2O3 : < 1 ,0% B2O3: < 1.0%
Fe2Ü3 + TiÜ2 : < 0,60% autres espèces : < 1 ,0% avec un rapport (K2O/1 ,52) /(Na2O + K2O/1 ,52) supérieur à 0,62, de préférence supérieur à 0,65, de préférence supérieur à 0,70. Fe2Ü3 + TiÜ2: < 0.60% other species: < 1.0% with a ratio (K 2 O/1.52) / (Na2O + K 2 O/1.52) greater than 0.62, preferably greater at 0.65, preferably greater than 0.70.
Suivant un mode de réalisation particulier, le produit réfractaire fondu et coulé selon l’invention comprend, en pourcentages massiques sur la base des oxydes : According to a particular embodiment, the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
ZrO2 + HfO2 : 39,0% à 49,5%, voire 42,5% à 49,5% ZrO 2 + HfO 2 : 39.0% to 49.5%, or even 42.5% to 49.5%
SiO2 : 10,5% à 14,0%, voire 10,5% à 13,0% SiO 2 : 10.5% to 14.0%, or even 10.5% to 13.0%
AI2O3 : complément à 100%, de préférence < 44,0% AI2O3: 100% supplement, preferably < 44.0%
Na2Ü + K2O : 1 ,00% à 2,50% Na2Ü + K2O: 1.00% to 2.50%
Na2Û : < 0,50%, voire < 0,30% Na2Û: < 0.50%, even < 0.30%
K2O : < 2,00%, voire 0,60% à 1 ,80% K 2 O: <2.00%, or even 0.60% to 1.80%
B2O3 : < 1 ,0%, voire < 0,5% avec un rapport (K2O/1 ,52) /(Na2O + K2O/1 ,52) supérieur à 0,60, voire supérieur à 0,65.B2O3: < 1.0%, even < 0.5% with a ratio (K 2 O/1.52) / (Na2O + K 2 O/1.52) greater than 0.60, even greater than 0.65 .
Suivant un mode de réalisation particulier, le produit réfractaire fondu et coulé selon l’invention comprend, en pourcentages massiques sur la base des oxydes : According to a particular embodiment, the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
ZrO2 + HfO2 : 42,5% à 49,5% ZrO 2 + HfO 2 : 42.5% to 49.5%
SiO2 : 10,5% à 13,0% SiO 2 : 10.5% to 13.0%
AI2O3 : complément à 100%, de préférence < 44,0% AI2O3: 100% supplement, preferably < 44.0%
Na2Ü + K2O : 1 ,00% à 2,00% Na2Ü + K2O: 1.00% to 2.00%
Na2Û : < 0,60% Na2Û: <0.60%
K2O : < 2,00% B2O3 : < 0,5% avec un rapport (K2O/1 ,52) /(Na2O + K2O/1 ,52) supérieur à 0,50. K 2 O: < 2.00% B 2 O 3 : < 0.5% with a ratio (K 2 O/1.52) / (Na 2 O + K 2 O/1.52) greater than 0.50.
Suivant un mode de réalisation particulier, le produit réfractaire fondu et coulé selon l’invention comprend, en pourcentages massiques sur la base des oxydes : According to a particular embodiment, the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
ZrO2 + HfO2 : 42,5% à 49,5% ZrO 2 + HfO 2 : 42.5% to 49.5%
SiO2 : 10,5% à 13,0% SiO 2 : 10.5% to 13.0%
AI2O3 : complément à 100%, de préférence < 44,0% AI 2 O 3 : 100% complement, preferably < 44.0%
Na2O + K2O : 1 ,00% à 2,00% Na 2 O + K 2 O: 1.00% to 2.00%
Na2O : < 1 ,00% Na 2 O: <1.00%
K2O : < 2,00% K 2 O: < 2.00%
B2O3 : < 0,5% avec un rapport (K2O/1 ,52) /(Na2O + K2O/1 ,52) supérieur à 0, 60. B 2 O 3 : < 0.5% with a ratio (K 2 O/1.52) / (Na 2 O + K 2 O/1.52) greater than 0.60.
Suivant un mode de réalisation particulier, le produit réfractaire fondu et coulé selon l’invention comprend, en pourcentages massiques sur la base des oxydes : According to a particular embodiment, the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
AI2O3 : < 44,0% AI 2 O 3 : < 44.0%
ZrO2 + HfO2 : 42,5% à 49,5%, voire 43,5% à 48,0% ZrO 2 + HfO 2 : 42.5% to 49.5%, or even 43.5% to 48.0%
SiO2 : 10,5% à 14,0%, de préférence 10,5% à 13,5% SiO 2 : 10.5% to 14.0%, preferably 10.5% to 13.5%
Na2O + K2O : 1 ,00% à 2,00% Na 2 O + K 2 O: 1.00% to 2.00%
Na2O : < 0,60% Na 2 O: < 0.60%
K2O : < 2,00%, de préférence 0,30% à 1 ,80% avec un rapport (K2O/1 ,52) /(Na2O + K2O/1 ,52) de préférence supérieur à 0,60, de préférence supérieur à 0,62, voire supérieur à 0,65, à 0,70, ou à 0,75. K 2 O: <2.00%, preferably 0.30% to 1.80% with a ratio (K 2 O/1.52)/(Na 2 O + K 2 O/1.52) preferably higher at 0.60, preferably greater than 0.62, or even greater than 0.65, 0.70, or 0.75.
Dans un mode de réalisation particulier, le produit réfractaire fondu et coulé selon l’invention comprend, en pourcentages massiques sur la base des oxydes : In a particular embodiment, the melted and cast refractory product according to the invention comprises, in mass percentages based on the oxides:
ZrO2 : 45,5% à 48,0% ZrO 2 : 45.5% to 48.0%
SiO2 : 10,5% à 13,0% SiO 2 : 10.5% to 13.0%
Na2O + K2O : 1 ,00% à 2,00% Na 2 O + K 2 O: 1.00% to 2.00%
Na2O : < 0,60% Na 2 O: < 0.60%
K2O : < 2,00% avec un rapport (K2O/1 ,52) /(Na2O + K2O/1 ,52) supérieur à 0,65. K 2 O: <2.00% with a ratio (K 2 O/1.52) /(Na 2 O + K 2 O/1.52) greater than 0.65.
Dans la mesure où les caractéristiques optionnelles ci-dessus ne sont pas incompatibles techniquement entre elles, elles peuvent être combinées. L’invention concerne également un procédé de fabrication d’un produit réfractaire selon l’invention, comprenant les étapes successives suivantes : a) mélange de matières premières de manière à former une charge de départ, b) fusion de ladite charge de départ jusqu’à obtention d’une matière en fusion, c) coulage et solidification de ladite matière en fusion, par refroidissement, de manière à obtenir un produit réfractaire, ce procédé étant remarquable en ce que lesdites matières premières sont choisies de manière que ledit produit réfractaire soit conforme à l’invention. To the extent that the optional features above are not technically incompatible with each other, they can be combined. The invention also relates to a process for manufacturing a refractory product according to the invention, comprising the following successive steps: a) mixing of raw materials so as to form a starting charge, b) melting of said starting charge until obtaining a molten material, c) casting and solidifying said molten material, by cooling, so as to obtain a refractory product, this process being remarkable in that said raw materials are chosen so that said refractory product is in accordance with the invention.
De préférence, on ajoute systématiquement et méthodiquement les oxydes pour lesquels une teneur minimale est nécessaire, ou des précurseurs de ces oxydes. De préférence, on tient compte des teneurs de ces oxydes dans les sources des autres oxydes où ils sont présents comme impuretés. Preferably, the oxides for which a minimum content is necessary, or precursors of these oxides, are added systematically and methodically. Preferably, the contents of these oxides are taken into account in the sources of other oxides where they are present as impurities.
De préférence, le refroidissement est contrôlé, de préférence de manière à être effectué à une vitesse inférieure à 20°C par heure, de préférence à la vitesse d’environ 10°C par heure. Preferably, the cooling is controlled, preferably so as to be carried out at a rate of less than 20°C per hour, preferably at a rate of approximately 10°C per hour.
L’invention concerne aussi un four de fusion de verre comportant un produit réfractaire selon l’invention, ou un produit réfractaire fabriqué ou susceptible d’avoir été fabriqué suivant un procédé selon l’invention, en particulier dans une région destinée à être en contact avec du verre en fusion, en particulier dans une cuve de four de fusion de verre, en particulier pour constituer un bloc porte électrode, par exemple dans une sole d’une telle cuve. The invention also relates to a glass melting furnace comprising a refractory product according to the invention, or a refractory product manufactured or likely to have been manufactured according to a process according to the invention, in particular in a region intended to be in contact with molten glass, in particular in a glass melting furnace tank, in particular to constitute an electrode holder block, for example in a floor of such a tank.
L’invention concerne ainsi un four de fusion de verre comportant une cuve destinée à contenir ou contenant du verre en fusion, la cuve comportant un bloc en un produit selon l’invention. The invention thus relates to a glass melting furnace comprising a tank intended to contain or containing molten glass, the tank comprising a block of a product according to the invention.
L’invention concerne enfin un procédé de contrôle d’un four de fusion de verre selon l’invention, ledit procédé comportant les opérations suivantes : The invention finally relates to a method for controlling a glass melting furnace according to the invention, said method comprising the following operations:
- application d’une onde électromagnétique à un bloc en un produit réfractaire selon l’invention, de préférence une onde de type radar, d’une fréquence de préférence comprise entre 1 et 10 gigahertz, voire entre 1 et 6 gigahertz ; - application of an electromagnetic wave to a block of a refractory product according to the invention, preferably a radar type wave, with a frequency preferably between 1 and 10 gigahertz, or even between 1 and 6 gigahertz;
- analyse du signal reçu en réponse à ladite application de manière à déterminer une information relative audit bloc ou à un changement de milieu, traduisant notamment une interface entre le bloc et le milieu. - analysis of the signal received in response to said application so as to determine information relating to said block or to a change of medium, reflecting in particular an interface between the block and the medium.
Dans un mode de réalisation, l’application de l’onde électromagnétique est réalisée alors que le four est en service, le bloc étant optionnellement en contact avec du verre en fusion. L’application de l’onde électromagnétique et l’analyse peuvent être réalisées par toutes les techniques connues, par exemple à l’aide du dispositif SmartMelter® proposé par PaneraTech. In one embodiment, the application of the electromagnetic wave is carried out while the furnace is in service, the block optionally being in contact with molten glass. The application of the electromagnetic wave and the analysis can be carried out by all known techniques, for example using the SmartMelter® device offered by PaneraTech.
Définitions Definitions
Un produit est classiquement dit « fondu » lorsqu'il est obtenu par un procédé mettant en œuvre une fusion d’une charge jusqu’à obtention d’une matière en fusion, puis une solidification de cette matière par refroidissement. A product is conventionally said to be “molten” when it is obtained by a process involving melting a charge until a molten material is obtained, then solidifying this material by cooling.
Un bloc est un objet dont toutes les dimensions sont supérieures à 10 mm. Toutes les dimensions d’un bloc selon l’invention sont de préférence supérieures à 50 mm, de préférence supérieures à 100 mm. Un bloc selon l’invention peut par exemple avoir une forme générale parallélépipédique ou bien une forme spécifique adaptée à son utilisation. A la différence d’une couche, un bloc en un produit réfractaire fondu et coulé est classiquement obtenu par un procédé comportant des opérations de moulage et de démoulage. A block is an object with all dimensions greater than 10 mm. All dimensions of a block according to the invention are preferably greater than 50 mm, preferably greater than 100 mm. A block according to the invention can for example have a general parallelepiped shape or a specific shape adapted to its use. Unlike a layer, a block of a melted and cast refractory product is conventionally obtained by a process comprising molding and demolding operations.
Le bloc en un produit selon l’invention, avant ou après démasselottage/usinage, peut présenter une, voire deux ou trois dimensions hors tout (épaisseur, longueur, ou largeur) d'au moins 150 mm, de préférence d'au moins 250 mm, voire d'au moins 400 mm, voire d'au moins 500 mm, voire d'au moins 600 mm, voire d'au moins 800 mm ou même d'au moins 1000 mm, et/ou inférieure(s) à 2000 mm, The block in one product according to the invention, before or after dismantling/machining, can have one, or even two or three overall dimensions (thickness, length, or width) of at least 150 mm, preferably at least 250 mm, or even at least 400 mm, or even at least 500 mm, or even at least 600 mm, or even at least 800 mm or even at least 1000 mm, and/or less than 2000mm,
Sauf mention contraire, toutes les teneurs en oxydes dans un produit selon l’invention sont des pourcentages massiques sur la base des oxydes. Une teneur massique d’un oxyde d’un élément métallique se rapporte à la teneur totale de cet élément exprimée sous la forme de l'oxyde le plus stable, selon la convention habituelle de l'industrie. Unless otherwise stated, all oxide contents in a product according to the invention are mass percentages based on the oxides. A mass content of an oxide of a metallic element refers to the total content of this element expressed in the form of the most stable oxide, according to the usual industry convention.
HfO2 n'est pas chimiquement dissociable de ZrO2. Cependant, selon la présente invention, HfO2 n'est pas ajouté volontairement dans la charge. HfO2 ne désigne donc que les traces d'oxyde d'hafnium, cet oxyde étant toujours naturellement présent dans les sources d’oxyde de zirconium à des teneurs généralement inférieures à 5%, généralement inférieures à 2%. Dans un bloc selon l’invention, la teneur massique en HfO2 est inférieure à 5%, de préférence inférieure à 3%, de préférence inférieure à 2%. Par souci de clarté, on peut désigner indifféremment la teneur totale en oxyde de zirconium et en traces d'oxyde d'hafnium par « ZrO2 » ou par « ZrO2 + HfO2 ». HfO2 n'est donc pas compris dans les "autres espèces". HfO 2 is not chemically dissociable from ZrO 2 . However, according to the present invention, HfO 2 is not added voluntarily to the feed. HfO 2 therefore only designates traces of hafnium oxide, this oxide always being naturally present in sources of zirconium oxide at contents generally less than 5%, generally less than 2%. In a block according to the invention, the mass content of HfO 2 is less than 5%, preferably less than 3%, preferably less than 2%. For the sake of clarity, the total content of zirconium oxide and traces of hafnium oxide can be designated either as “ZrO 2 ” or as “ZrO 2 + HfO 2 ”. HfO 2 is therefore not included in the “other species”.
Par « impuretés », on entend les constituants inévitables, introduits avec les matières premières ou résultant de réactions avec ces constituants. Les impuretés ne sont pas des constituants nécessaires, mais seulement tolérés. Par exemple, les composés faisant partie du groupe des oxydes, nitrures, oxynitrures, carbures, oxycarbures, carbonitrures et espèces métalliques de fer, titane, vanadium et chrome sont des impuretés. By “impurities” we mean the inevitable constituents, introduced with the raw materials or resulting from reactions with these constituents. Impurities are not constituents necessary, but only tolerated. For example, compounds belonging to the group of oxides, nitrides, oxynitrides, carbides, oxycarbides, carbonitrides and metallic species of iron, titanium, vanadium and chromium are impurities.
La porosité totale, en pourcentage, est classiquement égale à 100 x (1 - le rapport de la densité géométrique divisée par la densité absolue). Total porosity, as a percentage, is typically equal to 100 x (1 - the ratio of geometric density divided by absolute density).
La densité géométrique est mesurée suivant la norme ISO 5016:1997 ou EN 1094-4 et exprimée en g/cm3. Elle est classiquement égale au rapport de la masse de l'échantillon divisée par le volume apparent. Geometric density is measured according to standard ISO 5016:1997 or EN 1094-4 and expressed in g/cm 3 . It is conventionally equal to the ratio of the mass of the sample divided by the apparent volume.
La valeur de densité absolue, exprimée en g/cm3, peut être mesurée en divisant la masse d'un échantillon par le volume de cet échantillon broyé de manière à sensiblement supprimer la porosité. The absolute density value, expressed in g/cm 3 , can be measured by dividing the mass of a sample by the volume of that sample ground so as to substantially eliminate porosity.
Description détaillée detailed description
Dans les produits fondus et coulés selon l’invention, la teneur en ZrÛ2 + HfO2 permet de répondre aux exigences de haute résistance à la corrosion. En revanche, de trop fortes teneurs sont nuisibles pour la faisabilité industrielle de blocs. In the melted and cast products according to the invention, the ZrÛ2 + HfO2 content makes it possible to meet the requirements of high corrosion resistance. On the other hand, too high contents are harmful for the industrial feasibility of blocks.
L’oxyde d’hafnium, HfC>2, présent dans le produit selon l’invention est de préférence l’oxyde d’hafnium naturellement présent dans les sources de ZrO2. Sa teneur dans un produit selon l’invention est donc inférieure à 4%, généralement inférieure à 2%, voire inférieure à 1%. The hafnium oxide, HfC>2, present in the product according to the invention is preferably the hafnium oxide naturally present in ZrO 2 sources. Its content in a product according to the invention is therefore less than 4%, generally less than 2%, or even less than 1%.
La présence de SiC>2 permet notamment la formation d’une phase vitreuse intergranulaire contribuant à la faisabilité des produits car apte à accommoder de manière efficace les déformations en température. La teneur massique de SiC>2 est de préférence limitée afin de limiter la quantité de phase vitreuse. The presence of SiC>2 allows in particular the formation of an intergranular vitreous phase contributing to the feasibility of the products because it is able to effectively accommodate temperature deformations. The mass content of SiC>2 is preferably limited in order to limit the quantity of glassy phase.
La présence de Na2O+K2O contribue à la faisabilité des produits. La teneur massique de Na2O+K2O est de préférence limitée afin de limiter la quantité de phase vitreuse et notamment conserver une bonne résistance à la corrosion par le verre en fusion ainsi qu’une bonne propagation des ondes. The presence of Na2O+K 2 O contributes to the feasibility of the products. The mass content of Na2O+K 2 O is preferably limited in order to limit the quantity of vitreous phase and in particular to maintain good resistance to corrosion by molten glass as well as good wave propagation.
La présence K2O est nécessaire pour avoir un rapport (K2O/1 ,52) / (Na2Û + K2O/1 ,52) supérieur à 0,30, voire supérieur à 0,40, voire supérieur à 0,50, voire supérieur à 0,60, voire supérieur à 0,62, voire supérieur à 0,65, et permettre une bonne pénétration des ondes dans le bloc. Na2Û a un effet un effet défavorable sur la bonne pénétration des ondes dans le bloc. La teneur massique en oxyde de sodium Na2O doit donc rester limitée. The presence of K 2 O is necessary to have a ratio (K 2 O/1.52) / (Na2Û + K 2 O/1.52) greater than 0.30, or even greater than 0.40, or even greater than 0, 50, or even greater than 0.60, or even greater than 0.62, or even greater than 0.65, and allow good penetration of the waves into the block. Na2Û has an unfavorable effect on the good penetration of waves into the block. The mass content of sodium oxide Na2O must therefore remain limited.
B2O3 peut avoir un effet un effet défavorable sur la faisabilité. La teneur massique en oxyde de bore B2O3doit donc rester limitée. B2O3 may have an adverse effect on feasibility. The mass content of boron oxide B 2 O3 must therefore remain limited.
Y2O3 peut avoir un effet un effet défavorable sur la faisabilité. La teneur massique en Y2O3 doit donc rester limitée. Y2O3 may have an adverse effect on feasibility. The mass content of Y2O3 must therefore remain limited.
Selon l’invention, la teneur massique de Fe20s + TiÛ2 est inférieure à 0,60%, de préférence inférieure à 0,50%, de préférence inférieure à 0,30%. De préférence, la teneur massique de P2O5 est inférieure à 0,05%. En effet, ces oxydes sont néfastes, notamment pour l’exsudation des produits réfractaires ou la coloration du verre et leur teneur doit être limitée à des traces introduites à titre d’impuretés avec les matières premières. According to the invention, the mass content of Fe20s + TiO2 is less than 0.60%, preferably less than 0.50%, preferably less than 0.30%. Preferably, the mass content of P2O5 is less than 0.05%. In fact, these oxides are harmful, particularly for the exudation of refractory products or the coloring of glass and their content must be limited to traces introduced as impurities with the raw materials.
Les « autres espèces » sont les espèces oxydes qui ne sont pas listées ci-dessus, à savoir les espèces autres que ZrC>2, HfC>2, SiC>2, AI2O3, Na2Û, K2O, B2O3, Y2O3, TiC>2 et Fe20s. Dans un mode de réalisation, les « autres espèces » sont limitées à des espèces dont la présence n’est pas particulièrement souhaitée et qui sont généralement présentes à titre d’impuretés dans les matières premières. The “other species” are the oxide species which are not listed above, namely species other than ZrC>2, HfC>2, SiC>2, Al2O3, Na2Û, K 2 O, B2O3, Y2O3, TiC> 2 and Fe20s. In one embodiment, the "other species" are limited to species whose presence is not particularly desired and which are generally present as impurities in the raw materials.
De préférence, le produit selon l’invention se présente sous la forme d’un bloc, de préférence d’un bloc dont au moins une, de préférence au moins deux, voire toutes les dimensions hors-tout sont supérieures à 150 mm. Preferably, the product according to the invention is in the form of a block, preferably a block of which at least one, preferably at least two, or even all of the overall dimensions are greater than 150 mm.
La porosité totale du produit selon l’invention est inférieure à 15%, voire inférieure à 10%, voire inférieure à 5%, voire inférieure à 2%, voire inférieure à 1%. The total porosity of the product according to the invention is less than 15%, or even less than 10%, or even less than 5%, or even less than 2%, or even less than 1%.
Un produit selon l’invention peut être classiquement fabriqué suivant les étapes a) à c) décrites ci-dessous : a) mélange de matières premières de manière à former une charge de départ, b) fusion de ladite charge de départ jusqu’à obtention d’une matière en fusion, c) solidification de ladite matière en fusion, par refroidissement, de manière à obtenir un produit réfractaire selon l’invention. A product according to the invention can be conventionally manufactured following steps a) to c) described below: a) mixing of raw materials so as to form a starting charge, b) melting of said starting charge until obtaining of a molten material, c) solidification of said molten material, by cooling, so as to obtain a refractory product according to the invention.
A l’étape a), les matières premières sont choisies de manière à garantir les teneurs en oxydes dans le produit fini obtenu à l’issue de l’étape c). L’homme du métier sait parfaitement choisir les matières premières à cet effet. A l’étape b), la fusion est de préférence réalisée grâce à l’action combinée d’un arc électrique assez long, ne produisant pas de réduction, et d’un brassage favorisant la réoxydation des produits. In step a), the raw materials are chosen so as to guarantee the oxide contents in the finished product obtained at the end of step c). A person skilled in the art knows perfectly well how to choose the raw materials for this purpose. In step b), the fusion is preferably carried out thanks to the combined action of a fairly long electric arc, not producing reduction, and stirring promoting the reoxidation of the products.
Il est préférable d'opérer la fusion dans des conditions oxydantes pour les applications visées.It is preferable to carry out the fusion under oxidizing conditions for the intended applications.
Préférentiellement, on utilise le procédé de fusion à l'arc long décrit dans le brevet français n°1 208 577 et ses additions n°75893 et 82310. Preferably, the long arc fusion process described in French patent No. 1,208,577 and its additions No. 75893 and 82310 is used.
Ce procédé consiste à utiliser un four à arc électrique dont l'arc jaillit entre la charge et au moins une électrode écartée de cette charge et à régler la longueur de l'arc pour que son action réductrice soit réduite au minimum, tout en maintenant une atmosphère oxydante au-dessus du bain en fusion et en brassant ledit bain, par exemple par l'action de l'arc lui-même. This process consists of using an electric arc furnace whose arc flashes between the load and at least one electrode spaced from this load and in adjusting the length of the arc so that its reducing action is reduced to a minimum, while maintaining a oxidizing atmosphere above the molten bath and by stirring said bath, for example by the action of the arc itself.
A l’étape c), le refroidissement est de préférence effectué à une vitesse inférieure à 20°C par heure, de préférence à la vitesse d’environ 10°C par heure, de préférence dans un moule aux dimensions souhaitées, compte tenu du masselottage et d’un éventuel usinage après l’étape c).In step c), the cooling is preferably carried out at a speed of less than 20°C per hour, preferably at a speed of approximately 10°C per hour, preferably in a mold of the desired dimensions, taking into account the weighting and possible machining after step c).
Tout procédé conventionnel de fabrication de produits fondus à base de zircone destinés à des applications dans des fours de fusion de verre peut être mis en œuvre, pourvu que la composition de la charge de départ permette d’obtenir des produits présentant une composition conforme à celle d’un produit selon l’invention. Any conventional process for manufacturing zirconia-based melted products intended for applications in glass melting furnaces can be implemented, provided that the composition of the starting charge makes it possible to obtain products having a composition conforming to that of a product according to the invention.
Exemples Examples
Les exemples non limitatifs suivants sont donnés dans le but d’illustrer l’invention. The following non-limiting examples are given for the purpose of illustrating the invention.
Dans ces exemples, on a employé les matières premières suivantes : In these examples, the following raw materials were used:
- de la zircone Q1 contenant en moyenne 99% de ZrC>2 + HfC>2, - Q1 zirconia containing on average 99% ZrC>2 + HfC>2,
- de la silice « Sable BE01 Bédouin » contenant en moyenne 99% de SiC>2, - “Sable BE01 Bédouin” silica containing on average 99% SiC>2,
- de l’alumine de type AC34 contenant en moyenne 99% d’ALOs, - AC34 type alumina containing on average 99% ALOs,
- du carbonate de sodium contenant en moyenne 99,5% Na2COs comme source de Na2Û,- sodium carbonate containing on average 99.5% Na2COs as a source of Na2Û,
- du carbonate de potassium contenant en moyenne 99,5% K2CO3 comme source de K2O.- potassium carbonate containing on average 99.5% K2CO3 as a source of K2O.
Les produits ont été préparés selon le procédé classique de fusion en four à arc, puis coulés dans un moule pour obtenir des blocs de format minimum 150 mm x 250 mm x 500 mm après démasselottage.
Figure imgf000013_0001
The products were prepared using the classic arc furnace melting process, then poured into a mold to obtain blocks with a minimum size of 150 mm x 250 mm x 500 mm after unblocking.
Figure imgf000013_0001
L’analyse chimique moyenne des produits obtenus est donnée dans le tableau 1 ; il s’agit d’une analyse chimique de la charge liquide coulée dans le moule, donnée en pourcentages massiques. Les espèces autres que ZrÛ2, HfO2, SiO2, AI2O3, B2O3, Na2Û et K2O, en particulier Fe2Os, TiO2 et Y2O3 (éventuellement présents) sont des impuretés, avec Y2O3 < 0,2% et Fe2Os + TO2 < 0,3%.The average chemical analysis of the products obtained is given in Table 1; this is a chemical analysis of the liquid filler poured into the mold, given in mass percentages. Species other than ZrO2, HfO2, SiO2, AI2O3, B2O3, Na2O and K 2 O, in particular Fe2Os, TiO2 and Y2O3 (if present) are impurities, with Y2O3 < 0.2% and Fe2Os + TO2 < 0.3 %.
Dans le tableau 1 , la teneur en HfO2 est toujours inférieure à 4%. Le rapport (K2O/1 ,52) / (Na2Û + K2O/1 ,52) est noté « Ratio ». In table 1, the HfO2 content is always less than 4%. The ratio (K 2 O/1.52) / (Na2Û + K 2 O/1.52) is denoted “Ratio”.
Faisabilité Feasibility
L’état extérieur des produits obtenus est observé. Leur taille, avec les trois dimensions supérieures à 150 mm et au moins une dimension d’au moins 400 mm, permet d’estimer la faisabilité industrielle. En cas de présence d’une fente traversante, la faisabilité est jugée insatisfaisante. Les produits sont ensuite coupés en deux pour observer le remplissage. En cas de remplissage incorrect, la faisabilité est jugée insatisfaisante. Sinon, la faisabilité est jugée satisfaisante. Tous les exemples de l’invention présentent une faisabilité satisfaisante. The external state of the products obtained is observed. Their size, with the three dimensions greater than 150 mm and at least one dimension of at least 400 mm, makes it possible to estimate industrial feasibility. If a through slot is present, the feasibility is considered unsatisfactory. The products are then cut in half to observe the filling. In case of incorrect filling, the feasibility is considered unsatisfactory. Otherwise, the feasibility is considered satisfactory. All examples of the invention present satisfactory feasibility.
Mesure de la propagation des ondes Measurement of wave propagation
Sur les différents exemples de blocs réalisés, des barreaux cylindriques de produit d’environ 4 mm de diamètre et de 13 mm de hauteur ont été pénétrés par une onde de 2,4 gigahertz à 1000°C (correspondant à une température proche de celle de la face externe des blocs de cuve). On étudie le signal reçu pour évaluer la profondeur à laquelle l’onde a perdu la moitié de sa puissance (« half power depth » en anglais, ou HPD) ; celle-ci est ensuite divisée par la valeur obtenue pour la référence (Exemple 1 *) et multipliée par 100 pour donner un indice P de propagation des ondes. On the various examples of blocks produced, cylindrical bars of product of approximately 4 mm in diameter and 13 mm in height were penetrated by a wave of 2.4 gigahertz at 1000°C (corresponding to a temperature close to that of the external face of the tank blocks). We study the received signal to evaluate the depth at which the wave has lost half of its power (“half power depth” in English, or HPD); this is then divided by the value obtained for the reference (Example 1 *) and multiplied by 100 to give an index P of wave propagation.
[Tableau 1]
Figure imgf000014_0001
signifie « hors invention » [Table 1]
Figure imgf000014_0001
means “outside invention”
Il apparaît que l’indice P augmente lorsque le Ratio augmente. L’enrichissement des produits en oxyde de potassium par rapport à la quantité d’oxyde de sodium de manière que le Ratio soit supérieur à 0,30 lorsque la teneur en Na2Û est inférieure à 0,60%, ou de manière que le Ratio soit supérieur à 0,60, permet de favoriser la pénétration des ondes dans le produit réfractaire, et ainsi améliorer la qualité du suivi, sans détérioration de la faisabilité. It appears that the P index increases when the Ratio increases. The enrichment of products with potassium oxide in relation to the quantity of sodium oxide so that the Ratio is greater than 0.30 when the Na2Û content is less than 0.60%, or so that the Ratio is greater than 0.60, makes it possible to promote the penetration of waves into the refractory product, and thus improve the quality of monitoring , without deterioration of feasibility.
Comme cela apparaît clairement, l’invention fournit donc un produit qui présente des performances remarquables dans l’environnement d’une cuve de four de fusion de verre. As is clear, the invention therefore provides a product which exhibits remarkable performance in the environment of a glass melting furnace tank.
Bien entendu, l’invention n’est pas limitée aux modes de réalisation décrits et représentés, fournis à des fins illustratives seulement. Of course, the invention is not limited to the embodiments described and represented, provided for illustrative purposes only.

Claims

Revendications Claims
1 . Produit réfractaire fondu et coulé comportant, en pourcentages massiques sur la base des oxydes et pour un total de 100% : 1. Melted and cast refractory product comprising, in mass percentages based on oxides and for a total of 100%:
ZrC>2 + HfC>2 : 39,0% à 55,0% avec HfC>2 < 5% ZrC>2 + HfC>2: 39.0% to 55.0% with HfC>2 < 5%
SiO2 : 10,5% à 14,0% SiO 2 : 10.5% to 14.0%
AI2O3 : complément à 100% AI2O3: 100% supplement
Na2O + K2O : 0,80% à 3,00% Na 2 O + K 2 O: 0.80% to 3.00%
B2O3 : < 1 ,0 % B2O3: <1.0%
Fe2Ü3 + TiÜ2 : < 0,60% autres espèces : < 1 ,0% Fe2Ü3 + TiÜ2: < 0.60% other species: < 1.0%
- le rapport (K2O/1 ,52) / (Na2Û + K2O/1 ,52) étant supérieur à 0,30 avec Na2Û < 0,60%, ou - the ratio (K 2 O/1.52) / (Na2Û + K 2 O/1.52) being greater than 0.30 with Na2Û < 0.60%, or
- le rapport (K2O/1 ,52) / (Na2Û + K2O/1 ,52) étant supérieur à 0,60. - the ratio (K 2 O/1.52) / (Na2Û + K 2 O/1.52) being greater than 0.60.
2. Produit selon la revendication précédente, dans lequel le rapport (K2O/1 ,52) / (Na2Û + K2O/1 ,52) est supérieur à 0,40. 2. Product according to the preceding claim, in which the ratio (K 2 O/1.52) / (Na2Û + K2O/1.52) is greater than 0.40.
3. Produit selon la revendication immédiatement précédente, dans lequel le rapport (K2O/1 ,52) / (Na2Û + K2O/1 ,52) est supérieur à 0,50. 3. Product according to the immediately preceding claim, in which the ratio (K2O/1.52) / (Na2Û + K2O/1.52) is greater than 0.50.
4. Produit selon la revendication immédiatement précédente, dans lequel le rapport (K2O/1 ,52) / (Na2Û + K2O/1 ,52) est supérieur à 0,60. 4. Product according to the immediately preceding claim, in which the ratio (K2O/1.52) / (Na2Û + K2O/1.52) is greater than 0.60.
5. Produit selon la revendication immédiatement précédente, dans lequel le rapport (K2O/1 ,52) / (Na2Û + K2O/1 ,52) est supérieur à 0,62. 5. Product according to the immediately preceding claim, in which the ratio (K2O/1.52) / (Na2Û + K2O/1.52) is greater than 0.62.
6. Produit selon la revendication immédiatement précédente, dans lequel le rapport (K2O/1 ,52) / (Na2Û + K2O/1 ,52) est supérieur à 0,65. 6. Product according to the immediately preceding claim, in which the ratio (K2O/1.52) / (Na2Û + K2O/1.52) is greater than 0.65.
7. Produit selon l’une quelconque des revendications précédentes, dans lequel la teneur massique en ZrC>2 + HfC>2 est supérieure à 42,5%. 7. Product according to any one of the preceding claims, in which the mass content of ZrC>2 + HfC>2 is greater than 42.5%.
8. Produit selon la revendication immédiatement précédente, dans lequel la teneur massique en ZrC>2 + HfC>2 est supérieure à 43,5%. 8. Product according to the immediately preceding claim, in which the mass content of ZrC>2 + HfC>2 is greater than 43.5%.
9. Produit selon la revendication immédiatement précédente, dans lequel la teneur massique en ZrÛ2 + HfC>2 est supérieure à 44,5%. 9. Product according to the immediately preceding claim, in which the mass content of ZrÛ2 + HfC>2 is greater than 44.5%.
10. Produit selon l’une quelconque des revendications précédentes, dans lequel la teneur massique en ZrC>2 + HfC>2 est inférieure à 52,5%. 10. Product according to any one of the preceding claims, in which the mass content of ZrC>2 + HfC>2 is less than 52.5%.
11 . Produit selon la revendication immédiatement précédente, dans lequel la teneur massique en ZrC>2 + HfC>2 est inférieure à 51 ,0%. 11. Product according to the immediately preceding claim, in which the mass content of ZrC>2 + HfC>2 is less than 51.0%.
12. Produit selon la revendication immédiatement précédente, dans lequel la teneur massique en ZrC>2 + HfC>2 est inférieure à 49,5%. 12. Product according to the immediately preceding claim, in which the mass content of ZrC>2 + HfC>2 is less than 49.5%.
13. Produit selon la revendication immédiatement précédente, dans lequel la teneur massique en ZrC>2 + HfC>2 est inférieure à 48,0%. 13. Product according to the immediately preceding claim, in which the mass content of ZrC>2 + HfC>2 is less than 48.0%.
14. Produit selon l’une quelconque des revendications précédentes, dans lequel la teneur massique en SiC>2 est inférieure à 13,5%. 14. Product according to any one of the preceding claims, in which the mass content of SiC>2 is less than 13.5%.
15. Produit selon la revendication immédiatement précédente, dans lequel la teneur massique en SiC>2 est inférieure à 13,0%. 15. Product according to the immediately preceding claim, in which the mass content of SiC>2 is less than 13.0%.
16. Produit selon l’une quelconque des revendications précédentes, dans lequel la teneur massique en SiC>2 est supérieure à 11 ,0%. 16. Product according to any one of the preceding claims, in which the mass content of SiC>2 is greater than 11.0%.
17. Produit selon l’une quelconque des revendications précédentes, dans lequel la teneur massique en Na2Û est inférieure à 0,60%. 17. Product according to any one of the preceding claims, in which the mass content of Na2Û is less than 0.60%.
18. Produit selon la revendication immédiatement précédente, dans lequel la teneur massique en Na2Û est inférieure à 0,55%. 18. Product according to the immediately preceding claim, in which the mass content of Na2Û is less than 0.55%.
19. Produit selon la revendication immédiatement précédente, dans lequel la teneur massique en Na2Û est inférieure à 0,50%. 19. Product according to the immediately preceding claim, in which the mass content of Na2Û is less than 0.50%.
20. Produit selon l’une quelconque des revendications précédentes, dans lequel, en pourcentages massiques sur la base des oxydes : Na2Û + K2O : 0,80% à20. Product according to any one of the preceding claims, in which, in mass percentages based on the oxides: Na2Û + K 2 O: 0.80% at
2,50%, de préférence 0,80% à 2,00% 2.50%, preferably 0.80% to 2.00%
Na2Û : < 0,60%, de préférence < 0,55% Y1 avec un rapport (K2O/1 ,52) /(Na2O + K2O/1 ,52) supérieur à 0,60, de préférence supérieur à 0,62, voire supérieur à 0,65. Na2Û: <0.60%, preferably <0.55% Y1 with a ratio (K 2 O/1.52)/(Na2O + K 2 O/1.52) greater than 0.60, preferably greater than 0.62, or even greater than 0.65.
21 . Produit selon l’une quelconque des revendications précédentes, dans lequel la teneur massique en K2O est supérieure à 0,60% et inférieure à 2,00%. 21. Product according to any one of the preceding claims, in which the mass content of K 2 O is greater than 0.60% and less than 2.00%.
22. Produit selon l’une quelconque des revendications précédentes, dans lequel la teneur massique en K2O est supérieure à 0,70%. 22. Product according to any one of the preceding claims, in which the K 2 O mass content is greater than 0.70%.
23. Produit selon la revendication immédiatement précédente, dans lequel la teneur massique en K2O est supérieure à 0,80%. 23. Product according to the immediately preceding claim, in which the mass content of K 2 O is greater than 0.80%.
24. Produit selon la revendication immédiatement précédente, dans lequel la teneur massique en K2O est supérieure à 1 ,00%. 24. Product according to the immediately preceding claim, in which the mass content of K 2 O is greater than 1.00%.
25. Produit selon l’une quelconque des revendications précédentes, dans lequel la teneur massique en K2O est inférieure à 1 ,80%. 25. Product according to any one of the preceding claims, in which the mass content of K 2 O is less than 1.80%.
26. Produit selon l’une quelconque des revendications précédentes, dans lequel la teneur massique en Na2O + K2O est inférieure à 2,50%. 26. Product according to any one of the preceding claims, in which the mass content of Na 2 O + K 2 O is less than 2.50%.
27. Produit selon la revendication immédiatement précédente, dans lequel la teneur massique en Na2O + K2O est inférieure à 2,00%. 27. Product according to the immediately preceding claim, in which the mass content of Na 2 O + K 2 O is less than 2.00%.
28. Produit selon l’une quelconque des revendications précédentes, dans lequel la teneur massique en AI2O3 est inférieure à 44,0% et supérieure à 30,0%. 28. Product according to any one of the preceding claims, in which the mass content of AI 2 O 3 is less than 44.0% and greater than 30.0%.
29. Produit réfractaire fondu et coulé comportant, en pourcentages massiques sur la base des oxydes et pour un total de 100% : 29. Melted and cast refractory product comprising, in mass percentages on the basis of oxides and for a total of 100%:
ZrO2 + HfO2 : 39,0% à 51 ,0%, de préférence 39,0% à 49,5%, de préférence 42,5% à 49,5% ZrO 2 + HfO 2 : 39.0% to 51.0%, preferably 39.0% to 49.5%, preferably 42.5% to 49.5%
SiO2 : 10,5% à 13,0% SiO 2 : 10.5% to 13.0%
AI2O3 : complément à 100%, de préférence < 44,0%AI 2 O 3 : 100% complement, preferably < 44.0%
K2O : 1 ,00% à 2,00%, de préférence 1 ,10% à 1 ,80%K 2 O: 1.00% to 2.00%, preferably 1.10% to 1.80%
Na2O : < 0,50%, de préférence < 0,40%, de préférence < 0,30%Na 2 O: <0.50%, preferably <0.40%, preferably <0.30%
B2O3 : < 1 ,0% B 2 O 3 : < 1.0%
Fe2O3 + TiO2 : < 0,60% autres espèces : < 1 ,0% avec un rapport (K2O/1 ,52) /(Na2O + K2O/1 ,52) supérieur à 0,65, voire supérieur à 0,70. Four de fusion de verre comportant une une cuve destinée à contenir ou contenant du verre en fusion, la cuve comportant un bloc en un produit selon l’une quelconque des revendications précédentes. Procédé de contrôle d’un four de fusion de verre, ledit procédé comportant les opérations suivantes : Fe 2 O 3 + TiO 2 : < 0.60% other species: < 1.0% with a ratio (K2O/1.52) /(Na2O + K2O/1.52) greater than 0.65, or even greater than 0.70. Glass melting furnace comprising a tank intended to contain or containing molten glass, the tank comprising a block of a product according to any one of the preceding claims. Method for controlling a glass melting furnace, said method comprising the following operations:
- application d’une onde électromagnétique à un bloc en un produit réfractaire selon l’une quelconque des revendications 1 à 29 ; - analyse du signal reçu en réponse à ladite application de manière à déterminer une information relative audit bloc ou à un changement de milieu, traduisant notamment une interface. - application of an electromagnetic wave to a block of a refractory product according to any one of claims 1 to 29; - analysis of the signal received in response to said application so as to determine information relating to said block or to a change of environment, reflecting in particular an interface.
PCT/EP2023/078573 2022-10-14 2023-10-13 Alumina-zirconia-silica refractory product WO2024079356A1 (en)

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