EP4602015A1 - Feuerfestes produkt aus aluminiumoxid-zirkonoxid-siliciumdioxid - Google Patents

Feuerfestes produkt aus aluminiumoxid-zirkonoxid-siliciumdioxid

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Publication number
EP4602015A1
EP4602015A1 EP23790296.0A EP23790296A EP4602015A1 EP 4602015 A1 EP4602015 A1 EP 4602015A1 EP 23790296 A EP23790296 A EP 23790296A EP 4602015 A1 EP4602015 A1 EP 4602015A1
Authority
EP
European Patent Office
Prior art keywords
product according
less
mass content
na2û
ratio
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.)
Pending
Application number
EP23790296.0A
Other languages
English (en)
French (fr)
Inventor
Isabelle Cabodi
Olivier Citti
Isabell GROSS
Pierrick VESPA
Michel Gaubil
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
Priority date (The priority date 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 date listed.)
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 EP4602015A1 publication Critical patent/EP4602015A1/de
Pending 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
    • C04B35/10—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)
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
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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
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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.
  • 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.
  • the invention proposes a melted and cast refractory product comprising, in mass percentages on the basis of oxides and for a total of 100%:
  • 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 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;
  • 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%;
  • 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:
  • 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;
  • 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.
  • 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 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.
  • 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%.
  • 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 %.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Composite Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
EP23790296.0A 2022-10-14 2023-10-13 Feuerfestes produkt aus aluminiumoxid-zirkonoxid-siliciumdioxid Pending EP4602015A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2210621A FR3140880A1 (fr) 2022-10-14 2022-10-14 PRODUIT REFRACTAIRE Alumine-Zircone-Silice
PCT/EP2023/078573 WO2024079356A1 (fr) 2022-10-14 2023-10-13 Produit refractaire alumine-zircone-silice

Publications (1)

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EP4602015A1 true EP4602015A1 (de) 2025-08-20

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EP23790296.0A Pending EP4602015A1 (de) 2022-10-14 2023-10-13 Feuerfestes produkt aus aluminiumoxid-zirkonoxid-siliciumdioxid

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EP (1) EP4602015A1 (de)
JP (1) JP2025535786A (de)
CN (1) CN120051448A (de)
FR (1) FR3140880A1 (de)
WO (1) WO2024079356A1 (de)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2438552A (en) 1940-10-14 1948-03-30 Corhart Refractories Co Cast refractory product
FR75893E (fr) 1959-06-11 1961-08-18 Electro Refractaire Perfectionnements à la fabrication de produits réfractaires électrofondus contenant des oxydes minéraux
FR1208577A (fr) 1958-07-07 1960-02-24 Electro Refractaire Perfectionnements à la fabrication de produits réfractaires électrofondus contenant des oxydes minéraux
FR82310E (fr) 1962-04-07 1964-01-24 Electro Refractaire Perfectionnements à la fabrication de produits réfractaires électro-fondus contenant des oxydes minéraux
DE69901468T2 (de) 1998-02-26 2002-11-28 Asahi Glass Co., Ltd. Schmelzgegossenes Aluminiumoxid-Zirkonoxid-Siliziumoxid-Feuerfestmaterial und Glasschmelzofen, in den dieses eingesetzt wird
FR2961506B1 (fr) 2010-06-21 2014-03-14 Saint Gobain Ct Recherches Bloc refractaire et four de fusion de verre
WO2017115608A1 (ja) * 2015-12-28 2017-07-06 コニカミノルタ株式会社 π共役系化合物、有機エレクトロルミネッセンス素子材料、発光材料、電荷輸送材料、発光性薄膜、有機エレクトロルミネッセンス素子、表示装置及び照明装置
CN107555971B (zh) * 2017-09-29 2021-02-02 淄博艾杰旭刚玉材料有限公司 高温下高电阻率的电熔azs砖及其制备方法
CN111278789B (zh) * 2017-11-07 2022-12-27 旭硝子陶瓷株式会社 氧化铝/氧化锆/二氧化硅质熔融铸造耐火物和玻璃熔融窑

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Publication number Publication date
FR3140880A1 (fr) 2024-04-19
CN120051448A (zh) 2025-05-27
JP2025535786A (ja) 2025-10-28
WO2024079356A1 (fr) 2024-04-18

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