Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
• • 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
  • C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
  • C04B35/10—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
  • C04B35/101—Refractories from grain sized mixtures
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
  • C04B35/10—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
  • C04B35/101—Refractories from grain sized mixtures
  • C04B35/105—Refractories from grain sized mixtures containing chromium oxide or chrome ore
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
  • C04B35/10—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
  • C04B35/101—Refractories from grain sized mixtures
  • C04B35/106—Refractories from grain sized mixtures containing zirconium oxide or zircon (ZrSiO4)
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
  • C04B35/12—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 chromium oxide
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
  • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
  • C04B35/481—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing silicon, e.g. zircon
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
  • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
  • C04B35/482—Refractories from grain sized mixtures
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/72—Repairing or restoring existing buildings or building materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
  • C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/54—Particle size related information
  • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
  • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
  • C04B2235/54—Particle size related information
  • C04B2235/5463—Particle size distributions
  • C04B2235/5472—Bimodal, multi-modal or multi-fraction
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
  • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F27—FURNACES; KILNS; OVENS; RETORTS
  • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
  • F27D1/00—Casings; Linings; Walls; Roofs
  • F27D1/16—Making or repairing linings ; Increasing the durability of linings; Breaking away linings
  • F27D2001/1605—Repairing linings
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F27—FURNACES; KILNS; OVENS; RETORTS
  • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
  • F27D1/00—Casings; Linings; Walls; Roofs
  • F27D1/16—Making or repairing linings ; Increasing the durability of linings; Breaking away linings
  • F27D2001/1605—Repairing linings
  • F27D2001/161—Hot repair

Definitions

• the present invention relates to a packaged product consisting of a wet unshaped product placed in a hermetic package.
• the wet unshaped product is in particular intended for a glass furnace, in particular for the repair of a glass furnace.
• the industry particularly the glass industry, generally uses melted and cast refractory products, or those obtained by sintering, for the construction of its furnaces, which are highly resistant to corrosion by glass, and come in the form of blocks or slabs.
• Unshaped products can be used for the construction and/or repair of said ovens. These unshaped products are generally in the form of a dry powder, in order to facilitate their storage. This powder is moistened on site to obtain a wet unshaped product which can then be put in place:
• a specific quantity of powder for example 500 kg of powder, a setting activator and water are poured into a mixer.
• the batch of activated product obtained can be poured into the hopper of a pump to be transported to the destination site.
• the mixer can be reloaded for the next cycle.
• a second mixer is generally used to supply activated product to the pump during the reloading phase of the first mixer. The two mixers work alternately so that the pump hopper is never empty.
• Preparation is time-consuming, especially when the quantities of unprocessed products to be used are large. It also requires tools such as large mixers and/or pumps, which clutter the construction site area.
• An aim of the present invention is to satisfy, at least partially, this need.
• the binder precursor being chosen from:
• colloidal silica having a specific surface area less than or equal to 150 m2 /g, and preferably greater than 50 m2 /g, and
• colloidal silica in an amount greater than or equal to 0.5% by mass percentage based on the mass of the wet unshaped product, having a specific surface area of less than 500 m 2 /g, preferably less than 320 m 2 /g, and preferably greater than 50 m 2 /g, and
• the ceramic powder being made up of ceramic particles, without taking into account the particles of colloidal silica.
• the invention allows long-term storage of the unshaped product in a wet state. After storage, the wet unshaped product can be put in place very quickly, possibly after simple mixing, optionally after adding a setting activator.
• a product packaged according to the invention may also include one or more of the following optional features:
• - the binder precursor is chosen from:
• colloidal silica having a specific surface area greater than 50 m2 /g
• colloidal silica in an amount greater than or equal to 0.5% by mass percentage based on the mass of the wet unshaped product, having a specific surface area less than 320 m 2 /g and greater than 50 m 2 /g, and
• the binder precursor does not contain siloxane or hydrolyzed silane, and the colloidal silica has a specific surface area of less than 130 m 2 /g, preferably less than 90 m 2 /g;
• the total amount of hydrolyzed silane and siloxane represents less than 20% and more than 3% of the mass of colloidal silica
• the hydrolyzed silane comprises at least one hydrophobic functional group
• said hydrolyzed silane is chosen from alkylsilanes, vinylsilanes, sulfur silanes, mercaptosilanes, epoxysilanes, methacrylate silanes, aromatic silanes, fluoroalkylsilanes, and mixtures thereof;
• said hydrolyzed silane is an aromatic silane chosen from arylsilanes, or is an alkylsilane chosen from methylsilanes, ethylsilanes, propylsilanes, butylsilanes, octylsilanes and their mixtures;
• said hydrolyzed silane is an alkylsilane chosen from methylsilanes
• the siloxane comprises at least one hydrophobic functional group
• siloxane is chosen from alkylsiloxanes, vinylsiloxanes, sulfur siloxanes, mercaptosiloxanes, epoxysiloxanes, methacrylate siloxanes, aromatic siloxanes, fluoroalkylsiloxanes, and mixtures thereof;
• the ceramic powder is made up of more than 80% by mass of particles whose main constituents are alumina and/or zirconia and/or silica and/or chromium oxide; - ceramic powder, binder precursor and water together represent more than 98% of the mass of the wet unshaped product.
• the invention also relates to a method of manufacturing a packaged product according to the invention, comprising the following successive steps: a) preparation of the wet unshaped product; b) packaging of the wet unshaped product in the hermetic packaging so as to obtain said packaged product.
• step a) comprises a mixture of a starting charge consisting of more than 95%, by mass:
• the binder precursor being chosen from:
• colloidal silica having a specific surface area less than or equal to
• colloidal silica being provided in the form of an aqueous suspension
• colloidal silica in an amount greater than or equal to 0.5%, as a mass percentage based on the mass of the wet unshaped product, having a specific surface area of less than 500 m 2 /g, preferably between 50 m 2 /g and 320 m 2 /g, said colloidal silica being provided in the form of an aqueous suspension, and
• the invention finally relates to a method for repairing a furnace, preferably a glass furnace, or for manufacturing a block, preferably intended for such a furnace, said method comprising the following successive steps:
• Activation in step 3) may be simultaneous with step 4) if the mold or the region of an oven to be repaired is at a temperature suitable for activating the binder precursor.
• Step 5) may also be simultaneous with steps 3) and 4), in particular when the product is used to repair a hot oven, i.e. at a temperature typically above 500°C.
• binder precursor is meant a constituent capable of forming a binder rigidly holding the particles of this powder together, so as to form a solid mass.
• the binder precursor In the wet unshaped product, the binder precursor is in an "unactivated” state, i.e. in a state in which it does not provide cohesion between the particles of the ceramic powder (unlike the binder to which activation of the binder precursor leads, in the hardened product).
• the binder precursor is also not in a process leading to such cohesion, in which it is called an "activated binder precursor".
• the binder precursor can be transformed into an activated binder precursor by "activation” using a “setting activator” or if it is placed in an environment at a sufficiently high temperature.
• the activated binder precursor tends to harden the initially wet unshaped product.
• the wet unshaped product containing the activated binder precursor is called an "activated product".
• the binder therefore results from a reaction of the binder precursor with the setting activator and/or from a transformation under the effect of a sufficiently high temperature.
• binder precursor is conventionally provided in the form of a suspension, its quantity is measured without taking water into account.
• a distinction is made between water and colloidal silica (binder precursor).
• the wet unshaped product is the product to be stored and intended for the manufacture of a block or for repair. Once packaged, it is called “packaged product”. After being unpacked, and after activation of the binder precursor, the wet unshaped product enters a hardening phase, which may be of short duration, particularly during hot repair; it is then called “activated product”. After hardening, it is called “cured product”.
• ceramic powder means “ceramic powder other than colloidal silica”.
• ceramic powder we mean a powder consisting of particles of a ceramic material, i.e. neither organic nor metallic.
• Colloidal silica is a collection of silica particles suspended in a liquid, preferably water, each having a size less than 200 nm, the size being deduced from the specific surface area measurement assuming that all particles are spherical and of the same size, the specific surface area being evaluated using the Sears method, as described in “Determination of specific surface area of colloidal silica by titration with sodium hydroxide”, G. W. Sears, Anal. Chem. 1956, 28, 12, 1981-1983.
• Hermetic packaging is packaging that isolates the moist unprocessed product it contains from the ambient air, particularly under storage conditions.
• a “hydrolyzed silane” is a silane that contains at least one silanol group Si-OH.
• a hydrolyzed silane may be a fully or partially hydrolyzed silane.
• a “hydrolyzable silane” is a silane other than a hydrolyzed silane, and which, upon contact with water, forms a hydrolyzed silane (in other words, a hydrolyzable silane does not contain a Si-OH group and upon contact with water, it forms a silane containing at least one Si-OH group).
• the 10 (Dio), 50 (D50), 90 (D90) and 99.5 (099.5) percentiles or "percentiles" of a powder are the particle sizes corresponding to the percentages, by mass, of 10%, 50%, 90% and 99.5% respectively, on the cumulative particle size distribution curve of the particles of the powder, the particle sizes being ranked in ascending order. For example, 10%, by mass, of the particles of the powder have a size less than D 10 and 90% of the particles in mass have a size greater than Dio.
• the percentiles can be determined using a particle size distribution carried out using a laser particle size analyzer.
• main constituents we mean the constituents whose mass proportions are the highest.
• Zirconia is the name given to zirconium oxide ZrO2.
• Z1O2 zirconium oxide
• HIO2+HfO2 zirconium oxide
• the packaged product comprises a sealed package and a moist unshaped product contained within the sealed package.
• the hermetic packaging is a sealed plastic drum or bag. It preferably has a volume sufficient to contain more than 1 kg, more than 5 kg, more than 10 kg, more than 20 kg, and/or less than 500 kg, preferably less than 250 kg, preferably less than 100 kg, preferably less than 50 kg of wet unformed product.
• the wet unshaped product consists of a mixture of a ceramic powder, a binder precursor and water.
• the nature and particle size distribution of the ceramic powder are chosen according to the destination of the wet unshaped product. All ceramic powders used for the manufacture of hardened products intended for glass furnaces can be considered in particular.
• the fraction of particles of the ceramic powder having a size of less than 40 pm is distributed, in percentages by mass relative to the mass of the ceramic powder, as follows: fraction ⁇ 0.5 pm: > 4%, preferably > 5%, and/or ⁇ 6.5%, and fraction ⁇ 2 pm: > 5%, preferably > 8%, preferably > 10%, preferably > 13% and/or ⁇ 18%, and fraction ⁇ 10 pm: > 16%, preferably > 22%, preferably > 24% and/or ⁇ 35%, preferably ⁇ 34%, and fraction ⁇ 40 pm: 29-45%, preferably > 30% and/or ⁇ 40%.
• fractions can be determined using a particle size distribution carried out using a laser particle size analyzer.
• the 99.5 percentile of the ceramic powder is less than or equal to 10 mm, preferably less than or equal to 8 mm, preferably less than or equal to 5 mm.
• the fraction of particles of the ceramic powder with a size of less than 500 pm represents more than 50% by mass of said ceramic powder.
• the fraction of particles of the ceramic powder with a size between 40 pm and 500 pm is between 15 and 30%, preferably greater than 17%, greater than 18% and/or less than 28%, less than 25%, less than 22%, relative to the mass of said ceramic powder.
• Ceramic powder may contain particles:
• the ceramic powder does not include silica particles.
• the binder precursor is chosen from:
• colloidal silica having a specific surface area less than or equal to 150 m2 /g
• a colloidal silica is only suitable if it has a specific surface area of less than or equal to 500 m 2 /g, provided that it is associated with a hydrolyzed silane and/or a siloxane if its specific surface area is greater than 150 m 2 /g.
• a hydrolyzed silane and/or a siloxane may also be present if said specific surface area is less than or equal to 150 m 2 /g, but this presence is then optional.
• the colloidal silica is such that it gels when mixed with 15% magnesia, as a percentage of the mass of silica contained in the colloidal silica.
• the binder precursor is supplied in suspension, i.e. supplied with water.
• the amount of binder precursor is greater than or equal to 0.5%, preferably greater than or equal to 0.8%, preferably greater than or equal to 1%, preferably greater than 1.2%, preferably greater than 1.4%, and less than 3.2%, preferably less than 3.0%, preferably less than 2.8%, preferably less than 2.4%, in mass percentages based on the mass of the wet unshaped product.
• the colloidal silica has, in suspension, a negative zeta potential value.
• the colloidal silica has a specific surface area greater than 60 m 2 /g and preferably less than 130 m 2 /g, preferably less than 110 m 2 /g, preferably less than 90 m 2 /g.
• the binder precursor is a mixture consisting of a colloidal silica on the one hand, and a hydrolyzed silane and/or a siloxane on the other hand
• the amount of colloidal silica is greater than or equal to 0.5%, preferably greater than or equal to 0.8%, preferably greater than or equal to 1%, preferably greater than 1.2%, preferably greater than 1.4%, and less than 3.2%, preferably less than 3.0%, preferably less than 2.8%, preferably less than 2.6%, preferably less than 2.4%, in mass percentages based on the mass of the wet unshaped product.
• the total amount of hydrolyzed silane and siloxane preferably represents less than 20%, preferably less than 15%, preferably less than 10%, and/or more than 3%, preferably more than 4% of the mass of colloidal silica.
• the total amount of hydrolyzed silane and siloxane is preferably greater than 0.05%, preferably greater than 0.07%, and preferably less than 1%, preferably less than 0.8%, preferably less than 0.6%, preferably less than 0.5%, preferably less than 0.4%, preferably less than 0.3%, in mass percentages based on the mass of the wet unshaped product.
• the hydrolyzed silane comprises at least one hydrophobic functional group.
• said hydrolyzed silane is chosen from:
• the alkylsilanes are chosen from methylsilanes, ethylsilanes, propylsilanes, butylsilanes, octylsilanes and their mixtures, preferably from methylsilanes.
• the alkylsilane is potassium methylsilanetriolate.
• the aromatic silanes are selected from arylsilanes.
• the hydrolyzed silane is potassium methylsilanetriolate.
• the siloxane comprises at least one hydrophobic functional group. More preferably, said siloxane is chosen from:
• the water preferably comes from the added raw materials, and in particular from the colloidal silica suspension, and from a specific addition of water.
• the total amount of water in the wet unshaped product is greater than 5%, preferably greater than 6%, and/or preferably less than 14%, preferably less than 12%, preferably less than 10%, in mass percentages based on the mass of the wet unshaped product.
• the ceramic powder, the binder precursor and the water together preferably represent more than 95%, more than 96%, more than 97%, more than 98%, more than 99% of the mass of the wet unshaped product.
• the balance to 100% preferably consists of an optional surfactant, an optional anti-segregation adjuvant, an optional biocide and constituents, preferably organic, different from the binder precursor, said optional surfactant, said anti-segregation adjuvant and said biocide.
• Any conventional surfactant may be used, for example a modified polycarboxylate ether, a polyacrylate, in particular a sodium polyacrylate, a polyphosphate, in particular a sodium polyphosphate.
• the amount of surfactant in the wet unshaped product is greater than 0.05%, preferably greater than 0.1%, preferably greater than 0.15%, and/or preferably less than 0.30%, preferably less than 0.25%, preferably less than 0.20%, in mass percentages based on the mass of the wet unshaped product.
• Any conventional anti-segregation adjuvant can be used, for example starch ethers.
• the amount of anti-segregation adjuvant in the wet unshaped product is greater than 0.02%, preferably greater than 0.03%, and/or preferably less than 0.5%, preferably less than 0.35%, preferably less than 0.25%, preferably less than 0.20%, preferably less than 0.15%, preferably less than 0.10%, in mass percentages based on the mass of the wet unshaped product.
• biocide Any conventional biocide can be used.
• known biocides are the Preventol® range of biocides, including Preventol® P301, marketed by Lanxess, and the Adins range of biocides marketed by Toisa.
• the amount of biocide in the wet unshaped product is greater than 0.01%, preferably greater than 0.02%, preferably greater than 0.03%, and/or preferably less than 0.15%, preferably less than 0.10%, in mass percentages based on the mass of the wet unshaped product.
• the process for manufacturing the packaged product according to the invention does not pose any particular difficulty.
• This process comprises the following successive steps: a) mixing of a starting charge consisting of more than 95%, preferably more than 96%, preferably more than 97%, preferably more than 98%, preferably more than 99% by mass:
• the binder precursor being chosen from:
• colloidal silica being provided in the form of an aqueous suspension, and - a mixture consisting of:
• colloidal silica in an amount greater than or equal to 0.5%, as a mass percentage based on the mass of the wet unshaped product, having a specific surface area of less than 500 m 2 /g, preferably between 50 m 2 /g and 320 m 2 /g, said colloidal silica being provided in the form of an aqueous suspension, and
• step a) placing the wet unshaped product obtained in step a) in hermetic packaging.
• the process can be adapted, without particular difficulty, so that the packaged product obtained at the end of step b) has one or more of the optional characteristics described above.
• the resulting packaged product has one or more of the following optional characteristics:
• - the binder precursor is chosen from:
• colloidal silica having a specific surface area greater than 50 m2 /g
• colloidal silica in an amount greater than or equal to 0.5% by mass percentage based on the mass of the wet unshaped product, having a specific surface area less than 320 m 2 /g and greater than 50 m 2 /g, and
• the binder precursor does not contain siloxane or hydrolyzed silane, and the colloidal silica has a specific surface area of less than 130 m 2 /g, preferably less than 90 m 2 /g;
• the total amount of hydrolyzed silane and siloxane represents less than 20% and more than 3% of the mass of colloidal silica
• the hydrolyzed silane comprises at least one hydrophobic functional group
• said hydrolyzed silane is chosen from alkylsilanes, vinylsilanes, sulfur silanes, mercaptosilanes, epoxysilanes, methacrylate silanes, aromatic silanes, fluoroalkylsilanes, and mixtures thereof;
• said hydrolyzed silane is an aromatic silane chosen from arylsilanes, or is an alkylsilane chosen from methylsilanes, ethylsilanes, propylsilanes, butylsilanes, octylsilanes and their mixtures;
• said hydrolyzed silane is an alkylsilane chosen from methylsilanes; - the siloxane comprises at least one hydrophobic functional group;
• the ceramic powder is made up of more than 80% by mass of particles whose main constituents are alumina and/or zirconia and/or silica and/or chromium oxide;
• the binder precursor may however be not only a hydrolyzed silane and/or a siloxane (as in the wet unshaped product), but also a hydrolyzable silane.
• the hydrolyzable silane comes into contact with water and is transformed into hydrolyzed silane.
• the hydrolyzable silane may in particular be chosen so as to be hydrolyzable in the form of a hydrolyzed silane chosen from the hydrolyzed silanes described above.
• the hydrolyzed silane and/or siloxane preferably exhibit(s) the preferred characteristics relating to the hydrolyzed silane and/or siloxane described above for the packaged product, respectively.
• the hydrolyzable silane is chosen from hydrolyzable silanes comprising at least one hydrophobic functional group, preferably from:
• the hydrolyzable silane comprises at least one group selected from alkoxy groups, the chloro group and their mixtures.
• the alkoxyl group is selected from the methoxy group, the ethoxy group, the propoxy group and their mixtures.
• the hydrolyzable silane is chosen from alkylsilanes, vinylsilanes, sulfur silanes, mercaptosilanes, epoxysilanes, methacrylate silanes, aromatic silanes, fluoroalkylsilanes and mixtures thereof, and said hydrolyzable silane comprises at least one group chosen from alkoxyl groups, the chloro group and mixtures thereof.
• the colloidal silica is provided in the form of an aqueous suspension.
• Conventional colloidal silica suspensions may be used.
• the amount of colloidal silica represents more than 10%, more than 20%, more than 30%, more than 40% or more than 45%, and/or less than 55% of the mass of said aqueous suspension.
• the packaging is chosen so that, during storage, typically at atmospheric pressure and at a temperature between 10°C and 30°C, the moist unshaped product is isolated from the ambient air, i.e. there is no gas exchange between the inside and the outside of the packaging.
• the product packaged according to the invention is very simple to implement.
• step 1) the wet unshaped product can be advantageously stored for a long period. Storage is preferably at atmospheric pressure and at a temperature between 10°C and 30°C.
• step 2) it is extracted from the packaging.
• the humidity advantageously prevents the emission of dust.
• the wet unshaped product has been stored for more than 2 weeks, more than 1 month, more than 3 months, more than 4 months or more than 6 months, it is mixed. It can be mixed before being removed from the packaging, i.e. between steps 1) and 2), in particular if the packaging is rigid, for example if the packaging is a drum, or after this extraction, i.e. between steps 2) and 3), for example if the packaging is a bag.
• the wet unshaped product is mixed with a setting activator after removal from the package.
• the setting activator may also be mixed with the wet unshaped product in the package after it has been opened, for example if the wet unshaped product is contained in a drum.
• the amount of setting activator is greater than 0.2%, preferably greater than 0.4% and less than 2%, preferably less than 1.5%, preferably less than 1%, preferably less than 0.8%, as a percentage by weight based on the weight of the wet unshaped product.
• the setting activator is selected to activate the binder precursor. It is then preferably selected from magnesia, sodium silicate, a cement, and mixtures thereof. In one embodiment, the setting activator is a mixture of cement and magnesia. Preferably, the cement is an aluminous cement.
• the setting activator is magnesia.
• the invention also relates to the activated mixture resulting from the addition of a setting activator to a wet unshaped product according to the invention.
• Mixing with a setting activator is particularly useful in cases where the wet unshaped product is used in an environment at a temperature of 500°C or less. At a higher temperature, the silica can act as a hot binder. It is then not necessary to add a setting activator. The activation then results from the application of this temperature.
• the activated product sets in mass. It can therefore be handled immediately after activation, which, in step 4), allows it to be placed and shaped on the site where it is to harden.
• the site may be, for example, an area to be repaired, resulting for example from wear due to the flow of molten glass or metal or from corrosion due to contact with molten glass or metal or with slag.
• the site may be a sole, preferably a sole of a glassmaking furnace.
• the activated product is advantageously self-leveling, which allows it to be poured, for example by gravity.
• the activated product can also be poured into a mould to make a block, for example a block of more than 1 kg or more than 5 kg and/or preferably less than 1000 kg. After hardening, the block is removed from the mould.
• the hardened product is sintered, preferably at a temperature of 900°C and/or less than 1600°C.
• the sintering may result from the temperature prevailing in the furnace, in particular the operating temperature of the furnace.
• the specific surface area of colloidal silica in suspension form is estimated using the Sears method as described in “Determination of specific surface area of colloidal silica by titration with sodium hydroxide,” G. W. Sears, Anal. Chem. 1956, 28, 12, 1981-1983.
• the activated product is then immediately poured into a previously oiled hopper, in the shape of a truncated pyramid, arranged point downwards, and having a height of 320 mm, an upper inlet opening with a square section of 350 mm x 350 mm and a lower outlet opening (towards the tip of the pyramid) with a square section of 130 x 130 mm initially closed by a hatch.
• the hopper hatch is then opened with a sharp blow and the activated product pours under its own weight, through the outlet opening, into the upper end (700 mm from the ground) of a rectilinear semi-circular PVC gutter previously oiled, with a diameter of 170 mm and a length of 1600 mm, the lower end of the gutter being 380 mm from the ground.
• the activated product flows into the gutter and pours into a mold placed under the gutter, under the lower end of the gutter.
• the mold is a wooden mold measuring 300 mm x 300 mm x 60 mm, oiled and placed horizontally on the ground.
• the activated product we then wait for the activated product to harden in the form of a slab.
• the thickness of the slab is measured at both ends and at the middle of the length of the face.
• the self-levelling character (“AN”) is acquired if the upper surface of the slab appears noticeably smooth to the eye and if, for each of the four side faces, the difference “E” between the smallest measured thickness and the largest measured thickness is less than or equal to 2 mm.
• the slab After drying at 110°C for 24 hours, the slab is sawn in two through its centre, exposing two sawn faces. Segregation causes the larger particles to migrate away from the upper face of the slab. Segregation is considered to have occurred when the sawn faces reveal a surface layer of laitance extending from the upper face of the slab to a depth “e” of 3 mm or more.
• the shelf life of the unformed wet product is assessed by the following test.
• the unformed wet product is packaged in an airtight container in the form of a jar with a capacity of 500 ml and a diameter of 90 mm, closed with a lid.
• the packaged product thus formed is stored in a room at an average temperature of between 21 °C and 25 °C for six months.
• the packaging cover is removed, and the wet unshaped product is placed on the tray of a TX700 texture analyzer model 151500 equipped with a cleaver probe reference 130064, marketed by the company Lamy Rheology.
• the tip of the cleaver probe is positioned so as to touch the upper surface of the wet unshaped product, in the centre of said surface.
• the probe then gradually descends into the wet unshaped product to a depth of 45 mm and the maximum force required for this purpose is recorded. If the consistency of the wet unformed product strongly opposes the penetration of the probe, the force applied by the analyzer reaches or even exceeds 380 N. The analyzer then temporarily stops applying the penetration force. The measurement is then stopped. The depth reached by the probe for the maximum force applied is then measured.
• the measurement is carried out at room temperature.
• a value of D less than 40 N/mm preferably less than 35 N/mm, preferably less than 30 N/mm, preferably less than 25 N/mm, preferably less than 20 N/mm, preferably less than 15 N/mm, corresponds to a wet unshaped product which can be quickly implemented, after a storage period of six months, without a long mixing operation.
• examples 1 and 3 according to the invention below could be used, and even cast, after simple mixing using a portable electric plasterer's mixer (with a power of 1600 W, equipped with a turbine for mortar and paint, with a diameter equal to 140 mm).
• ER1681 grains having the following chemical analysis, in mass percentages: Z1O2: 32.5%, SiCL: 15%, AI2O3: 50.9%, 1.6% of other compounds, a percentile 10 (D10) equal to 2 mm, a percentile 90 (D90) equal to 3.5 mm and a median size (D50) equal to 2.5 mm,
• ER1681 grains having the following chemical analysis, in mass percentages: Z1O2: 32.5%, SiCL: 15%, AI2O3: 50.9%, 1.6% of other compounds, a percentile 10 (D10) equal to 0.46 mm, a percentile 90 (D90) equal to 1.7 mm and a median size (D50) equal to 1 mm,
• ER1681 grains having the following chemical analysis, in mass percentages: Z1O2: 32.5%, SiCL: 15%, AI2O3: 50.9%, 1.6% of other compounds, a 10th percentile (Dio) equal to 0.03 mm, 90th percentile (D90) equal to 0.38 mm and median size (D50) equal to 0.16 mm,
• an electrofused alumina powder having a mass content of AI2O3 greater than 99%, a mass content of Na2O less than 0.2%, and a median size (D50) equal to 100 pm,
• SIKAGARD® facade protection marketed by the company SIKA, containing the hydrolyzed silane potassium methylsilanetriolate,
• Table 1 provides the composition of the wet unshaped products, in mass percentages based on the mass of said wet unshaped product.
• the colloidal silica suspension is introduced into the tank of a Perrier-type paddle mixer. Then, while the mixer is running, water (for examples 1 and 2 only) is added, then the modified polycarboxylate ether, then the SIKAGARD façade protection. Mixing continues for 1 minute. Then the ceramic powder is added and mixing is continued for a further 9 minutes.
• the wet unshaped product is obtained at the end of this mixing time.
• Each wet unformed product is then hermetically packaged so that its shelf life can be measured, as described above. After being stored for 6 months, self-levelling and segregation are measured.
• Table 2 provides the results of the tests carried out.
• Example 1 whose binder precursor is a colloidal silica having a specific surface area of between 60 m 2 /g and 90 m 2 /g, has a D value equal to 15 N/mm measured after a storage period equal to 6 months.
• Example 2 outside the invention, whose binder precursor is a colloidal silica having a specific surface area equal to 250 m2 /g, has a D value equal to 105 N/mm measured after a storage period equal to 6 months.
• example 2 has a D value equal to 105 N/mm, much higher than that of example 3 (D value equal to 19 N/mm).
• the invention provides a wet unshaped product which can be stored for a prolonged period and which after storage can be rapidly and simply processed, substantially without dust emission.

Landscapes

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

Applications Claiming Priority (2)

Publications (1)

Family

ID=87281003

Family Applications (1)

Country Status (4)

Family Cites Families (2)

• 2023
  • 2023-03-09 FR FR2302182A patent/FR3146471B1/fr active Active
• 2024
  • 2024-03-08 CN CN202480017286.6A patent/CN120835869A/zh active Pending
  • 2024-03-08 WO PCT/EP2024/056162 patent/WO2024184509A1/fr not_active Ceased
  • 2024-03-08 EP EP24710080.3A patent/EP4676901A1/de active Pending

Also Published As

Similar Documents

Legal Events