Product for repairing furnace

Abstract

The invention relates to a packaged product comprising:-a sealed package; and-a wet unshaped product provided in the sealed package and consisting, for more than 95% by weight, of:-from 4% to 15% by weight, based on the weight of the wet unshaped product, of water; -from 0.5% to 3.2%, by weight percent, based on the weight of the wet unshaped product, of a binder precursor; -a ceramic powder, said binder precursor being selected from the group consisting of:-colloidal silica having a specific surface area of at least 150 m2 / g; and-a mixture consisting of:-colloidal silica having a specific surface area of at least 500 m2 / g, the amount of said colloidal silica being 0.5% or greater by weight, based on the weight of said wet unshaped product; and-a hydrolyzed silane and / or siloxane wherein the ceramic powder consists of ceramic particles, irrespective of colloidal silica particles.

Description

Technical Field

[0001] The present invention relates to a packaged product consisting of a wet, unshaped product placed in a sealed package. The wet, unshaped product is particularly intended for use in glass furnaces, in particular for repairing glass furnaces. Background Art

[0002] Industry, and in particular the glass industry, generally uses for the construction of its furnaces fused-cast refractory products or refractory products obtained by sintering, which are very resistant to glass corrosion and are in the form of blocks or plates.

[0003] The unshaped products can be used for the construction and / or repair of the furnace. These unshaped products are usually in the form of a dry powder to facilitate their storage. This powder is moistened at the construction site to obtain a wet unshaped product, which can then be put into place:

[0004] Conventionally, a predetermined amount of powder (e.g., 500 kg of powder), a setting activator, and water are poured into a mixer. After mixing, the resulting batch of activated product can be poured into the hopper of a pump for delivery to the construction site. The mixer can be refilled for the next cycle. To ensure that the pump is fed as continuously as possible, a second mixer is often used to supply the pump with activated product during the refilling phase of the first mixer. The two mixers operate alternately, ensuring that the pump hopper is never empty.

[0005] When dry powder is loaded into the mixer, dust is generated, which is harmful to personnel safety.

[0006] Preparation is time consuming, especially when working with large quantities of unformed product. It also requires tools such as large mixers and / or pumps that take up space in the work area.

[0007] Therefore, there is a need for an unformed product that can be stored for long periods of time and, after storage, can be used quickly by lightweight facilities (such as a simple stucco mixer) and that generates little dust.

[0008] It is an object of the present invention to at least partially meet this need. Summary of the Invention

[0009] According to the present invention, this object is achieved by a packaging product comprising:

[0010] - sealed packaging, and

[0011] - a moist, unformed product disposed in said sealed package and consisting, for greater than 95% by mass, of:

[0012] - 4% to 15% of water, by mass percentage, based on the mass of the wet unshaped product,

[0013] - 0.5% to 3.2% of binder precursor, by mass percentage, based on the mass of the wet unshaped product,

[0014] - a ceramic powder,

[0015] The binder precursor is chosen from:

[0016] - a colloidal silica having a specific surface area less than or equal to 150 m 2 / g and preferably greater than 50 m 2 / g, and

[0017] - a mixture consisting of:

[0018] - a colloidal silica, the amount of which is greater than or equal to 0.5%, by mass percentage, based on the mass of the wet unshaped product, the colloidal silica having a specific surface area less than 500 m 2 / g, preferably less than 320 m 2 / g and preferably greater than 50 m 2 / g, and

[0019] - a hydrolysed silane and / or siloxane,

[0020] The ceramic powder consists of ceramic particles, without taking into account the colloidal silica particles.

[0021] As will be seen in more detail in the following description, the application allows long-term storage of the unshaped product in a wet state. After storage, the wet unshaped product can be placed in position very quickly, optionally after simple mixing, optionally after the addition of a coagulation activator.

[0022] In particular, said mixing can be carried out by a mixer of a conventional feed hopper equipped with a pump, when the unshaped product is moved by a pump. A stirrer is no longer necessary.

[0023] Thus, the preparation can be carried out on site, without the need for expensive and bulky equipment, for example using a hand mixer. Finally, since the unshaped mixture is wet, this preparation does not generate any significant amount of dust.

[0024] The packaged product according to the application can also comprise one or more of the following optional features:

[0025] - the binder precursor is chosen from:

[0026] - a colloidal silica having a specific surface area greater than 50 m 2 / g, and

[0027] - a mixture consisting of:

[0028] - a colloidal silica in an amount greater than or equal to 0.5% by mass percentage based on the mass of the wet unshaped product, the colloidal silica having a specific surface area less than 320 m 2 / g and greater than 50 m 2 / g, and

[0029] - a hydrolyzed silane and / or a siloxane;

[0030] - the binder precursor does not contain any siloxane or hydrolyzed silane, and the colloidal silica has a specific surface area less than 130 m 2 / g, preferably less than 90 m 2 / g;

[0031] - the total amount of hydrolyzed silane and siloxane is less than 20% and greater than 3% by mass of the colloidal silica;

[0032] - the hydrolyzed silane comprises at least one hydrophobic functional group;

[0033] - preferably, the hydrolyzed silane is selected from the group consisting of alkylsilane, vinylsilane, thiosilane, mercaptosilane, epoxysilane, methacrylate silane, aromatic silane, fluoroalkylsilane, and mixtures thereof;

[0034] - preferably, the hydrolyzed silane is an aromatic silane selected from arylsilane, or an alkylsilane selected from the group consisting of methylsilane, ethylsilane, propylsilane, butylsilane, octylsilane, and mixtures thereof;

[0035] - preferably, the hydrolyzed silane is an alkylsilane selected from methylsilane;

[0036] - the siloxane comprises at least one hydrophobic functional group;

[0037] - preferably, the siloxane is selected from the group consisting of alkylsiloxane, vinylsiloxane, thiosiloxane, mercaptosiloxane, epoxysiloxane, methacrylate siloxane, aromatic siloxane, fluoroalkylsiloxane, and mixtures thereof;

[0038] - the ceramic powder consists for more than 80% by mass of particles whose main constituent is alumina and / or zirconia and / or silica and / or chromium oxide;

[0039] - the ceramic powder, the binder precursor and the water together represent more than 98% by mass of the wet unshaped product.

[0040] The present invention also relates to a method for manufacturing a packaged product according to the present invention, the method comprising the following successive steps:

[0041] a) preparing a wet unshaped product;

[0042] b) packaging the wet unshaped product in a sealed package to obtain the packaged product.

[0043] Preferably, step a) comprises mixing a starting feed, the starting feed consisting for more than 95% by mass of:

[0044] based on the mass of the starting feed, by mass percentage,

[0045] - from 4% to 15% of water,

[0046] - from 0.5% to 3.2% of a binder precursor,

[0047] - a ceramic powder different from colloidal silica,

[0048] the binder precursor being selected from:

[0049] - a colloidal silica having a specific surface area less than or equal to 150 m 2 / g and preferably greater than 50 m 2 / g, said colloidal silica being provided in the form of an aqueous suspension, and

[0050] - a mixture consisting of:

[0051] - a colloidal silica, the amount of colloidal silica being greater than or equal to 0.5% by mass percentage based on the mass of the wet unshaped product, the colloidal silica having a specific surface area 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

[0052] - a hydrolyzable silane and / or a hydrolyzable siloxane and / or a hydrolyzable silane to obtain the wet unshaped product.

[0053] Finally, the present invention relates to a method for repairing a furnace, preferably a glass furnace, or for manufacturing a block, preferably a block for such a furnace, said method comprising the following successive steps:

[0054] 1) storing the product packaged according to the invention or manufactured according to the manufacturing method according to the invention for more than 2 weeks, preferably more than 1 month, preferably more than 2 months, preferably more than 4 months, preferably more than 6 months;

[0055] 2) unpacking the product packaged according to the invention in order to extract therefrom the wet unshaped product, before or after said extraction, optionally carrying out a mixing of the wet unshaped product;

[0056] 3) activating the binder precursor of the wet unshaped product by mixing with a coagulation activator and / or by placing the wet unshaped product in an environment at a temperature suitable for activating the binder precursor, thereby obtaining an activated product;

[0057] 4) placing the activated product in a mold or in the area of the furnace to be repaired;

[0058] 5) optionally, after hardening, if the activated product has been hardened in a mold, sintering, preferably after removal from the mold.

[0059] The activation in step 3) can be performed simultaneously with step 4) if the mold or the area of the furnace to be repaired is at a temperature suitable for activating the binder precursor. Step 5) can also be performed simultaneously with steps 3) and 4), in particular when the product is used to repair a hot (i.e. at temperatures typically above 500°C) furnace.

[0060] Definitions

[0061] The term "binder precursor" means a constituent suitable for forming a binder that firmly binds the particles of such a powder together to form a solid mass.

[0062] 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 (this is different from the binder formed in the hardened product after activation of the binder precursor). The binder precursor is also not in a process that leads to such cohesion, in which it is referred to as "activated binder precursor". The binder precursor can be transformed into activated binder precursor by means of a "coagulation activator" or by "activation" if placed in an environment at a sufficiently high temperature. The activated binder precursor tends to harden the initially wet unshaped product. By extension, the wet unshaped product containing the activated binder precursor is referred to as "activated product". Thus, in the hardened product, the binder is the result of the reaction of the binder precursor with the coagulation activator and / or the result of the transformation under the action of a sufficiently high temperature.

[0063] Although the binder precursor is usually provided in the form of a suspension, the measurement of its quantity does not take into account the water. For example, in a colloidal silica suspension, a distinction is made between water and colloidal silica (binder precursor).

[0064] For the sake of clarity, a distinction is made between "packaged product", "wet unshaped product", "activated product" and "hardened product". The wet unshaped product is the product to be stored and to be used for manufacturing blocks or for repair. Once packaged, it is called "packaged product". After unpacking and after activation of the adhesive precursor, the wet unshaped product enters the hardening phase, which can be short, in particular during high temperature repair; then it is called "activated product". After hardening, it is called "hardened product".

[0065] For the sake of clarity, the term "ceramic powder" means "ceramic powder different from colloidal silica", unless otherwise stated.

[0066] The term "ceramic powder" means a powder composed of particles of a ceramic material, i.e. neither organic nor metallic.

[0067] Colloidal silica is a collection of silica particles suspended in a liquid, preferably water, each particle having a size smaller than 200 nm, this size being deduced from specific surface area measurements, using the Sears method to evaluate the specific surface area, 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, considering that all particles are spherical and have the same size.

[0068] A "sealed" package is a package that isolates the wet unshaped product it contains from the ambient air, in particular under storage conditions.

[0069] A "hydrolysed silane" is a silane containing at least one Si-OH silanol group. The hydrolysed silane can be a fully or partially hydrolysed silane.

[0070] A "hydrolysable silane" is a silane different from a hydrolysed silane and forming a hydrolysed silane upon contact with water (in other words, a hydrolysable silane does not contain any Si-OH group and upon contact with water, it forms a silane containing at least one Si-OH group).

[0071] A compound containing one or more Si-O-Si bond(s) in the molecule is called "siloxane". Conventionally, and for the purpose of the present specification, polysiloxane is thus a siloxane. Siloxanes can be obtained by polycondensation of silanes.

[0072] 10 (D 10 ), 50 (D 50 ), 90 (D90 ) and 99.5 (D 99.5 ) Percentiles or "centiles" are the particle sizes corresponding to 10%, 50%, 90% and 99.5% of the mass percent on the cumulative particle size distribution curve of the powder particles, the particle sizes being sorted in ascending order. For example, 10 mass% of the powder particles have a size smaller than D 10 , 90 mass% of the particles have a size greater than D 10 Percentiles can be determined by the particle size distribution with a laser particle size analyzer.

[0073] The term "main ingredient" means the ingredient with the highest proportion by mass.

[0074] Zirconium oxide Zr02 is also called "zirconia". When referring to Zr02, this should be understood as (Zr02+Hf02). Specifically, a small amount of Hf02 that cannot be chemically separated from Zr02 and has similar properties is always naturally present in the zirconia source in a content usually lower than 2% during the conventional zirconia manufacturing process. Therefore, hafnium oxide is not considered as an impurity.

[0075] The terms "comprises" or "comprising" or "has" or "having" should be interpreted non- restrictively. DETAILED DESCRIPTION

[0076] Wet unshaped product

[0077] The packaged product comprises a sealed package and a wet unshaped product contained in the sealed package.

[0078] Any rigid or flexible sealed package can be suitable. Preferably, the sealed package is a sealed plastic bag or a drum. 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 unshaped product.

[0079] The wet unshaped product comprises a mixture of a ceramic powder, a binder precursor and water.

[0080] The properties and the particle size distribution of the ceramic powder are chosen according to the intended use of the wet unshaped product. All ceramic powders used for the manufacture of hardening products for glass furnaces can be particularly considered.

[0081] Preferably, the ceramic powder consists, for more than 80% of its mass, preferably for more than 90% of its mass, preferably for more than 95% of its mass, of particles whose main constituent is alumina (AI2O3) and / or zirconia (ZrO2) and / or silica (SiO2) and / or chromium oxide (Cr2O3).

[0082] Preferably, the fraction of ceramic powder particles having a size of less than 40 pm is distributed in the following way, in percentage by mass with respect to the mass of the ceramic powder:

[0083] - the fraction of < 0.5 pm: > 4%, preferably > 5% and / or < 6.5%, and

[0084] - the fraction of < 2 pm: > 5%, preferably > 8%, preferably > 10%, preferably > 13% and / or < 18%, and

[0085] - the fraction of < 10 pm: > 16%, preferably > 22%, preferably > 24% and / or < 35%, preferably < 34%, and

[0086] - the fraction of < 40 pm: 29% to 45%, preferably > 30% and / or < 40%.

[0087] These fractions can be determined by the particle size distribution, carried out with a laser particle size analyser.

[0088] Preferably, 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.

[0089] Preferably, the fraction of ceramic powder particles having a size of less than 500 pm is greater than 50% by mass of the ceramic powder.

[0090] Preferably, the fraction of ceramic powder particles having a size of 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% with respect to the mass of the ceramic powder.

[0091] The ceramic powder can comprise particles of:

[0092] - electrically fused refractory products, such as ER-1681 or ER-1711 produced and sold by the Société Européenne des Produits Réfractaires. These two products contain, in percentage by mass on the basis of oxides, between 32% and 54% of ZrO2, between 36% and 51% of AI2O3, between 10% and 16% of SiO2, and between 0.2% and 1.5% of Na2O;

[0093] - mullite;

[0094] - zirconium oxide;

[0095] -aluminum oxide;

[0096] -Chromium oxide.

[0097] In one embodiment, the ceramic powder does not include any silica particles.

[0098] The binder precursor is selected from:

[0099] -Specific surface area less than or equal to 150m 2 / g of colloidal silica, and

[0100] - On the one hand, the specific surface area is less than 500m 2 / g of colloidal silica on the one hand and a mixture of hydrolyzed silanes and / or siloxanes on the other hand.

[0101] Specifically, the inventors found that colloidal silica is only effective when the specific surface area is less than or equal to 500m 2 / g is applicable only if its specific surface area is greater than 150m 2 / g, provided that it is used in combination with hydrolyzed silane and / or siloxane. Of course, if the specific surface area is less than or equal to 150m 2 / g, hydrolyzed silanes and / or siloxanes may also be present, but their presence is optional.

[0102] Preferably, the colloidal silica is such that it gels when mixed with 15% (as a percentage by mass of the silica contained in the colloidal silica) of magnesium oxide.

[0103] In practice, the binder precursor is provided in the form of a suspension, ie together with water.

[0104] The amount of binder precursor (especially when the binder precursor consists 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 2.4%, based on the mass of the wet, unformed product.

[0105] All colloidal silicas come into consideration.

[0106] Preferably, the colloidal silica has a negative zeta potential value in the suspension. Preferably, when the binder precursor does not contain any siloxane or hydrolyzed silane, the specific surface area of ​​the colloidal silica is greater than 60 m 2 / g, and preferably less than 130m 2 / g, preferably less than 110m 2 / g, preferably less than 90m2 / g.

[0107] When the binder precursor is a mixture consisting of colloidal silica on the one hand and hydrolyzed silane and / or 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% by mass percentage based on the mass of the wet unshaped product.

[0108] The total amount of hydrolyzed silane and siloxane is preferably less than 20%, preferably less than 15%, preferably less than 10% and / or greater than 3%, preferably greater than 4% of the mass of the colloidal silica.

[0109] 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% by mass percentage based on the mass of the wet unshaped product.

[0110] Preferably, the hydrolyzed silane comprises at least one hydrophobic functional group. More preferably, the hydrolyzed silane is selected from:

[0111] - alkylsilane,

[0112] - vinylsilane,

[0113] - thiosilane,

[0114] - mercaptosilane,

[0115] - epoxysilane,

[0116] - methacrylate silane,

[0117] - aromatic silane,

[0118] - fluoroalkylsilane,

[0119] - and mixtures thereof.

[0120] Preferably, the alkylsilane is selected from methylsilane, ethylsilane, propylsilane, butylsilane, octylsilane and mixtures thereof, preferably from methylsilane.

[0121] Preferably, the alkylsilane is potassium methylsilanetriolate.

[0122] In one embodiment, the aromatic silane is selected from arylsilane.

[0123] Preferably, the hydrolyzed silane is potassium methyl silanetriol.

[0124] Preferably, the siloxane comprises at least one hydrophobic functional group. More preferably, the siloxane is selected from:

[0125] - alkylsiloxane,

[0126] - vinylsiloxane,

[0127] - thiosiloxane,

[0128] - mercaptosiloxane,

[0129] - epoxysiloxane,

[0130] - methacrylate siloxane,

[0131] - aromatic siloxane,

[0132] - fluoroalkylsiloxane,

[0133] - and mixtures thereof.

[0134] Water is preferably from added starting materials, in particular from the colloidal silica suspension and from water specifically added. Preferably, 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%, by mass percentage based on the mass of the wet unshaped product.

[0135] The ceramic powder, the binder precursor and the water together preferably make up more than 95%, more than 96%, more than 97%, more than 98%, more than 99% of the mass of the wet unshaped product. The remainder up to 100% is preferably composed of: optional surfactant; optional anti-segregation adjuvant; optional antimicrobial agent; and an ingredient, preferably an organic ingredient, different from the binder precursor, the optional surfactant, the anti-segregation adjuvant, and the antimicrobial agent.

[0136] Any conventional surfactant can be used, for example modified polycarboxylic acid ethers, polyacrylate salts (in particular sodium polyacrylate), polyphosphate salts (in particular sodium polyphosphate).

[0137] The choice of surfactant from those commonly used by the person skilled in the art can be guided by the results of simple tests (for example those described in the present specification) according to the desired properties (ease of use, density of the wet unshaped product after application).

[0138] Preferably, 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%, by mass percentage based on the mass of the wet unshaped product.

[0139] Any conventional anti-segregation adjuvant can be used, for example starch ethers.

[0140] Preferably, 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%, by mass percentage based on the mass of the wet unshaped product.

[0141] Any conventional antimicrobial agent can be used. Examples of known antimicrobial agents are the antimicrobial agents of the series sold by the company Lanxess, in particular P301, and the antimicrobial agents of the Adins series sold by the company Tolsa.

[0142] Preferably, the amount of antimicrobial agent 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%, by mass percentage based on the mass of the wet unshaped product.

[0143] Manufacturing process

[0144] The method for manufacturing the packaged product according to the application does not pose any particular difficulty.

[0145] The method comprises the following successive steps:

[0146] a) mixing a starting feed, for more than 95% of the mass, preferably for more than 96% of the mass, preferably for more than 97% of the mass, preferably for more than 98% of the mass, preferably for more than 99% of the mass, consisting of:

[0147] - 4% to 15% of water, by mass percentage based on the mass of the starting feed,

[0148] - 4% to 15% of water, by mass percentage based on the mass of the starting feed,

[0149] - 0.5% to 3.2% of a binder precursor,

[0150] - optionally, 0.05% to 0.30% of a surfactant,

[0151] - optionally, 0.02% to 0.5% of an anti-segregation adjuvant,

[0152] - optionally, 0.01% to 0.15% of an antimicrobial agent,

[0153] - a ceramic powder other than colloidal silica,

[0154] The binder precursor is chosen from:

[0155] - a colloidal silica having a specific surface area less than or equal to 150 m 2 / g and preferably greater than 50 m 2 / g, said colloidal silica being provided in the form of an aqueous suspension, and

[0156] - a mixture consisting of:

[0157] - a colloidal silica, the amount of which is greater than or equal to 0.5% by mass percentage based on the mass of the wet unshaped product, the colloidal silica having a specific surface area 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

[0158] - a hydrolysed silane and / or siloxane and / or hydrolysable silane to obtain a wet unshaped product,

[0159] b) placing the wet unshaped product obtained in step a) in a sealed package.

[0160] The method can be adjusted without any particular difficulty so that the packaged product obtained at the end of step b) has one or more of the optional features described above.

[0161] In particular, the method is preferably adjusted to ensure that the packaged product obtained at the end of step b) has one or more of the following optional features:

[0162] The binder precursor is chosen from:

[0163] - a colloidal silica having a specific surface area greater than 50 m 2 / g, and

[0164] - a mixture consisting of:

[0165] - a colloidal silica, the amount of which is greater than or equal to 0.5% by mass percentage based on the mass of the wet unshaped product, the colloidal silica having a specific surface area less than 320 m 2 / g and greater than 50 m 2 / g, and

[0166] - hydrolyzed silanes and / or siloxanes;

[0167] - the binder precursor contains no siloxanes or hydrolyzed silanes, and the colloidal silica has a specific surface area of less than 130 m2 / g, preferably less than 90 m2 / g; 2 2 - the colloidal silica has a specific surface area of less than 130 m2 / g, preferably less than 90 m2 / g;

[0168] - the total amount of hydrolyzed silanes and siloxanes is less than 20% and more than 3% of the mass of the colloidal silica;

[0169] - the hydrolyzed silanes comprise at least one hydrophobic functional group;

[0170] - preferably, the hydrolyzed silanes are selected from the group consisting of alkylsilanes, vinylsilanes, thiosilanes, mercaptosilanes, epoxysilanes, methacrylate silanes, aromatic silanes, fluoroalkylsilanes, and mixtures thereof;

[0171] - preferably, the hydrolyzed silanes are aromatic silanes selected from arylsilanes, or alkylsilanes selected from the group consisting of methylsilanes, ethylsilanes, propylsilanes, butylsilanes, octylsilanes, and mixtures thereof;

[0172] - preferably, the hydrolyzed silanes are alkylsilanes selected from methylsilanes;

[0173] - the siloxanes comprise at least one hydrophobic functional group;

[0174] - preferably, the siloxanes are selected from the group consisting of alkylsiloxanes, vinylsiloxanes, thiosiloxanes, mercaptosiloxanes, epoxysiloxanes, methacrylate siloxanes, aromatic siloxanes, fluoroalkylsiloxanes, and mixtures thereof;

[0175] - the ceramic powder consists for more than 80% of the mass of particles whose main constituent is alumina and / or zirconia and / or silica and / or chromium oxide;

[0176] - the ceramic powder, the binder precursor and the water together represent more than 98% of the mass of the wet unshaped product.

[0177] However, in the starting feed, the binder precursor can not only be hydrolyzed silanes and / or siloxanes (as in the wet unshaped product), but also hydrolysable silanes. In particular, during the preparation of the wet unshaped product, the hydrolysable silanes are in contact with water and are converted into hydrolyzed silanes. The hydrolysable silanes can be chosen in particular so as to hydrolyze into a form of hydrolyzed silane selected from the aforementioned hydrolyzed silanes.

[0178] The hydrolyzed silanes and / or siloxanes preferably have the preferred characteristics mentioned above for the hydrolyzed silanes and / or siloxanes used for packaging the product, respectively.

[0179] ​Preferably, the hydrolysable silane is selected from the group consisting of hydrolysable silanes comprising at least one hydrophobic functional group, preferably from the group consisting of:

[0180] - alkylsilanes,

[0181] - vinylsilanes,

[0182] - thiosilanes,

[0183] - mercaptosilanes,

[0184] - epoxysilanes,

[0185] - methacrylate silanes,

[0186] - aromatic silanes,

[0187] - fluoroalkylsilanes,

[0188] - and mixtures thereof.

[0189] Preferably, the hydrolysable silane comprises at least one group selected from the group consisting of alkoxy groups, chloro groups, and mixtures thereof.

[0190] Preferably, the alkoxy groups are selected from the group consisting of methoxy groups, ethoxy groups, propoxy groups, and mixtures thereof.

[0191] Preferably, the hydrolysable silane is selected from the group consisting of alkylsilanes, vinylsilanes, thiosilanes, mercaptosilanes, epoxysilanes, methacrylate silanes, aromatic silanes, fluoroalkylsilanes, and mixtures thereof, and the hydrolysable silane has at least one group selected from the group consisting of alkoxy groups, chloro groups, and mixtures thereof.

[0192] The colloidal silica is provided in the form of an aqueous suspension. Conventional colloidal silica suspensions can be used. Preferably, the amount of colloidal silica is greater than 10%, greater than 20%, greater than 30%, greater than 40%, or greater than 45%, and / or less than 55% of the mass of the aqueous suspension.

[0193] In step b), the packaging is chosen to ensure that the wet unshaped product is isolated from the ambient air during storage, typically at atmospheric pressure and at a temperature of 10°C to 30°C, i.e. there is no gas exchange between the inner part and the outer part of the packaging.

[0194] Use

[0195] The product packaged according to the application is very easy to use.

[0196] In step 1), the wet unshaped product can advantageously be stored for a long period of time. The storage is preferably at atmospheric pressure and at a temperature of 10°C to 30°C.

[0197] In step 2), it is taken out of the packaging. Moisture advantageously prevents the emission of dust. Preferably, the moist unshaped product is mixed, in particular if it 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. The moist unshaped product can be mixed before being taken out of the packaging, i.e. between steps 1) and 2), in particular if the packaging is rigid, for example if the packaging is a tub; or after this taking out, i.e. between steps 2) and 3), for example if the packaging is a bag.

[0198] In step 3), in one embodiment, the moist unshaped product is mixed with a solidification activator after being taken out of the packaging. The solidification activator can also be mixed with the moist unshaped product in the packaging after opening the packaging, for example if the moist unshaped product is packed in a tub.

[0199] Preferably, the amount of solidification 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%, by mass percentage, based on the mass of the moist unshaped product.

[0200] Preferably, the solidification activator is chosen to activate the binder precursor. It is then preferably chosen from magnesium oxide, sodium silicate, cement, and mixtures thereof. In one embodiment, the solidification activator is a mixture of cement and magnesium oxide. Preferably, the cement is high-alumina cement.

[0201] Preferably, the solidification activator is magnesium oxide.

[0202] The application also relates to the activated mixture resulting from the addition of a solidification activator to the moist unshaped product according to the application.

[0203] Mixing with a solidification activator is particularly useful in the case where the moist unshaped product is used in an environment at a temperature lower than or equal to 500°C. At higher temperatures, the silica can act as a thermal binder. There is then no need to add a solidification activator. Activation is then induced by the application of this temperature.

[0204] The activated product solidifies as a solid. It can thus be handled immediately after activation, in step 4), allowing it to be placed in the location to be hardened and shaped in this location. This location can be, for example, a zone to be repaired, resulting from wear caused, for example, by the flow of molten glass or metal, or from corrosion caused by contact with molten glass or metal or with slag.

[0205] The location can be a furnace bottom, preferably of a glass melting furnace. The activated product is advantageously self-leveling, which enables it to flow, for example by gravity.

[0206] The activated product can also be poured into a mould to produce blocks, for example blocks of greater than 1 kg or greater than 5 kg and / or preferably less than 1000 kg. After hardening, the blocks are removed from the mould.

[0207] In step 5), in a preferred embodiment, the hardened product is sintered, preferably at a temperature between 900° C. and / or less than 1600° C. Sintering can be caused by the temperature existing in the furnace, in particular by the operating temperature of the furnace.

[0208] Examples

[0209] To illustrate the present invention, the following non-limiting examples are given.

[0210] Characterization protocol

[0211] The specific surface area of ​​colloidal silica in suspension form was estimated using the Sears method (as described in "Determination of specific surface area of ​​colloidal silica by titration with sodium hydroxide", GW Sears, Anal. Chem. 1956, 28, 12, 1981-1983).

[0212] The "self-leveling" properties and segregation are evaluated by the following tests:

[0213] 25 kg of activated product were prepared in the following manner.

[0214] 24.875 kg of wet, unformed product that had been stored for six months was placed in a container. The wet, unformed product was then mixed for one minute using a portable electric mortar mixer (maximum power of 1600 W, equipped with a mortar and paint impeller with a diameter of 140 mm). 0.125 kg of "dead-burned B / C" magnesium oxide powder sold by Grecian Magnesite was then added as a setting activator, with a median particle size of 20 μm, and the mixture was mixed for one minute using the mortar mixer. This resulted in an "activated" product. The preparation of the activated product is advantageously very quick and simple.

[0215] The activated product is then immediately loaded into a pre-oiled hopper in the shape of a truncated pyramid with its tip facing downwards, 320 mm in height, an upper inlet hole with a square cross section measuring 350 mm x 350 mm and a lower outlet hole with a square cross section (towards the cone tip) measuring 130 mm x 130 mm, the hopper being initially closed by a hatch.

[0216] The hatch of the hopper is then suddenly opened and the activated product pours by gravity through the outlet hole into the upper end of a straight, pre-oiled, semi-circular PVC gutter of 170 mm in diameter and 1600 mm in length, placed 700 mm from the ground, the lower end of the gutter being 380 mm from the ground.

[0217] The activated product flows into the gutter and pours into a mold placed below the gutter, below 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.

[0218] The activated product is then allowed to harden into the form of a slab.

[0219] The thickness of the slab is measured on each of the four sides of the slab, at the two ends of the face and at the middle of the length of the face.

[0220] The self-leveling (“SL”) property is achieved if the upper surface of the slab is substantially smooth to the naked eye and if, for each of the four sides, the difference “E” between the minimum measured thickness and the maximum measured thickness is less than or equal to 2 mm.

[0221] After 24 hours of firing in the oven at 110°C, the slab is sawn in half from its center, thus revealing two sawn faces. Segregation is said to occur when the sawn faces show that the surface layer of slurry extends from the upper surface of the slab to a depth “e” of 3 mm or more. Segregation is said to occur when the sawn faces show that the surface layer of slurry extends from the upper surface of the slab to a depth “e” of 3 mm or more.

[0222] The storage stability of the wet unshaped product is evaluated by the following test.

[0223] After manufacture, the wet unshaped product is packaged in a sealed container in the form of a jar, the capacity of which is equal to 500 mL and the diameter of which is equal to 90 mm, and is capped with a lid. The packaged product thus constituted is stored in a room at an average temperature between 21 °C and 25 °C for six months.

[0224] At the end of this phase, the lid of the packaging is removed and the wet unshaped product is placed on the platform of a texture analyzer of model TX700 type 151500, equipped with a reference split probe 130064, sold by the company Lamy Rheology.

[0225] The tip of the split probe is placed so as to lightly touch the upper surface of the wet unshaped product at its center.

[0226] The following individual steps are then performed:

[0227] - the “COMPRESSION” tab on the digital display screen is selected,

[0228] - Select the "single compression" program,

[0229] - Enter the following parameters: descent speed: 0.1 mm / s, detection threshold: 0.1 N, X axis: distance, maximum depth: 45 mm, upper position: 10 mm, force application point: 0 mm,

[0230] - Confirm

[0231] - Press "zero force",

[0232] - Start the measurement by pressing "start".

[0233] The probe is then gradually lowered into the wet unshaped product, to a depth of 45 mm, and the maximum force required for this purpose is recorded.

[0234] If the consistency of the wet unshaped product strongly resists the penetration of the probe, the force applied by the analyser reaches 380 N or even exceeds 380 N. The analyser then temporarily stops applying the penetration force. The measurement is then stopped. The depth reached by the probe under the maximum force applied is then measured.

[0235] "D" is defined as the ratio of the maximum force FMax (in Newton) reached during the measurement period to the penetration depth p (in mm) to reach said maximum force: D = FMax / p.

[0236] The measurement is carried out at room temperature.

[0237] The inventors believe that a value 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 that can be used quickly after a six-month storage period, without long mixing operations.

[0238] In particular, after storage, the wet unshaped product of example 2, outside the invention, has a consistency that makes it impossible to fluidify it for casting. On the contrary, in the following examples 1 and 3 according to the invention, it can be used and even poured after simple mixing with a portable electric mortar mixer (power 1600 W, equipped with mortar and paint impeller, diameter 140 mm).

[0239] Manufacturing protocol

[0240] The following starting materials were used:

[0241] - an ER1681 granular powder having the following chemical analysis, in mass percentage: Zr02: 32.5%, Si02: 15%, AI2O3: 50.9%, 1.6% of other compounds, 10th percentile (D 10 ) equal to 2 mm, 90th percentile (D 90 ) equal to 3.5 mm, median particle size (D 50 ) equal to 2.5 mm,

[0242] - an ER1681 granular powder having the following chemical analysis, in mass percentage: Zr02: 32.5%, Si02: 15%, AI2O3: 50.9%, 1.6% of other compounds, 10th percentile (D 10 ) equal to 0.46 mm, 90th percentile (D 90 ) equal to 1.7 mm, median particle size (D 50 ) equal to 1 mm,

[0243] - an ER1681 granular powder having the following chemical analysis, in mass percentage: Zr02: 32.5%, Si02: 15%, AI2O3: 50.9%, 1.6% of other compounds, 10th percentile (D 10 ) equal to 0.03 mm, 90th percentile (D 90 ) equal to 0.38 mm, median particle size (D 50 ) equal to 0.16 mm,

[0244] - a zirconia powder sold by the Société Européenne des Produits Réfractaires under the name CC10, having a median particle size (D 50 ) equal to 3.5 pm, a mass content of Zr02greater than 98.5%,

[0245] - an electrofused alumina powder, having a mass content of AI2O3greater than 99%, a mass content of Na20 less than 0.2%, a median particle size (D 50 ) equal to 100 pm,

[0246] - an alumina powder CL370 sold by the company ALMATIS,

[0247] - an alumina powder CT3000SG sold by the company ALMATIS.

[0248] Other ingredients include:

[0249] - a colloidal silica suspension sold by the company GRACE PW 50X, according to the technical data sheet, having a specific surface area between 60 m 2 / g and 90 m2 between 50 and 100 g / l, and the mass content of colloidal silica, expressed as a percentage by mass based on the mass of the colloidal silica suspension, is equal to 50%,

[0250] - the colloidal silica suspension sold by the company NOURYON under the name NOVARSIL®FO1440, the specific surface area of which is equal to 250 m FO1440, the specific surface area of which is equal to 250 m 2 between 50 and 100 g / l, and the mass content of colloidal silica, expressed as a percentage by mass based on the mass of the colloidal silica suspension, is equal to 50%,

[0251] - the SIKAGARD exterior wall protector sold by the company SIKA, comprising a hydrolysed silane methyl silane triol potassium salt,

[0252] - a modified polycarboxylic acid ether,

[0253] - an anti-segregation adjuvant from the family of starch ethers.

[0254] Table 1 below provides the composition of the wet unshaped product, expressed as a percentage by mass based on the mass of the wet unshaped product.

[0255] [Table 1]

[0256]

[0257] The wet unshaped products were manufactured in the following manner:

[0258] The colloidal silica suspension was placed in the tank of a Perrier-type paddle mixer. Then, while the mixer was running, the water (only for Examples 1 and 2) was added, then the modified polycarboxylic acid ether was added, then the SIKAGARD exterior wall protector was added. The mixing was continued for 1 minute. The ceramic powder was then added and the stirring was continued for 9 more minutes.

[0259] The wet unshaped product was obtained at the end of this mixing time.

[0260] Each wet unshaped product was then sealed so as to be able to measure its storage stability as described above.

[0261] After 6 months of storage, the self-leveling and segregation properties were measured.

[0262] Table 2 provides the results of the tests carried out.

[0263] [Table 2]

[0264] Example 1 Example 2* Example 3 Specific surface area (m 2 / g)]]> 60 to 90 250 250 Hydrolytic silane and / or siloxane No No Yes Storage stability: D (N / mm) 15 105 19 E (mm) 1 n.m. 0 Self-levelling? Yes No Yes e (mm) 1 n.m. 1 Segregation? No n.m. No

[0265] *: outside the invention n.m.: not measurable result The following findings can be drawn:

[0266] According to example 1 of the application, the binder precursor is a colloidal silica having a specific surface area between 60 m 2 / g and 90 m 2 / g, the D value measured after a storage period equal to 6 months is equal to 15 N / mm.

[0267] Example 2 outside the application, the binder precursor is a colloidal silica having a specific surface area equal to 250 m 2 / g, the D value measured after a storage period equal to 6 months is equal to 105 N / mm.

[0268] The comparison of example 2 outside the application and example 3 according to the application shows the effect of the addition of 0.08% of hydrolysed silane (potassium methylsilanetriol) : the D value of example 2 is equal to 105 N / mm, significantly higher than the D value of example 3 (D value equal to 19 N / mm).

[0269] The products of example 1 and example 3 are self-leveling after mixing with a portable electric mortar mixer and after activation with the addition of magnesium oxide powder, they do not segregate after application, their preparation generates only a small amount of dust.

[0270] It can now be clearly seen that the present application provides a wet, unshaped product, which can be stored for a long period of time and which can be used quickly and easily after storage, substantially without any dust emissions.

[0271] Naturally, the present application is not limited to the described or illustrated embodiments, which are provided as illustrative examples, without limitation.

Claims

1. A packaged product comprising: - a sealed package, and - a wet unshaped product, said wet unshaped product being disposed in said sealed package and consisting for more than 95% of mass of: - 4 to 15% of water by mass percentage based on the mass of the wet unshaped product, - 0.5 to 3.2% of a binder precursor by mass percentage based on the mass of the wet unshaped product, - a ceramic powder, said binder precursor being selected from: - a colloidal silica having a specific surface area of less than or equal to 150 m2 / g, and 2 - a colloidal silica having a specific surface area of less than or equal to 150 m2 / g, and - a mixture consisting of: - a specific surface area less than 500 m2 / g 2 - an amount of colloidal silica greater than or equal to 0.5% by mass percentage based on the mass of the wet unshaped product, the colloidal silica having a specific surface area of less than 500 m2 / g, and - a hydrolyzed silane and / or a siloxane, said ceramic powder consisting of ceramic particles, colloidal silica particles being not considered.

2. The packaged product of claim 1, wherein, said binder precursor being selected from: - a specific surface area greater than 50 m 2 g of colloidal silica, and - a mixture consisting of: - a specific surface area lower than 320 m2 / g and greater than 50 m2 / g 2 - a specific surface area lower than 320 m2 / g and greater than 50 m2 / g 2 - colloidal silica having a specific surface area lower than 320 m2 / g and greater than 50 m2 / g, the amount of colloidal silica being greater than or equal to 0.5% by mass percentage based on the mass of the wet unshaped product, and - a hydrolyzed silane and / or a siloxane.

3. The packaged product according to any one of the preceding claims, wherein, The total amount of hydrolyzed silane and siloxane is less than 20% and more than 3% of the mass of colloidal silica.

4. The product according to any one of the preceding claims, wherein, said hydrolyzed silane comprises at least one hydrophobic functional group, and / or wherein said siloxane comprises at least one hydrophobic functional group.

5. The packaged product according to the immediately preceding claim, wherein, said hydrolyzed silane is selected from: - an alkylsilane, - a vinylsilane, - a sulfur silane, - a mercapto silane, - an epoxy silane, - a methacrylate silane, - an aromatic silane, - a fluoroalkylsilane, - and mixtures thereof, and / or wherein, said siloxane is selected from: - an alkylsiloxane, - a vinylsiloxane, - a sulfur siloxane, - a mercapto siloxane, - an epoxy siloxane, - a methacrylate siloxane, - an aromatic siloxane, - a fluoroalkylsiloxane, - and mixtures thereof.

6. The packaged product according to the immediately preceding claim, wherein, said hydrolyzed silane is an aromatic silane selected from arylsilanes, or is an alkylsilane selected from methylsilanes, ethylsilanes, propylsilanes, butylsilanes, octylsilanes, and mixtures thereof.

7. The packaged product according to the immediately preceding claim, wherein, said hydrolyzed silane is an alkylsilane selected from methylsilanes.

8. The packaged product of claim 1 or 2, wherein, The adhesive precursor contains no siloxanes or any hydrolyzed silanes, and the colloidal silica has a specific surface area of less than 130 m 2 / g.

9. The packaged product according to the immediately preceding claim, wherein, The colloidal silicon dioxide has a specific surface area of less than 90 m 2 / g.

10. The packaged product according to any one of the preceding claims, wherein, said ceramic powder consists for more than 80% of mass of particles whose main component is alumina and / or zirconia and / or silica and / or chromium oxide.

11. The packaged product according to any one of the preceding claims, wherein, said ceramic powder, said binder precursor and water together represent more than 98% of the mass of the wet unshaped product.

12. A method for manufacturing a packaged product according to any one of the preceding claims, said method comprising the following successive steps: a) preparing the wet unshaped product; b) packaging the wet unshaped product in the sealed package to obtain the packaged product.

13. The manufacturing method according to the preceding claim, wherein, Step a) comprises mixing starting feeds consisting for more than 95% of mass of: by mass percentage based on the mass of the starting feeds, - 4 to 15% of water, - 0.5 to 3.2% of a binder precursor, - a ceramic powder different from colloidal silica, said binder precursor being selected from: - a specific surface area of less than or equal to 150 m2 / g and preferably greater than 50 m2 / g 2 - a specific surface area of less than or equal to 150 m2 / g and preferably greater than 50 m2 / g 2 - a colloidal silica having a specific surface area of less than or equal to 150 m2 / g and preferably greater than 50 m2 / g, said colloidal silica being provided in the form of an aqueous suspension, and - a mixture consisting of: - a specific surface area less than 500 m2 / g, preferably between 50 m2 / g and 320 m2 / g, 2 - a specific surface area less than 500 m2 / g, preferably between 50 m2 / g and 320 m2 / g, 2 - a specific surface area less than 500 m2 / g, preferably between 50 m2 / g and 320 m2 / g, 2 - a colloidal silica having a specific surface area greater than or equal to 0.5% by mass percentage based on the mass of the wet unshaped product, the colloidal silica being provided in the form of an aqueous suspension, and - a hydrolyzed silane and / or a siloxane and / or a hydrolysable silane, to obtain the wet unshaped product.

14. A method for repairing a furnace, said method comprising the following successive steps: 1) storing a packaged product according to any one of claims 1 to 11 or manufactured according to the method of claim 12 or 13 for more than 2 weeks; 2) unpacking the packaged product so as to withdraw a wet unshaped product therefrom; 3) activating the adhesive precursor of the wet unshaped product by mixing with a coagulation activator and / or by placing the wet unshaped product at a temperature suitable for activating the adhesive precursor, to obtain an activated product; 4) placing the activated product in the area to be repaired, step 4) being carried out simultaneously with step 3) if the area to be repaired of the furnace is at a temperature suitable for activating the adhesive precursor, or step 4) being carried out after step 3), until a hardened product is obtained.

15. The method according to the immediately preceding claim, comprising the following step after step 4): 5) sintering the hardened product.

16. The method according to any of the two immediately preceding claims, wherein, In step 1), the packaged product is stored for more than 4 months.

17. A method for manufacturing a block for furnaces, the method comprising the following steps in succession: 1) storing a packaged product according to any one of claims 1 to 11 or manufactured according to the method of claim 12 or 13 for more than 2 weeks; 2) unpacking the packaged product so as to extract a wet unshaped product therefrom; 3) activating the adhesive precursor of the wet unshaped product by mixing with a coagulation activator and / or by placing the wet unshaped product at a temperature suitable for activating the adhesive precursor, to obtain an activated product; 4) placing the activated product in a mould, step 4) being carried out simultaneously with step 3) if the mould is at a temperature suitable for activating the adhesive precursor, or step 4) being carried out after step 3), until a hardened product is obtained.

18. The method according to the immediately preceding claim, comprising the following step after step 4): 5) sintering the hardened product.

19. The method according to any of the two immediately preceding claims, wherein, In step 1), the packaged product is stored for more than 4 months.

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