Product for repairing a furnace

Abstract

The invention relates to a packaged product comprising: - a hermetically sealed package, and - a foam of a wet unshaped product containing a ceramic powder, said foam being contained in the hermetically sealed package. Use for repairing a furnace.

Description

[0001] Description

[0002] Title: OVEN REPAIR PRODUCT

[0003] technical field

[0004] The present invention relates to a packaged product consisting of a foam in a moist, unshaped form, arranged in a hermetically sealed package. The foam is particularly intended for use in glass furnaces, specifically for repairing glass furnaces.

[0005] Previous art

[0006] The industry, particularly the glass industry, generally uses refractory products, either cast and molten or obtained by sintering, which are highly resistant to corrosion by glass and come in the form of blocks or slabs, for the construction of its furnaces.

[0007] Unshaped products can be used for the construction and / or repair of these furnaces. These unshaped products are generally in the form of a dry powder to facilitate storage. This powder is moistened on-site to obtain a wet, unshaped product that can then be installed.

[0008] Typically, a predetermined quantity of powder, for example 500 kg, a setting activator, and water are poured into a mixer. After mixing, the resulting batch of activated product can be poured into a pump hopper for transport to the destination site. The mixer can then be refilled for the next cycle. To ensure the most continuous supply to the pump, a second mixer is usually used to provide activated product while the first mixer is being refilled. The two mixers operate alternately so that the pump hopper never runs dry.

[0009] Pouring dry powders into mixers generates dust clouds.

[0010] Preparation is time-consuming, especially when large quantities of unprocessed products are involved. It also requires equipment such as large mixers and / or pumps, which clutter the work area.

[0011] There is therefore a need for an unshaped product that can be stored for extended periods and, after storage, can be quickly used with simple equipment, for example, a basic plaster mixer, and with minimal dust generation. One objective of the present invention is to satisfy, at least partially, this need.

[0012] Summary of the invention

[0013] According to the invention, this goal is achieved by means of a packaged product comprising:

[0014] - airtight packaging, and

[0015] - a foam of a moist, unshaped product containing a ceramic powder, said foam being disposed of in said airtight packaging.

[0016] As will be explained in more detail later in the description, the inventors discovered that the foaming form stabilizes the unmolded, moist product and allows for its long-term storage in airtight packaging. After storage, the foaming form can be removed by simply mixing it with an antifoaming agent, optionally after adding a binder precursor and / or a setting activator. A defoamed, unmolded, moist product can thus be placed very quickly.

[0017] Furthermore, the preparation can be carried out on-site, without expensive and bulky equipment, for example using a hand mixer. Finally, since the foam is wet, this preparation generates virtually no dust.

[0018] In airtight packaging, the unshaped, wet product is neither hardened nor activated, unlike concrete in the form of a solid foam. The production of this type of concrete requires the stabilization of a non-solid intermediate foam to maintain its shape and, in particular, to prevent it from collapsing. This stability is only required for a very short period, typically a few minutes. The foamy form of this intermediate foam is not intended to preserve the product it constitutes, especially for long-term storage, but rather to give the concrete a foamy structure. Furthermore, the goal is to stabilize the foamy form, not to preserve the properties of the product it comprises.

[0019] The stabilization of the intermediate foam can also limit sedimentation.

[0020] The present invention is a continuation of a prior invention, the subject of unpublished patent application PCT / EP2024 / 056162 as of the filing date of this application, based on the ability of certain specific binder precursors to preserve a moist, unshaped product during storage. However, that application does not disclose any foam.

[0021] A product packaged according to the invention may further include one or more of the following optional features: - the foam contains enough bubbles so that debubbling of a volume V m of said foam, at a constant temperature, can lead to a volume Vi such that the ratio V m / Vi is greater than 1.10;

[0022] - the foam contains a limited quantity of bubbles so that no debubbling of a volume Vm of the foam, at a constant temperature, can lead to a volume Vi such that the ratio V m / Vi is greater than 1.60;

[0023] - the foam contains a binder precursor capable of binding the ceramic powder particles under the effect of activation by contact with a setting activator and / or an increase in temperature;

[0024] - the foam comprises, as a mass percentage based on the mass of the foam,

[0025] - colloidal silica, or a mixture of colloidal silica on the one hand and a hydrolyzed silane and / or a siloxane on the other hand, in an amount greater than or equal to 0.5% and less than 3.2%, or

[0026] - glass-ceramic particles and / or glass particles, in a quantity greater than 2% and less than 15%, or

[0027] - a phosphate chosen from aluminium phosphate, magnesium phosphate, and mixtures thereof, in a quantity greater than 0.15% and less than 1.2%;

[0028] - the foam contains an anti-foaming agent capable of acting chemically to de-foam the foam;

[0029] - ceramic powder:

[0030] - is composed, for more than 80% by mass, of particles whose main constituents are alumina and / or zirconia and / or silica and / or chromium oxide; and / or

[0031] - exhibits a particle size distribution such that the fraction of ceramic powder particles with a size less than 40 pm is distributed, as a percentage by mass relative to the mass of the ceramic powder, as follows:

[0032] - fraction < 0.5 pm: > 4%, and / or < 6.5%, and

[0033] - fraction < 2 pm: > 5%, and / or < 18%, and

[0034] - fraction < 10 pm: > 16%, and / or < 35%, and

[0035] - fraction < 40 pm: 29-52%; and / or

[0036] - has a 99.5 percentile less than or equal to 10 mm.

[0037] The invention also relates to a method of manufacturing a packaged product according to the invention, comprising the following successive steps: a) manufacturing a foam from a wet unshaped product containing a ceramic powder; b) packaging said foam in a hermetically sealed package.

[0038] In one embodiment, at step a), a starting charge is prepared, consisting of more than 96% by mass, expressed as mass percentages based on the mass of the starting charge.

[0039] - of a ceramic powder,

[0040] - water in a quantity between 4% and 15%,

[0041] - of a foaming agent in an amount greater than or equal to 0.0025% and less than or equal to 0.5%,

[0042] - preferably, a binder precursor in an amount between 0.5% and 15%,

[0043] - preferably, an anti-foaming agent in a quantity greater than or equal to 0.005% and less than or equal to 1%,

[0044] - optionally, a surfactant in an amount greater than or equal to 0.05% and less than or equal to 1%,

[0045] - optionally, an anti-segregation adjuvant in a quantity greater than or equal to 0.02% and less than or equal to 0.50%,

[0046] - optionally, of a biocide in a quantity greater than or equal to 0.01% and less than or equal to 1%.

[0047] The invention also relates to a method for repairing a furnace, preferably a glass furnace, said method comprising the following successive steps:

[0048] 1) storage of a product packaged according to the invention;

[0049] 2) unpacking and de-bubbling of the foam so as to obtain a wet, unshaped, de-bubbling product, the de-bubbling being able to be before or after unpacking;

[0050] 3) placement of said unshaped wet de-bubbling product in a repair area of ​​the oven, then hardening of said unshaped wet de-bubbling product.

[0051] A method for repairing a furnace according to the invention may further include one or more of the following optional features:

[0052] - in step 2), the composition of the initially unshaped wet product, in the form of a foam, is modified so that said unshaped wet product contains:

[0053] - a binder precursor and a setting activator for said binder precursor, the reaction of the binder precursor with the setting activator transforming the binder precursor into said binder; and / or

[0054] - a binder precursor capable of transforming, by increasing the temperature and then cooling, into said binder; and / or

[0055] - an anti-foaming agent, the said modification of composition being carried out

[0056] - before opening the packaging, or

[0057] - after opening the packaging, before or after extracting the foam from the packaging;

[0058] - in step 2), the composition of the foam is modified by adding a cement.

[0059] In one embodiment, said oven repair method comprises steps a) and b), prior to step 1).

[0060] Definitions

[0061] For clarity, we distinguish between "wet unformed product," "activated product," and "cured product." Wet unformed product is the product intended for block making or repair, as it appears before activation. It may be in the form of a foam or a de-bubbled liquid. After being unpacked and after activation of the binder precursor, the wet unformed product enters a curing phase, which may be short-lived, particularly in the case of a hot repair; it is then called "activated product." After curing, it is called "cured product."

[0062] The "packaged product" consists of the wet unshaped product foam and the packaging.

[0063] Unless otherwise specified, "foam" refers to wet, unshaped product foam.

[0064] By "foam" we mean a product that incorporates gas bubbles, preferably air bubbles, in such a quantity that degassing a volume V m foam, at a constant temperature, leads to a volume Vi such that the ratio V m / Vi must be greater than 1.05, the measurement of said ratio being carried out as described in the examples. The foam may be self-supporting or not.

[0065] The "de-bubbling" of a foam from a wet, unshaped product consists of reducing the amount of bubbles it contains.

[0066] The term "ceramic powder" refers to a powder composed of particles of a ceramic material, meaning neither organic nor metallic, called "ceramic particles." The term "binder precursor" refers to a constituent capable of forming, after activation, a binder that rigidly bonds the ceramic particles together to form a solid mass. Before activation, and particularly in foam, the binder precursor does not provide this bonding. Activation results from contacting the binder precursor with a "setting activator" or from heating. By extension, the unshaped, moist product containing an activated binder precursor is called an "activated product." In the hardened product, the binder therefore results from a reaction between the binder precursor and the setting activator and / or from a transformation under the effect of a sufficiently high temperature.

[0067] When the binder precursor is supplied conventionally as a suspension, as in the case of colloidal silica, its quantity is measured without taking water into account. For example, in a colloidal silica suspension, water and colloidal silica (the binder precursor) are separated.

[0068] A "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 measurement of specific surface area by considering that all the 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", GW Sears, Anal. Chem. 1956, 28, 12, 1981-1983.

[0069] A "hydrolyzed silane" is a silane that contains at least one silanol Si-OH group. A hydrolyzed silane can be a totally or partially hydrolyzed silane.

[0070] A "hydrolyzable silane" is a silane that is different from 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).

[0071] A compound containing one or more Si-O-Si bonds in its molecule is called a "siloxane." Classically, and for the purposes of this description, polysiloxanes are therefore siloxanes. A siloxane can be obtained by the polycondensation of a silane.

[0072] A "foaming agent" is defined as a substance which, when added to a starting material, leads to the formation of foam, for example, through agitation during mixing of the starting material or through a chemical reaction. An "antifoaming agent" is defined as a substance which, when added to foam, leads to the suppression of the foamy form, for example, through agitation during mixing of the foam.

[0073] The binder precursor, foaming agent, antifoaming agent, surfactant, anti-segregation agent, and biocide may contain water. However, to define the composition of the foam or starting charge, this potential water is counted along with the added water alone, separately from the other constituents of the binder precursor, foaming agent, antifoaming agent, surfactant, anti-segregation agent, and biocide. In other words, the quantity of any substance chosen from among the binder precursor, foaming agent, antifoaming agent, surfactant, anti-segregation agent, and biocide is equal to the ratio, expressed as a percentage, of

[0074] - the mass of this substance without taking into account any water it may contain,

[0075] - on the mass of the foam or starting charge, including water supplied separately and water supplied with said substances.

[0076] For example, a mass content of foaming agent refers to the mass of the foaming agent without any water it may contain.

[0077] A "hermetic" package is a package that isolates the foam it contains from the ambient air, particularly under storage conditions.

[0078] The 10th (D10), 50th (D50), 90th (D90), and 99.5th (D99.5) 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 powder's particles, with the particle sizes listed in ascending order. For example, 10% by mass of the powder's particles have a size smaller than D10, and 90% by mass have a size greater than or equal to D10. Percentiles can be determined using a particle size distribution obtained with a laser diffraction particle size analyzer.

[0079] By "main constituents" we mean the constituents whose mass proportions are the highest.

[0080] Zirconia is the name given to zirconium oxide (ZrOi). When Z1O2 is mentioned, it should be understood as (ZrOi + HfOi). Indeed, a small amount of HfOi, chemically inseparable from Z1O2 in a conventional zirconia manufacturing process and exhibiting similar properties, is always naturally present in zirconia sources at concentrations generally below 2%. Hafnium oxide is therefore not considered an impurity.

[0081] A component that would be both:

[0082] - a foaming agent or an anti-foaming agent, and

[0083] - a surfactant and / or an anti-segregation adjuvant and / or a biocide, is considered, in this application, to be exclusively a foaming agent or an anti-foaming agent, respectively.

[0084] “Contain” or “understand” or “present” should be interpreted in a non-limiting manner.

[0085] Detailed description

[0086] Wet unshaped product foam

[0087] The packaged product consists of airtight packaging and a moist, unshaped product foam contained within the airtight packaging.

[0088] The packaging is chosen so that, during storage, typically at atmospheric pressure and a temperature between 10°C and 30°C, the foam is isolated from the ambient air, i.e., there is no gas exchange between the inside and outside of the packaging.

[0089] Any airtight container, rigid or flexible, is suitable. Preferably, the airtight container is a drum or a sealed plastic bag. It preferably has a volume sufficient to hold 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 foam.

[0090] The foam consists of a mixture of ceramic powder, water and a foaming agent.

[0091] It is not solid and can be de-aired.

[0092] Preferably, the foam contains enough bubbles so that debubbling a volume Vm of the foam, at a constant temperature, particularly carried out according to the method described in the examples, can lead to a volume Vi such that the ratio V m / Vi is greater than 1.06, preferably greater than 1.08, preferably greater than 1.10, preferably greater than 1.13. Preferably, the foam contains a limited quantity of bubbles so that no debubbling of a volume V m foam, at a constant temperature, particularly when produced according to the method described in the examples, can lead to a volume Vi such that the ratio V m / V i is greater than 1.60, preferably greater than 1.50, preferably greater than 1.40, preferably greater than 1.30.

[0093] The foam can be self-supporting or not.

[0094] Ceramic powder

[0095] Preferably, the amount of ceramic powder in the foam is greater than 61.5%, preferably greater than 67.3%, preferably greater than 71.3%, preferably greater than 73.8%, preferably greater than 75.1%, preferably greater than 76.4%, preferably greater than 78.8% and / or preferably less than 95.9%, preferably less than 95%, preferably less than 94%, in mass percentages based on the mass of the foam.

[0096] The nature and particle size distribution of the ceramic powder are chosen according to the intended use of the unshaped wet product. In particular, all ceramic powders used for manufacturing hardened products intended for glassmaking furnaces can be considered.

[0097] Preferably, the ceramic powder consists of more than 80%, preferably more than 90%, preferably more than 95% by mass of particles whose main constituents are alumina (Al2O3) and / or zirconia (ZrCl) and / or silica (SiCl) and / or chromium oxide (CnCh).

[0098] Preferably, the ceramic powder consists of more than 80%, preferably more than 90%, preferably more than 95%, by mass percentage, of oxide(s).

[0099] In one embodiment, the ceramic powder consists of more than 80%, preferably more than 90%, preferably more than 95%, by mass percentage based on oxides, of Al2O3, SiCl3, and Z1O2, with

[0100] - preferably Al2O3 > 40%, preferably Al2O3 > 45%, preferably Al2O3 > 50% and Al2O3 < 65%, preferably Al2O3 < 60%, as a mass percentage based on oxides; and / or

[0101] - preferably SiCl > 8%, preferably SiCl > 12% and SiCl < 20%, preferably SiCl < 15%, as a mass percentage based on oxides; and / or

[0102] - preferably Z1O2 > 20%, preferably Z1O2 > 25%, preferably Z1O2 > 30% and Z1O2 < 45%, preferably Z1O2 < 40%, or even < 35%, as a mass percentage based on oxides.

[0103] In one embodiment, the ceramic powder consists of more than 80%, preferably more than 90%, preferably more than 95%, by mass percentage on the basis of oxides, of Al2O3 and SiCh, with preferably Al2O3 > 50% and Al2O3 < 80%, by mass percentage on the basis of oxides, and / or preferably SiCh > 20% and SiU2 < 50%, by mass percentage on the basis of oxides.

[0104] In one embodiment, the ceramic powder consists of more than 80%, preferably more than 90%, preferably more than 95%, by mass percentage on the basis of oxides, of SiCh and Z1O2, with preferably Z1O2 > 40%, preferably Z1O2 > 50%, preferably Z1O2 > 60% and Z1O2 < 80%, preferably Z1O2 < 70%, by mass percentage on the basis of oxides, and / or preferably SiCh > 20%, preferably SiC > 30% and SiC < 60%, preferably SiCh < 50%, preferably SiC < 40%, by mass percentage on the basis of oxides.

[0105] In one embodiment, the ceramic powder consists of more than 80%, preferably more than 90%, preferably more than 95%, by mass percentage on the basis of oxides, of SiC.

[0106] In one embodiment, the ceramic powder has a chemical analysis such that Z1O2 > 70%, preferably Z1O2 > 80%, preferably Z1O2 > 90% and Z1O2 < 98%, as a percentage by mass on the basis of the oxides.

[0107] In one embodiment, the ceramic powder has a chemical analysis such that Al2O3 > 90% and Al2O3 < 98%, as a percentage by mass on the basis of the oxides.

[0108] Preferably, the fraction of ceramic powder particles smaller than 40 pm is distributed, as a percentage by mass relative to the mass of the ceramic powder, as follows:

[0109] - fraction < 0.5 pm: > 4%, preferably > 5%, and / or < 6.5%, and

[0110] - fraction < 2 pm: > 5%, preferably > 8%, preferably > 10%, preferably > 13% and / or < 18%, and

[0111] - fraction < 10 pm: > 16%, preferably > 19%, preferably > 22%, preferably > 24% and / or < 35%, preferably < 34%, and

[0112] - fraction < 40 pm: 29-52%, preferably > 30% and / or < 45%, preferably

[0113] < 40%. These fractions can be determined using a particle size distribution carried out using a laser particle size analyzer.

[0114] 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.

[0115] Preferably, the fraction of ceramic powder particles smaller than 500 pm represents more than 50% by mass of said ceramic powder.

[0116] Preferably, the fraction of ceramic powder particles 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.

[0117] Advantageously, these particle size characteristics promote self-flowability, and therefore the placement in service position, of the unshaped wet debubbling product, that is to say obtained after debubbling of the foam.

[0118] Ceramic powder may contain particles:

[0119] - of electrofused refractory products such as ER-1681 or ER-1711 produced and marketed by the European Society of Refractory Products. These two products contain, as a percentage by mass, based on oxides, 32 to 54% of Z1O2, 36 to 51% of AhCh, 10 to 16% of SiCE and 0.2 to 1.5% of NaiO;

[0120] - of mullite;

[0121] - of zirconia;

[0122] - of alumina;

[0123] - chromium oxide.

[0124] In one embodiment, the ceramic powder does not contain silica particles.

[0125] Water

[0126] The water preferably originates from the raw materials, and in particular from the optional colloidal silica suspension, and from a specific addition of water. Preferably, the (total) water content in the foam is greater than 5%, preferably greater than 6%, and / or preferably less than 14%, preferably less than 12%, preferably less than 10%, as mass percentages based on the mass of the foam.

[0127] Foaming agent: The foaming agent works to transform the unformed, moist product into a foam. Foaming agents are well known.

[0128] The foaming agent is preferably chosen from soaps, Sika Betomouss marketed by the Sika company, and foaming agents from the Techcell range marketed by the Coisoimper company.

[0129] The amount of foaming agent depends on the nature of the foaming agent and a person in the trade knows how to adjust this amount, possibly through simple trials.

[0130] Preferably, the quantity of foaming agent is greater than or equal to 0.0025%, preferably greater than or equal to 0.003%, preferably greater than or equal to 0.004%, and preferably less than or equal to 0.5%, preferably less than or equal to 0.4%, preferably less than or equal to 0.3%, preferably less than or equal to 0.15%, preferably less than or equal to 0.10%, preferably less than or equal to 0.06%, in mass percentages based on the mass of the foam.

[0131] Binder precursor

[0132] The binder precursor, once activated, forms a bond that immobilizes the ceramic particles relative to one another. It may be present in the foam or added after opening the packaging, particularly during the foam degassing process. Therefore, its presence in the foam is optional.

[0133] Of course, when the foam contained in the airtight packaging contains a binder precursor that can be activated by a setting activator, it does not contain said setting activator.

[0134] In one embodiment, the foam preferably contains:

[0135] - colloidal silica, or

[0136] - a mixture of colloidal silica on the one hand and a hydrolyzed silane and / or a siloxane on the other hand, or

[0137] - glass-ceramic particles, particles in a glass, in particular in a glass precursor glass for glass-ceramics, and mixtures of these particles, or

[0138] - a phosphate chosen from an aluminium phosphate, a magnesium phosphate, and mixtures thereof.

[0139] In said embodiment, the foam preferably contains:

[0140] - colloidal silica, or - a mixture of colloidal silica on the one hand and a hydrolyzed silane and / or a siloxane on the other hand, or

[0141] - glass-ceramic particles, particles in a glass, in particular in a glass precursor of glass-ceramic, and mixtures of these particles.

[0142] All types of colloidal silica can be considered. Colloidal silica, in particular, can have a specific surface area greater than 150 m². 2 / g.

[0143] Preferably, 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.

[0144] In practice, colloidal silica is supplied in suspension, that is to say, supplied with water.

[0145] Preferably, colloidal silica has a negative zeta potential value when in suspension.

[0146] In one embodiment, the foam contains colloidal silica, preferably having a specific surface area less than or equal to 150 m² 2 / g, preferably less than 130 m 2 / g, preferably less than 110 m 2 / g, preferably less than 90 m 2 / g and preferably greater than 50 m 2 / g, preferably greater than 60 m 2 / g, in an amount greater than or equal to 0.5%, preferably greater than or equal to 0.8%, preferably greater than or equal to 1.0%, 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 foam.

[0147] In one embodiment, the foam contains a mixture of colloidal silica on the one hand and hydrolyzed silane and / or siloxane on the other, the colloidal silica preferably having a specific surface area of ​​less than 500 m² 2 / g, preferably between 50 m 2 / g and 320 m 2 / g, the quantity of said mixture being greater than or equal to 0.5%, preferably greater than or equal to 0.8%, preferably greater than or equal to 1.0%, 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%, as mass percentages based on the mass of the foam, the total quantity of hydrolyzed silane and siloxane representing preferably 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 inventors have discovered that colloidal silica is particularly well suited if it has a specific surface area less than or equal to 500 m². 2 / g, provided that it is associated with a hydrolyzed silane and / or a siloxane if its specific surface area is greater than 150 m² 2 / g. Of course, a hydrolyzed silane and / or a siloxane may also be present if said specific surface area is less than or equal to 150 m² 2 / g, but this presence is then optional.

[0148] The total amount of hydrolyzed silane and siloxane is preferably greater than 0.05%, preferably greater than 0.07%, and preferably less than 1.0%, 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%, as mass percentages on the basis of the mass of the foam.

[0149] Preferably, the hydrolyzed silane comprises at least one hydrophobic functional group. Even more preferably, said hydrolyzed silane is selected from:

[0150] - alkylsilanes,

[0151] - vinylsilanes,

[0152] - sulfur silanes (or "sulfur silanes" in English)

[0153] - mercaptosilanes,

[0154] - epoxy silanes,

[0155] - methacrylate silanes,

[0156] - aromatic silanes (or "aromatic silanes" in English),

[0157] - fluoroalkylsilanes, and

[0158] - their mixtures.

[0159] Preferably, alkylsilanes are chosen from among methylsilanes, ethylsilanes, propylsilanes, butylsilanes, octylsilanes and mixtures thereof, preferably from among methylsilanes.

[0160] Preferably, 1' alkylsilane is potassium methylsilanetriolate.

[0161] In one embodiment, the aromatic silanes are chosen from among the arylsilans.

[0162] Preferably, the hydrolyzed silane is potassium methylsilanetriolate.

[0163] Preferably, the siloxane comprises at least one hydrophobic functional group. Even more preferably, said siloxane is selected from:

[0164] - alkylsiloxanes,

[0165] - vinylsiloxanes, - sulfur siloxanes (or "sulfur siloxanes" in English),

[0166] - mercaptosiloxanes,

[0167] - epoxy siloxanes,

[0168] - methacrylate siloxanes,

[0169] - aromatic siloxanes (or "aromatic siloxanes" in English),

[0170] - fluoroalkylsiloxanes, and

[0171] - their mixtures.

[0172] In one embodiment, the foam contains a set of glass-ceramic particles and / or particles in a glass, in particular in a glass precursor of glass-ceramic, in a total quantity the quantity of said set of particles being preferably greater than 2%, preferably greater than 3% and preferably less than 15%, preferably less than 13%, preferably less than 12%, preferably less than 10%, preferably less than 9%, preferably less than 8%, in mass percentages on the basis of the mass of the foam.

[0173] The particles of glass-ceramics may all have the same composition or different compositions. The same applies to particles in a glass, particularly in glass-ceramic precursor glass.

[0174] Preferably, the particles in a glass have a glass transition temperature below 1100°C, preferably below 1000°C, preferably below 900°C, or even below 800°C.

[0175] In a particular embodiment, the foam comprises glass particles, preferably made up of glass particles, the glass particles having the following mass chemical composition:

[0176] - SiO2: 70% - 75%,

[0177] - AI2O3: < 2%,

[0178] - CaO: 8% - 12%,

[0179] - Na2O: 11% - 14%,

[0180] - K2O: < 4%,

[0181] - MgO: < 6%,

[0182] - Other constituents: < 3%, for a total of 100%. The unshaped product is then particularly well suited for use in a soda-lime glass melting furnace.

[0183] In a particular embodiment, the foam comprises glass particles, preferably made up of glass particles, the glass particles having the following mass chemical composition:

[0184] - SiO2: 57% - 65%,

[0185] - AI2O3: < 3%,

[0186] - CaO: 6% - 8%,

[0187] - Na2O: 14% - 18%,

[0188] - K2O: < 1%,

[0189] - MgO: 3% - 5%,

[0190] - B2O3: 5% - 12%,

[0191] - other constituents: < 3%, for a total of 100%.

[0192] The unshaped product is then particularly well suited for use in a glass melting furnace for insulation, or even a soda-lime glass melting furnace.

[0193] In a particular embodiment, the foam comprises glass particles, preferably made up of glass particles, the glass particles having the following mass chemical composition:

[0194] - SiO2: 54% - 63%,

[0195] - A12O3: 14% - 20%,

[0196] - CaO: 4% - 17%,

[0197] - Na2O: < 1%,

[0198] - MgO: < 5%,

[0199] - B2O3: 6% - 12%,

[0200] - SrO+BaO+ZnO: 3% - 12%, for a total of 100%.

[0201] The unshaped product is then particularly well suited for use in a strengthening glass melting furnace, and in a glass furnace for insulation, or even a soda-lime glass melting furnace.

[0202] Preferably, more than 50%, preferably more than 70%, preferably more than 90%, preferably more than 95%, preferably substantially 100% of the glass-ceramic particles, as a percentage by mass on the basis of the glass-ceramic particles, have a crystallization rate greater than 5%, preferably greater than 10%, or even greater than 15% and preferably less than 80%, preferably less than 70%, preferably less than 60%, preferably less than 50%.

[0203] Preferably, the glass-ceramic particles exhibit microcrystallites of wollastonite and / or pseudowollastonite and / or anorthite and / or gehlenite and / or virgilite and / or spodumene and / or indialite and / or cordierite and / or beta-quartz and / or cristobalite and / or tridymite and / or mullite and / or clinoenstatite and / or spinel and / or diopside and / or zirconolite and / or protoenstatite and / or forsterite and / or sapphirine and / or rankinite and / or bredigite and / or alite and / or grossite and / or albite.

[0204] Preferably, the glass precursor particles of glass ceramics have a chemical analysis suitable for forming, by heat treatment of crystallization, microcrystallites of wollastonite and / or pseudowollastonite and / or anorthite and / or gehlenite and / or virgilite and / or spodumene and / or indialite and / or cordierite and / or beta-quartz and / or cristobalite and / or tridymite and / or mullite and / or clinoenstatite and / or spinel and / or diopside and / or zirconolite and / or protoenstatite and / or forsterite and / or sapphirine and / or rankinite and / or bredigite and / or alite and / or grossite and / or albite.

[0205] Preferably, the precursor glass of glass-ceramic has a glass transition temperature above 700°C, or even above 750°C.

[0206] In a particular embodiment, the foam comprises particles of a glass precursor of glass ceramic, preferably consisting of particles of a glass precursor of glass ceramic, the particles of a glass precursor of glass ceramic having the following mass chemical composition, in mass percentages on the basis of oxides and for a total of more than 95%, more than 98%, preferably substantially 100%:

[0207] - SiO2: 45% - 75%, and

[0208] - AI2O3: 5% - 40%, and

[0209] - CaO + MgO + Li2O: 3% - 30%,

[0210] - nucleating agents, preferably selected from TiO2, ZrO2, P2Os and their mixtures, expressed in oxide form: 0.1% - 20%, preferably 1% - 10%, preferably 1% - 5%.In a particular embodiment, the foam comprises particles of a glass precursor of glass ceramic, preferably consisting of particles of a glass precursor of glass ceramic, said particles of a glass precursor of glass ceramic having a chemical analysis suitable for forming, by heat treatment of crystallization, microcrystallites of wollastonite and / or pseudowollastonite and / or anorthite and / or gehlenite and / or virgilite and / or spodumene and / or indialite and / or cordierite and / or beta-quartz and / or cristobalite and / or tridymite and / or mullite and / or clinoenstatite and / or spinel and / or diopside and / or zirconolite and / or protoenstatite and / or forsterite and / or sapphirine and / or rankinite and / or bredigite and / or alite and / or wholesale and / or albite.

[0211] In a particular embodiment, the foam comprises glass-ceramic particles, preferably consisting of glass-ceramic particles, said glass-ceramic particles having microcrystallites of wollastonite and / or pseudo-wollastonite and / or anorthite and / or gehlenite and / or virgilite and / or spodumene and / or indialite and / or cordierite and / or beta-quartz and / or cristobalite and / or tridymite and / or mullite and / or clinoenstatite and / or spinel and / or diopside and / or zirconolite and / or protoenstatite and / or forsterite and / or sapphirine and / or rankinite and / or bredigite and / or alite and / or grossite and / or albite.

[0212] In one embodiment, the foam comprises a phosphate selected from an aluminium phosphate, a magnesium phosphate, and mixtures thereof, the quantity of said phosphate being preferably greater than or equal to 0.15% and preferably less than or equal to 1.2%, in mass percentages based on the mass of the foam.

[0213] Some binder precursors listed above (colloidal silica particles, glass-ceramic particles, or particles in a glass, particularly in a glass-ceramic precursor) may be in a ceramic material, so they can be counted as either "ceramic particles" or "binder precursors," depending on the treatment the foam undergoes. If a passage in the foam description refers to both ceramic particles and binder precursor particles in a ceramic material, the binder precursor particles are not counted as ceramic particles. If a foam contains only ceramic particles of a single type, these particles are not considered binder precursor particles.The ceramic powder, foaming agent, water, and optional binder precursor together preferably constitute more than 96%, more than 97%, more than 98%, or more than 99% of the foam mass. The remainder to 100% preferably consists of an optional antifoaming agent and / or an optional surfactant and / or an optional anti-segregation adjuvant and / or an optional biocide and / or optional organic constituents, other than the antifoaming agent, surfactant, anti-segregation adjuvant, and biocide.

[0214] Anti-foaming agent

[0215] The anti-foaming agent facilitates the de-airing of the foam when the unmolded, moist product needs to be used after storage, particularly for repairs. Its action typically results from agitation, allowing it to remain present in the foam at rest during storage. Advantageously, the unmolded, moist product can then be used particularly simply and quickly, as no changes to its composition are required after unpacking.

[0216] The optional antifoaming agent is preferably chosen from the Foamaster range of antifoaming agents marketed by BASF, the Constraspum range of antifoaming agents marketed by Zschimmer & Schwartz and the Vinapor range of antifoaming agents marketed by BASF.

[0217] Preferably, when the unshaped wet product contains an antifoaming agent, the amount of antifoaming agent is greater than or equal to 0.005%, preferably greater than or equal to 0.01% and / or preferably less than or equal to 1%, preferably less than or equal to 0.9%, preferably less than or equal to 0.8%, preferably less than or equal to 0.7%, preferably less than or equal to 0.6%, preferably less than or equal to 0.5%, in mass percentages based on the mass of the foam.

[0218] The effectiveness of the antifoaming agent can be influenced by the nature and / or quantity of the foaming agent. Simple routine tests can determine the appropriate antifoaming agent.

[0219] Surfactant

[0220] Any conventional surfactant can be used, for example, a modified polycarboxylate ether, a polyacrylate, particularly sodium polyacrylate, or a polyphosphate, particularly sodium polyphosphate. The choice of a surfactant from among those commonly used by those skilled in the art can be guided by the results of simple tests, such as those described herein, based on the desired performance (ease of placement, density of the unshaped wet product after placement).

[0221] Preferably, the amount of surfactant in the foam is greater than or equal to 0.05%, preferably greater than or equal to 0.07%, preferably greater than or equal to 0.10%, and / or preferably less than or equal to 1.00%, preferably less than or equal to 0.80%, preferably less than or equal to 0.50%, as mass percentages based on the mass of the foam.

[0222] Anti-segregation adjuvant

[0223] Any conventional anti-segregation adjuvant can be used, for example starch ethers.

[0224] Preferably, the quantity of anti-segregation adjuvant in the foam is greater than or equal to 0.02%, preferably greater than or equal to 0.03%, preferably greater than or equal to 0.04%, and / or preferably less than or equal to 0.50%, preferably less than or equal to 0.40%, preferably less than or equal to 0.30%, preferably less than or equal to 0.20%, in mass percentages based on the mass of the foam.

[0225] Biocide

[0226] Any conventional biocide can be used.

[0227] Preferably, the quantity of biocide in the foam is greater than or equal to 0.01%, preferably greater than or equal to 0.02%, preferably greater than or equal to 0.03%, and / or preferably less than or equal to 1.0%, preferably less than or equal to 0.9%, preferably less than or equal to 0.8%, preferably less than or equal to 0.7%, preferably less than or equal to 0.5%, preferably less than or equal to 0.3%, as mass percentages based on the mass of the foam.

[0228] Manufacturing process

[0229] The manufacturing process for a packaged product according to the invention comprises the successive steps a) and b).

[0230] In step a), a starting material is prepared with a composition suitable for foam production. This adaptation presents no particular difficulty. The starting material is preferably composed of more than 96%, preferably more than 97%, preferably more than 98%, preferably more than 99%, expressed as mass percentages based on the mass of the starting material.

[0231] - of a ceramic powder,

[0232] - water, preferably in a quantity between 4% and 15%,

[0233] - of a foaming agent, preferably in an amount greater than or equal to 0.0025% and less than or equal to 0.5%,

[0234] - preferably, a binder precursor, preferably in an amount between 0.5% and 15%,

[0235] - preferably, an anti-foaming agent, preferably in an amount greater than or equal to 0.005% and less than or equal to 1%,

[0236] - optionally, a surfactant in an amount greater than or equal to 0.05% and less than or equal to 1%,

[0237] - optionally, an anti-segregation adjuvant in a quantity greater than or equal to 0.02% and less than or equal to 0.50%,

[0238] - optionally, of a biocide in a quantity greater than or equal to 0.01% and less than or equal to 1%.

[0239] The initial unshaped wet product is called the starting charge before it is transformed into foam.

[0240] In one embodiment, the transformation of the starting charge into foam does not change the composition of the starting charge so that the composition of the starting charge can be identical to that of the desired foam.

[0241] The starting charge can also be adapted so that the foam exhibits one or more of the optional characteristics described above. In particular, the hydrolyzed silane and / or siloxane preferably exhibit the preferred characteristics of the hydrolyzed silane and / or siloxane described above for the foam, respectively.

[0242] In one embodiment, the optional binder precursor introduced into the starting feedstock is a hydrolyzable silane. Contact of the hydrolyzable silane with water transforms it into hydrolyzed silane. The hydrolyzable silane can be specifically chosen to be hydrolyzable as a hydrolyzed silane selected from among the hydrolyzed silanes described above. Preferably, the hydrolyzable silane is selected from among the hydrolyzable silanes having at least one hydrophobic functional group, preferably from:

[0243] - alkylsilanes,

[0244] - vinylsilanes,

[0245] - sulfur-containing silanes,

[0246] - mercaptosilanes,

[0247] - epoxy silanes,

[0248] - methacrylate silanes,

[0249] - aromatic silanes (or "aromatic silanes" in English),

[0250] - fluoroalkylsilanes, and

[0251] - their mixtures.

[0252] Preferably, the hydrolyzable silane comprises at least one group selected from the alkoxy groups, the chloro group and mixtures thereof.

[0253] Preferably, the hydrolyzable silane comprises at least one alkoxyl group selected from the methoxy group, the ethoxy group and the propoxy group.

[0254] Preferably, the hydrolyzable silane is selected from alkylsilanes, vinylsilanes, sulfur silanes, mercaptosilanes, epoxysilanes, methacrylate silanes, aromatic silanes, fluoroalkylsilanes and mixtures thereof, and said hydrolyzable silane comprises at least one group selected from alkoxyl groups, the chloro group and mixtures thereof.

[0255] If available, colloidal silica is supplied in the form of an aqueous suspension. Conventional colloidal silica suspensions may be used. Preferably, 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.

[0256] The antifoaming agent is preferably added at the end of step a), so that it has little or no effect during step a). The presence of an antifoaming agent advantageously allows the product to be stored immediately usable, after simple defoaming.

[0257] The anti-foaming agent can also be added during a mixing operation after foam storage and before use of the unshaped wet product, preferably during the de-bubbling operation in step 2).

[0258] The initial charge is then transformed into a foam by the action of the foaming agent, preferably combined with a conventional mixture. In step b), the foam is placed in an airtight container.

[0259] Implementation

[0260] The product packaged according to the invention is very simple to implement.

[0261] In step 1), the foam can advantageously be stored for a long period, preferably for more than 2 weeks, preferably more than 1 month, preferably more than 2 months, preferably more than 3 months, preferably more than 4 months, preferably more than 6 months. Storage is preferably at atmospheric pressure and at a temperature between 10°C and 30°C.

[0262] In step 2), the packaging is opened and the foam is extracted. The humidity effectively prevents dust from escaping.

[0263] Before or after unpacking, the foam is de-bubbled, meaning that bubbles are extracted from it. Bubbles in the foam, preferably those typically filled with air, are thus destroyed.

[0264] Defoaming can in particular result from a chemical action, by the action of an antifoaming agent, preferably associated with a physical action on the foam, preferably agitation, for example mixing.

[0265] De-airing can be carried out:

[0266] - before opening the packaging if the foam stored in said packaging contains an anti-foaming agent;

[0267] - after opening the packaging, especially if the packaging is rigid, for example if it is a drum. De-airing can then be carried out before or after extracting the foam from the packaging, after adding an anti-foaming agent if the foam does not already contain one.

[0268] All conventional debubbling techniques can be used, in particular by combining the addition of an antifoaming agent and conventional mixing, kneading or agitation techniques.

[0269] De-bubbling preferably results from the action of an anti-foaming agent introduced in step a). However, if the foam does not contain an anti-foaming agent, one may be mixed into the foam after opening the packaging, either before or after foam extraction. The mixing time is preferably greater than 30 seconds, preferably greater than one minute, and preferably less than 5 minutes. De-bubbling extracts bubbles from the foam, and thus reduces its volume, preferably until the quantity of bubbles is substantially equal to that of the initial wet, unshaped product, i.e., before it is transformed into foam. De-bubbling is preferably carried out so that the initial volume V m the foam is reduced to a volume Vi such that the ratio V m / Vi is greater than 1.05. If the foam contains enough bubbles, degassing is preferably carried out so that the initial volume V mthe foam is reduced to a volume Vi such that the ratio V m / Vi is greater than 1.06, preferably greater than 1.08, preferably greater than 1.10, preferably greater than 1.13. The debubbling time is adjusted accordingly.

[0270] The degassing is pushed to an undetermined point, but the quantity of bubbles must be sufficient so that the ratio V m / Vi can become, by debubbling, preferably greater than 1.05, preferably greater than 1.06, preferably greater than 1.08, preferably greater than 1.10, preferably greater than 1.13. If the foam does not contain enough bubbles, debubbling will not allow such a value to be reached for the ratio, regardless of the technique used, and regardless of the intensity or duration of the debubbling.

[0271] The constraint of a minimum value for the ratio V m / Vi therefore allows for the unambiguous fixing of a minimum quantity of bubbles in the foam.

[0272] Preferably, the degassing is carried out so that the initial volume V m the foam is reduced to a volume Vi such that the ratio V m / Vi is less than 1.60, preferably less than 1.50, preferably less than 1.40, preferably less than 1.30.

[0273] Preferably, the de-airing is identical to that described in the examples or leads to an equivalent action.

[0274] A binder precursor, identical or different from the binder precursor optionally added to the starting load in step a), may be added after opening the packaging, before or after extraction, before, during, or after degassing the foam. It is preferably added before or during degassing so that it mixes with the other components during said degassing.

[0275] In a preferred embodiment, no addition is made in step 2) so that the unshaped wet debubbling product, in liquid form, has a composition identical to the foam.

[0276] In step 3), the unshaped, wet, de-bubbling product resulting from the previous step is placed in the service position, for example by pumping. The unshaped, wet, de-bubbling product is preferably self-leveling, allowing it to flow, for example by gravity.

[0277] In the service position, the unshaped wet debubbling product can be placed in particular in an area to be repaired, resulting for example from wear due to the flow of molten glass or metal or resulting from corrosion due to contact with molten glass or metal or with slag.

[0278] In the service position, the unshaped, moist, de-bubbling product can be placed on a hearth, preferably a hearth of a glass furnace.

[0279] The unshaped, wet, de-bubbling product is then hardened.

[0280] Hardening can result from the activation of a binder precursor, introduced into the starting charge in step a) and / or added in step 2).

[0281] Activation can result, depending on the nature of the binder precursor, from contacting the binder precursor with a setting activator, by mixing, and / or from exposing the binder precursor to an increase in temperature.

[0282] The setting activator is chosen according to the binder precursor. For example, the setting activator for colloidal silica can be magnesia. The amount of setting activator for colloidal silica is preferably 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 mass percentage based on the mass of the unformed, wet product at the time of activation.

[0283] Depending on the nature of the binder precursor, it may or may not be activated by a constituent present in the foam, which then acts as a setting activator. For example, the setting activator for cement is water, so cement can be activated by the water in the foam. It can then only be added in step 2).

[0284] Preferably, when the binder precursor contains, or is a cement, no water is added in step 2), the water from the foam being sufficient for cement activation.

[0285] The cement is preferably an aluminous cement, preferably containing between 50% and 85% alumina by mass. The amount of cement is preferably greater than 1%, preferably greater than 2%, and preferably less than 6%, preferably less than 5%, by mass percentage based on the mass of the unshaped, wet product at the time of activation. The setting activator for a binder precursor containing colloidal silica is preferably selected from magnesia, sodium silicate, and mixtures thereof. Preferably, the setting activator is magnesia.

[0286] In one embodiment, the binder precursor is a mixture of cement and colloidal silica. Particularly when the foam contains a binder precursor, a mixture with a setting activator (in step 2) is especially suitable for a destination site, for example, an area to be repaired, in an environment with a temperature of 500°C or lower.

[0287] Activation of the binder precursor by heat treatment is particularly well-suited when the destination site, especially an area to be repaired, is in an environment with a temperature above 500°C, preferably above 600°C, and preferably above 700°C, the binder precursor being colloidal silica and / or glass-ceramic particles and / or glass particles, particularly a glass precursor to glass-ceramics. In such cases, the addition of a setting activator is unnecessary. Activation then results from the application of this temperature.

[0288] Activation of the binder precursor by heat treatment is particularly well suited if the binder precursor is colloidal silica and / or glass particles as a binder precursor.

[0289] Hardening can also result from heat treatment without the activation of a binder precursor, for example, sintering after the wet, unshaped product has been placed in position. This sintering can then be described as hardening sintering.

[0290] In step 4), in a preferred embodiment, sintering is carried out after shaping and hardening by activation of a binder precursor. The sintering then consolidates the hardened product.

[0291] Sintering can therefore be carried out in addition to, or as an alternative to, the activation of a binder precursor.

[0292] In a preferred embodiment, the sintering, hardening or consolidation, takes place at a temperature between 900°C and / or below 1600°C. The sintering may result from the temperature prevailing in the furnace, in particular the furnace operating temperature.

[0293] Figure 1 illustrates an example of an implementation process. In step 1) (Figure 1(A)), the packaged product 10 comprises a container 11, in the form of a drum, containing a moist, unshaped product in the form of a foam 12M. The drum comprises a container 14 and a lid 16, hermetically sealing the container 14. The packaged product 10 is stored for several weeks, preferably several months.

[0294] In step 2), the drum is opened (figure 1(B)), which gives access to the foam. One or more constituents can be added, in particular an anti-foaming agent or a setting activator, or even a binder precursor.

[0295] The contents of container 14 are then mixed, which degasses the foam and transforms it into a wet, unshaped, degassed 12L product in liquid phase (Figure 1(C)). If necessary, contact between a binder precursor and a corresponding setting activator activates the wet, unshaped product, which then enters a hardening phase.

[0296] Before hardening, the 12L product is placed at the destination site, preferably a repair area R of a glass furnace, preferably by pumping (Figure 1(D)).

[0297] H is transformed into a hardened product 12D (figure 1(E)) by reaction of a binder precursor with a setting activator or by heating then cooling, depending on the composition of product 12L.

[0298] After hardening, the 12D hardened product can be consolidated by sintering.

[0299] The following non-limiting examples are given to illustrate the invention.

[0300] Characterization protocols

[0301] The specific surface area of ​​colloidal silica in the form of a suspension is evaluated 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.

[0302] The ratio Vm / Vi, equal to the ratio of the volume of the unshaped wet product in the form of a foam, to the volume of the unshaped wet product after debubbling, is evaluated as follows.

[0303] After opening the airtight packaging and before extracting the foam from said packaging, the volume occupied by said foam in said packaging is measured, V mThen, the foam is extracted from the airtight packaging using a trowel and placed in a Perrier-type paddle mixer. 0.03% CONTRASPUM W CONC (a liquid antifoaming agent) marketed by Zschimmer & Schwarz is added, as a mass percentage based on the mass of the foam, and the mixture is mixed for 3 minutes to eliminate the foamy form. After one minute of rest, the volume of the resulting liquid wet unformed product (de-bubbled wet unformed product), Vi, is measured. The ratio V m / Vi is then calculated.

[0304] This de-bubbling method results in an unshaped product that is almost identical to the initial unshaped product before foaming.

[0305] The "self-leveling" and "segregation" characteristics are evaluated by the following test, on a wet, unshaped product obtained by de-airing the foam, then activated:

[0306] 25 kg of the activated wet unshaped product are then immediately poured into a previously oiled hopper, in the shape of a truncated pyramid, positioned point down, and having a height of 320 mm, a top inlet opening with a square cross-section of 350 mm x 350 mm and a bottom outlet opening (towards the point of the pyramid) with a square cross-section of 130 x 130 mm initially closed by a hatch.

[0307] The hopper hatch is then opened with a sharp jerk and the activated product pours out under its own weight, through the outlet opening, into the upper end (700 mm from the ground) of a pre-oiled, semi-circular PVC straight gutter with a diameter of 170 mm and a length of 1600 mm, the lower end of the gutter being 380 mm from the ground.

[0308] The activated product flows into the gutter and empties into a mold placed beneath the gutter, under its lower end. The mold is a wooden mold measuring 300 mm x 300 mm x 60 mm, oiled and positioned horizontally on the ground.

[0309] We then wait for the activated product to harden into a slab.

[0310] On each of the four lateral faces of the slab, the thickness of the slab is measured at both ends and in the middle of the length of the face.

[0311] The self-leveling characteristic (“AN”) is acquired if the upper surface of the slab appears substantially smooth to the eye and if, for each of the four lateral faces, the difference “E” between the smallest measured thickness and the largest measured thickness is less than or equal to 2 mm.

[0312] After steaming at 110°C for 24 hours, the slab is sawn in half through its center, 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.

[0313] The suitability for preservation of the unshaped, moist product is assessed by the following test.

[0314] After manufacturing, the foam is packaged in an airtight container shaped like a 500 ml jar with a 90 mm diameter, sealed with a lid. The packaged product is then stored in a room at an average temperature between 21°C and 25°C for six months.

[0315] At the end of this period, the packaging lid is removed, and the foam is placed on the tray of a TX700 texture analyzer model 151500 equipped with a cleaver probe of reference 130064, marketed by the company Lamy Rheology.

[0316] The tip of the cutting probe is positioned so as to lightly touch the upper surface of the foam, in the center of said surface.

[0317] The measurement is taken at room temperature.

[0318] The following operations are performed:

[0319] - Select the "COMPRESSION" tab on the digital display,

[0320] - select the "simple compression" program,

[0321] - 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 at: 0 mm,

[0322] - to validate,

[0323] - press "zero force",

[0324] - Start the measurement by pressing "start".

[0325] The probe then gradually descends into the unshaped wet product to a depth of 45 mm, and the maximum force p required for this purpose is recorded. "D" is defined as the ratio of the maximum force, FMHX, ​​reached in the measurement cycle, in Newtons, to the penetration depth at which said maximum force, p, is reached, in mm: D = FMHX / p.

[0326] The inventors consider that a value of D less than 40 N / mm, preferably less than 30 N / mm, preferably less than 20 N / mm, preferably less than 10 N / mm, preferably less than 5 N / mm, corresponds to a wet unshaped product that can be quickly put into operation, after a storage period of six months, without a long mixing operation.

[0327] Manufacturing protocol

[0328] The following raw materials were used:

[0329] As ceramic powder:

[0330] - a powder of ER 1681 grains exhibiting the following chemical analysis, in mass percentages: Z1O2: 32.5%, SiCl: 15%, Al2O3: 50.9%, 1.6% other compounds, a 10th percentile (D10) equal to 2 mm, a 90th percentile (D90) equal to 3.5 mm and a median size (D50) equal to 2.5 mm,

[0331] - a powder of ER 1681 grains exhibiting the following chemical analysis, in mass percentages: Z1O2: 32.5%, SiCl: 15%, Al2O3: 50.9%, 1.6% other compounds, a 10th percentile (D10) equal to 0.46 mm, a 90th percentile (D90) equal to 1.7 mm and a median size (D50) equal to 1 mm,

[0332] - a powder of ER 1681 grains exhibiting the following chemical analysis, in mass percentages: Z1O2: 32.5%, SiCl: 15%, Al2O3: 50.9%, 1.6% other compounds, a 10th percentile (D10) equal to 0.03 mm, a 90th percentile (D90) equal to 0.38 mm and a median size (D50) equal to 0.16 mm,

[0333] - a zirconia powder, marketed by the European Refractory Products Company under the name CC10, whose median size (D50) is equal to 3.5 pm, and having a mass content of Z1O2 greater than 98.5%,

[0334] - an electrofused alumina powder, having a mass content of Al2O3 greater than 99%, a mass content of Na2 <D inférieure à 0,2%, et une taille médiane (D50) égale à 100 pm,

[0335] - a CL370 alumina powder marketed by the company ALMATIS,

[0336] - CT3000SG alumina powder marketed by ALMATIS. Other constituents include:

[0337] - a LUDOX® PW 50 X colloidal silica suspension marketed by the company GRACE, as a binder precursor, the colloidal silica having, according to the technical data sheet, a specific surface area of ​​between 60 m 2 / g and 90 m 2 / g and the suspension having a mass content of colloidal silica equal to 50%, as a mass percentage based on the mass of the colloidal silica suspension,

[0338] - a modified polycarboxylate ether, as a surfactant,

[0339] - an anti-segregation adjuvant from the starch ether family,

[0340] - of the 350 - Saniplages marketed by the company Socodif as a liquid foaming agent.

[0341] Table 1 below provides the composition of the tested foams, in mass percentages based on the mass of the foam.

[0342] [Table 1] The foam is manufactured in the following way:

[0343] The ceramic powder, modified polycarboxylate ether, and anti-segregation adjuvant are introduced into the bowl of a Perrier-type paddle mixer. Then, while the mixer is running, the colloidal silica suspension, water (a), and foaming agent are added, and mixing is continued for another 10 minutes.

[0344] The foam of the unshaped wet product is obtained at the end of this mixing time.

[0345] It is then placed in airtight packaging chosen according to the characterizations to be carried out later.

[0346] After 6 months of storage, the suitability for preservation D is measured according to the protocol described above.

[0347] The V report m / Vi is also measured according to the protocol described above.

[0348] After opening the airtight packaging and before extracting the foam from said packaging, 0.03% of CONTRASPUM W CONC (anti-foaming agent in liquid form) marketed by the company Zschimmer & Schwarz is added, as a mass percentage based on the mass of the foam of the wet unshaped product, and the whole is mixed for 3 minutes using a portable electric plasterer's mixer (with a power of 1600W, equipped with a turbine for mortar and paint, with a diameter of 140 mm), in order to remove, with the action of the anti-foaming agent, the foamy form and obtain a de-bubbling wet unshaped product.

[0349] The resulting unshaped wet product is then activated by adding 0.3% of a "dead burned B / C" magnesium oxide powder marketed by Grecian Magnesite. Mixing continues for 2 minutes after the powder is added. Self-leveling properties and segregation are measured immediately after activation according to the protocol described above.

[0350] Table 2 provides the results of the different tests carried out.

[0351] [Table 2]

[0352] The results allow us to make the following observations:

[0353] Example 1, according to the invention, being in the form of a foam and having colloidal silica as its binder precursor, has a D value of 0.6 N / mm² measured after a storage period of 6 months and a V ratio m / Vi equals 1.16. The product of Example 1, after mixing and activation by adding magnesium powder, exhibits self-leveling properties and shows no segregation after application. Its preparation generates only a small amount of dust.

[0354] As is now clear, the invention provides a wet unshaped product (in the form of a foam) which can be stored for a prolonged period and which, after storage, can be quickly and easily implemented, substantially without emission of dust.

[0355] Of course, the present invention is not limited to the embodiments described or represented, provided by way of illustrative and non-limiting examples.

Claims

DEMANDS 1. Packaged product comprising: - airtight packaging (11), and - a foam (12M) of a wet, unshaped product containing a ceramic powder and a quantity of water less than 15%, by mass percentage based on the mass of the foam, said foam being disposed in said airtight packaging, the ratio V m / Vi being greater than 1.05, V m and Vi being the volumes of said unprocessed wet product - in the form of said foam, and - after the foam has de-bubbled, respectively.

2. Product packaged according to the preceding claim, in which the quantity of water is less than 14%, as a mass percentage based on the mass of the foam.

3. Product packaged according to any one of the preceding claims, wherein the foam contains sufficient bubbles so that de-airing of a volume V mof said foam, at a constant temperature, can lead to a volume Vi such that the ratio V m / Vi is greater than 1.

10.

4. A packaged product according to any one of the preceding claims, wherein the foam contains a limited quantity of bubbles such that no debubbling of a volume Vm of the foam, at a constant temperature, can lead to a volume Vi such that the ratio V m / Vi is greater than 1.

60.

5. Product packaged according to any one of the preceding claims, wherein the foam comprises: - colloidal silica, or - a mixture of colloidal silica on the one hand and a hydrolyzed silane and / or a siloxane on the other hand, or - glass-ceramic particles, particles in a glass, in particular in a glass precursor glass for glass-ceramics, and mixtures of these particles, or - a phosphate chosen from an aluminium phosphate, a magnesium phosphate, and mixtures thereof.

6. Product packaged according to any one of the preceding claims, wherein the foam comprises, - colloidal silica, or a mixture of colloidal silica on the one hand and a hydrolyzed silane and / or a siloxane on the other hand, in an amount greater than or equal to 0.5% and less than 3.2%, or - glass-ceramic particles and / or glass particles, in a quantity greater than 2% and less than 15%, as a mass percentage based on the mass of the foam, or - a phosphate selected from aluminum phosphate, magnesium phosphate, and mixtures thereof, in an amount greater than 0.15% and less than 1.2%, the amount of any substance from colloidal silica, hydrolyzed silane, siloxane, and phosphate being equal to the ratio, in percentage, of - the mass of said substance without taking into account any water that said substance may contain, - on the mass of the foam.

7. Product packaged according to any one of the preceding claims, wherein the ceramic powder: - is composed, for more than 80% by mass, of particles whose main constituents are alumina and / or zirconia and / or silica and / or chromium oxide; and / or - exhibits a particle size distribution such that the fraction of ceramic powder particles with a size less than 40 pm is distributed, as a percentage by mass relative to the mass of the ceramic powder, as follows: - fraction < 0.5 pm: > 4%, and / or < 6.5%, and - fraction < 2 pm: > 5%, and / or < 18%, and - fraction < 10 pm: > 16%, and / or < 35%, and - fraction < 40 pm: 29-52%; and / or - has a 99.5 percentile less than or equal to 10 mm.

8. A method for manufacturing a packaged product according to any one of the preceding claims, comprising the following successive steps: a) manufacturing a foam from a wet unshaped product containing a ceramic powder; b) packaging said foam in a hermetically sealed package.

9. A method for repairing a furnace, preferably a glass furnace, said method comprising the following successive steps: 1) Storage for more than 2 weeks of a packaged product containing: - airtight packaging (11), and - a foam (12M) of a moist, unshaped product containing a ceramic powder, said foam being disposed of in said airtight packaging, the ratio V m / Vi being greater than 1.05, V m and Vi being the volumes of said unprocessed wet product - in the form of said foam, and - after the foam has de-bubbled, respectively; 2) Unpacking and degassing the foam to obtain a damp, unshaped, degassed product; the degassing may be - before opening the packaging, or - after opening the packaging, before or after extracting the foam from the packaging; 3) placing said unshaped wet product in a repair area of ​​the oven, hardening said unshaped wet product so as to obtain a hardened product; 4) Optionally, sintering of the hardened product.

10. A method according to the immediately preceding claim, wherein, in step 2), the composition of the foam is modified by adding an aluminous cement.

11. A method according to any one of the two immediately preceding claims, wherein the packaged product conforms to any one of claims 1 to 7.

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