Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B11/00—Calcium sulfate cements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B28—WORKING CEMENT, CLAY, OR STONE
  • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
  • B28B1/00—Producing shaped prefabricated articles from the material
  • B28B1/14—Producing shaped prefabricated articles from the material by simple casting, the material being neither forcibly fed nor positively compacted
  • B28B1/16—Producing shaped prefabricated articles from the material by simple casting, the material being neither forcibly fed nor positively compacted for producing layered articles
• • E—FIXED CONSTRUCTIONS
  • E04—BUILDING
  • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
  • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
  • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
  • E04C2/04—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of concrete or other stone-like material; of asbestos cement; of cement and other mineral fibres
  • E04C2/043—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of concrete or other stone-like material; of asbestos cement; of cement and other mineral fibres of plaster
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/20—Resistance against chemical, physical or biological attack
  • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures

Definitions

• the present invention relates to a gypsum-based composition that can be used to form products for the construction, in particular that can be used to form plates or plaster tiles intended in particular for the formation and / or covering of partitions or ceilings. of buildings, or to form joints, etc.
• the invention also relates to the use of such a composition for the manufacture of said products, as well as the products obtained.
• the raw material of the gypsum-based compositions used in the manufacture of construction products is di-hydrated calcium sulphate (or gypsum) of natural or synthetic origin.
• This calcium sulphate in powder form, is generally cooked which dehydrates it into calcium sulphate semihydrate or anhydrous calcium sulphate or a mixture of these two forms, this dehydrated product being commonly called plaster.
• Mixing this plaster with water gives a mixture which solidifies by reforming calcium sulphate dihydrate.
• the plaster can be molded, shaped to obtain various shapes, including plates (commonly known as plasterboard extension), or joints, etc.
• These plates are generally formed of a core based on plaster, this core possibly being coated with one or more layers, for example of protection and / or reinforcement, in particular of a reinforcing sheet (for example fiber-based or cardboard) on each side.
• gypsum boards In order to improve this resistance, it is in particular known for gypsum boards to add various additives to the plaster composition, making it possible, if necessary, to limit or delay the dimensional variation (or shrinkage) of the plates under the effect of heat, such as vermiculite, perlite, crystalline silica, or additives in the form of clay materials, boron compounds or silicon or aluminum, etc.
• additives such as vermiculite, perlite, crystalline silica, or additives in the form of clay materials, boron compounds or silicon or aluminum, etc.
• the use of certain additives may be tricky or these additives may result in significant additional cost, the improvement in fire resistance may also remain low.
• the present invention therefore sought to develop an improved product based on plaster, in particular of the plasterboard or plasterboard type or joint, having a particularly satisfactory dimensional stability at high temperature and more particularly at a very high temperature, while remaining simple embodiment, this product possibly requiring less glass fibers or can be made without glass fibers while maintaining good dimensional stability at high and very high temperature.
• composition based on plaster according to the invention characterized in that it comprises (as an additive, making it possible to improve the dimensional stability / to limit the shrinkage at high temperature, in particular at very high temperature ) nanometric boehmite and / or nanometric aluminum trihydroxide.
• said composition comprises (initially), in percentages by weight (or mass percentages) relative to the dry total mixture:
• the percentages by weight are given with respect to the dry total mixture (or dry extract, the total dry mixture including in particular plaster, boehmite and / or aluminum trihydroxide, and possibly vermiculite , fibers and one or more additives as mentioned later), that is to say the mixture devoid of (or after extraction of) any liquid medium used for the dispersion of the components, in particular devoid of water.
• the composition is formed from the indicated components, (usually mixed) in the given rates with respect to the dry blend.
• the composition may also comprise one or more additives and / or additional components usually used in this field and / or facilitating the use of the composition and / or improving its resistance, in particular to fire, and / or improving other properties, as specified later.
• the composition may also comprise:
• additives chosen in particular from vermiculite, mineral and / or refractory fibers, silica, clay (other possible additives such as surfactants, retarders or setting accelerators, etc. are also listed later), etc.
• the present invention also relates to the preparation of a composition ("flame retarded" or having improved fire resistance, particularly in the sense of having better dimensional stability at high temperature) based on plaster, comprising a step of preparing a mixture based on (at least) nanoscale plaster and boehmite and / or nanometric aluminum trihydroxide and / or to be added to a gypsum based composition of the nanometric boehmite and / or nanometric aluminum trihydroxide.
• a construction element in particular of small thickness relative to its surface, such as a plate
• a plaster-based composition comprising nanometric boehmite and / or trihydroxide of nanometric aluminum
• the invention also relates to a method for fireproofing a gypsum / gypsum based product formed from a plaster-based composition, in which nanoscale boehmite is added to said gypsum-based composition and or nanometric aluminum trihydroxide.
• nanometric boehmite and / or nanometric aluminum trihydroxide at a preferential rate of 0.1 to 10% by weight of nanometric boehmite and / or nanometric aluminum trihydroxide relative to the mixture dry total forming the composition
• the addition of nanometric boehmite and / or nanometric aluminum trihydroxide can be optionally initially in the plaster-based mixture or later in the composition before the final shaping of the portion of the product (usually the core of the product) based on this composition.
• the present invention also relates to the construction element (for example the plate or the joint) obtained from the composition and / or one or the other of the preceding processes and having improved fire resistance.
• the present invention also relates more generally to the use of nanometric boehmite and / or nanometric aluminum trihydroxide (especially the use of the composition described above) for the manufacture of products based on plaster.
• the present invention has demonstrated that the addition of nanometric boehmite and / or nanometric aluminum trihydroxide to a gypsum-based composition makes it possible to confer on a product (based on gypsum) prepared from this composition, properties of resistance or fire resistance, in particular dimensional stability at high temperature, and more particularly at very high temperature (above 850 ° C., in particular greater than 900 ° C., or even higher than 1000 ° C.), improved, and allows in particular to substitute with advantage (and all the more so that the performance is evaluated at very high temperature) all or part of the components usually added to improve the fire resistance, such as glass fibers, or vermiculite (Which do not allow if necessary to obtain sufficient dimensional stability at very high temperature).
• the term "plaster” is understood to mean a hydratable calcium sulphate (for example obtained by baking a gypsum), consisting in particular (in particular, for the majority or in all) of calcium sulphate hemihydrate, which whatever its crystalline form, and / or optionally anhydrous calcium sulphate, these components may be of natural or synthetic origin, this hydratable calcium sulphate may also include some impurities such as SiO 2 , MgO, etc. In particular, any plaster suitable for the preparation of conventional gypsum boards may be used.
• a hydratable calcium sulphate for example obtained by baking a gypsum
• this hydratable calcium sulphate may also include some impurities such as SiO 2 , MgO, etc.
• any plaster suitable for the preparation of conventional gypsum boards may be used.
• bohemite is meant an aluminum oxyhydroxide (also called alumina monohydrate, or alternatively (mono) hydroxide of aluminum oxide) of formula AIO (OH) (in particular the gamma polymorph); aluminum trihydroxide is understood to mean an aluminum (tri) hydroxide (also called (tri) hydrate of alumina, or alternatively (tri) hydrate of aluminum oxide) of formula AI (OH) 3 ; nanometric component (bohemite and / or aluminum trihydroxide) means particles (of or forming this component) having a size or size of less than 950 nanometers, preferably less than 750 nm, and in particular less than 500 nm, whatever the shape of these particles.
• the size of a particle is called its equivalent diameter, that is to say the diameter of the sphere which would behave identically during the particle size analysis (or of the powder formed of said particles) forming (initially) the component considered, the particle size distribution (set of particle sizes) being measured in particular by laser granulometry.
• x% by weight of nanoscale component means that the composition incorporates x% by weight of particles of this component having a size of less than 950 nm (preferably less than 750 nm). , and in particular less than 500 nm), other particles of this larger size component may however be present in the composition (in other words, x% of nanoscale component means x% of nanoscale particles (of this component) / less than 950 nm).
• the size of the particles is measured by laser granulometry, for example using a particle size sold under the reference Partica LA-950 by the company Horiba, the powders being analyzed in water, without the use of ultrasound.
• nanometric boehmite or nanometric aluminum trihydroxide makes it possible to significantly improve the fire resistance and / or to significantly reduce the amount of usual components such as glass fibers or vermiculite (used until the end of the process).
• the addition of nanometric boehmite is also particularly preferred over the addition of aluminum trihydroxide in the present invention.
• the content of nanometric boehmite and / or nanometric aluminum trihydroxide in the plaster composition defined according to the invention is greater than 0.2%, especially greater than 0.3%, in particular greater than 0.4%, or even greater than 0.5. % by weight, or even greater than 0.7% by weight.
• the content of one and / or the other of these compounds is less than 8%, especially less than 7%, in particular less than 6%, or even less than 5%, or even less than 4%. or 3%, or alternatively less than 2.5% by weight.
• the size of nanoscale boehmite particles and / or nanometric aluminum trihydroxide is advantageously less than 750 nanometers, or even less than 500 nm, or even less than 400 nm, especially less than 300 nm, in particular less than 200 nm. nm. It is also advantageously greater than 20 nm, especially greater than 50 nm, in particular greater than 60 nm, and even greater than 80 nm.
• the form factor (defined as the L / L ratio between the largest dimension L and the largest dimension I in the plane perpendicular to L) of the nanoscale boehmite particles and / or nanometric aluminum trihydroxide is less than 15, in particular less than 10, this factor also being preferably greater than 2, in particular greater than 3.
• nanoscale boehmite particles and / or nanometric aluminum trihydroxide particles are advantageously in the form of platelets. of substantially parallelepiped shape. The shape of the particles is in particular determined by scanning electron microscope.
• the composition according to the invention comprises from 0.5 to 6% by weight of boehmite particles having a size of less than 750 nm, preferably of size between 20 and 500 nm.
• Nanometric boehmite is particularly preferred in the present invention to obtain the desired plates having particular dimensional stability particularly satisfactory at very high temperature.
• the composition based on plaster is generally prepared by mixing the various components so as to obtain a powder (especially dispersible in water before use) or a more or less fluid paste (including a ready-to-use composition), the components in solid form or in the form of suspension or dispersion in particular, and water is optionally added.
• the plaster-based composition (obtained) according to the invention can thus be in solid (powder, etc.) or liquid (dispersion, etc.) form.
• Boehmite (respectively aluminum trihydroxide) may in particular be introduced into the mixture or into the pulp in the form of a powder (in particular particles having a size of less than 950 nm) or in the form of a colloidal suspension (dispersion in water or an acid in particular).
• this additive (boehmite and / or aluminum trihydroxide) is introduced in the form of a colloidal suspension comprising, for example, between 5 and 50% of nanometric boehmite and / or of nanometric aluminum trihydroxide, and between 50 and and 95% by weight of a medium such as water or an acid.
• the plaster used can be any usual plaster; it may be in the form of a powder or already in the form of a paste formed by mixing with water. More broadly, the mixture in which the nanometric boehmite and / or the nanometric aluminum trihydroxide is added may be any pre-existing gypsum-based mixture, optionally incorporating other additives. The proportion of plaster in the composition is at least 55% by weight in order to obtain sufficient strength.
• Water is, if necessary, added to the composition according to the invention in order to allow its implementation and its transformation to obtain for example a construction element (such as a plate). If necessary, at least a portion of the water may be added in the form of foam (or possibly foaming may be operated in the liquid composition) in particular to reduce the weight of the drywall.
• foaming agents may be added for obtaining the foam, such as ionic surfactants and / or nonionic surfactants, their level being for example between 0.01 and 2% by weight of the composition.
• the composition according to the invention may also comprise vermiculite.
• the vermiculite formed in particular of a silicate of alumina, iron, magnesium and potassium
• the level of vermiculite remains less than 10% by weight of the composition.
• the composition according to the invention may also comprise fibers, in particular mineral and / or refractory fibers, said fibers preferably being glass fibers.
• These fibers can be short (on the order of 3 to 6 mm on average), long (on the order of 10 to 24 mm on average), or intermediate dimensions. They may be in unbound form or in the form of a network of intersecting fibers, such as a mat of fibers or a fabric. These fibers contribute to increasing the mechanical strength of the products obtained, in particular at high temperature. Preferably, the fiber content remains below 10% by weight of the composition.
• fibers in the form of veil, fabric, mat, etc.
• other reinforcements sheet of cardboard, etc.
• additives or components may also be present in the composition according to the invention (provided, if appropriate, by certain other components or added independently to the composition).
• These additives may for example be one or more of the following agents: water-repellent agent (silicone, oil, wax, starch, polymer for example of the polyvinyl alcohol type (PVOH), polyvinyl acetate (PVAc), styrene-butadiene (SBR), etc.) , setting accelerator (fine gypsum powder, potassium sulphate, etc.) or setting retarder (of the protein or carboxylic acid type, for example), deformation inhibitor or anti-settling agent (starches, cellulose ethers, polymers PVOH, PVAc, SBR, etc.), recalcination inhibitor (sugar type, starch, boric acid, etc.), foam stabilizer, surfactant or foaming agent, binder, bactericide, fungicide, biocidal agent, pH adjuster, coloring agent, flame retardant and / or fill
• the invention also relates to the use of a composition according to the invention for the manufacture of an object, for example molded or extruded, in particular for the manufacture of a plaster tile or a plate plaster, or for the manufacture of seals, and relates to objects (molded or extruded) such as tiles or plates or seals, comprising (or obtained from) such a composition.
• the plates (or tiles or panels) of plaster are for example obtained by a method, preferably continuous, comprising the following steps: - Preparation of a paste by mixing the various constituents of the plaster composition as already mentioned (this composition to form the core of the plate), for example in a mixer;
• a plate is obtained in which the core is a composition based on gypsum (initially based on plaster).
• the invention also relates to joints or plasterboard (or tiles) obtained, the dimensions of the plates generally vary according to their destination.
• gypsum boards for the manufacture of partitions can reach 5 m in length and 1 .20 m in width and their thickness can vary between 6 and 35 mm.
• these plates have a density of between 0.5 and 2.0 g / cm 3 , preferably between 0.6 and 1.0 g / cm 3 .
• These plates may be provided with reinforcement (s) (based in particular on mineral or refractory or cellulosic fibers) on the surface, for example in the form of haze (s), fabric (s), paper (s), mat (s), grid (s), etc. or combination of these different reinforcing elements.
• reinforcement based in particular on mineral or refractory or cellulosic fibers
• the products according to the invention are enriched in aluminum (observation by chemical analysis), have nodules, consisting in particular of aluminum and oxygen, mixed with the structure in gypsum (observation by scanning electron microscope), and have a mass loss around 220-320 ° C for aluminum trihydroxide products and around 400-500 ° C for boehmite products (thermogravimetric analysis (TGA)).
• TGA thermogravimetric analysis
• Plasterboard 20 cm x 25 cm were prepared by mixing 100 parts by weight of plaster with 0.6 parts of starch (sold under the reference Cargill C Plus by the company Cargill) and where appropriate with the dry materials (in amounts also expressed in parts by weight (per 100 parts by weight of plaster)) given in Tables 1 to 3 below, and with demineralised water, then adjusting the density of the mixture with foamed water (obtained by mixing water and about 1% by weight relative to the water of sodium alkyl ether sulfate foaming agent sold under the reference Millifoam C by Huntsman Corporation) to obtain plates having a density 0.85 ⁇ 0.02 after drying for 19 minutes in a microwave oven (at the power of 750W) and then for about 12 hours in an oven at 40 ° C (to obtain a complete hardening of the plates).
• 200 mm and width equal to 150 mm were taken (in particular by cutting) and placed in an oven with a temperature rise speed programmed according to ISO834, the dimensional variation of the width of the sample being recorded continuously. After approximately 13 minutes, the temperature reaching 700 ° C., the withdrawal of the sample R700 was measured if necessary. After 60 minutes, the temperature reaching 945 ° C, the shrinkage of the R945 sample was measured. After 120 minutes, the temperature reaching 1049 ° C, the shrinkage of the R1049 sample was measured.
• the procedure was as in Reference Example 2, this time adding 0.8 parts by weight of glass fibers of 12 mm in length sold under the reference Duracore SF Plus type. M300 by the company Johns Mansville, and 2.5 parts by weight of a fluidifying agent (in the form of a sodium salt of a sulfonated polynaphthalene acid) sold under the reference Proletor PNS 747L by the company Protex.
• a fluidifying agent in the form of a sodium salt of a sulfonated polynaphthalene acid
• nanoscale boehmite powder (called B3 powder in the table) having particles in the form of spheres having (all) a size of less than 500 nm (and in particular a large content of particles smaller than 200 nm) or at least about 0.93% by weight of nanometric boehmite relative to the dry total mixture, these particles having a form factor of the order of 1.
• Example 4 The procedure was as in Example 4, replacing the B3 powder with the same level of another nanoscale boehmite powder (called B2 powder in the table), this time having particles in the form of rods having (all) a smaller size. at 500 nm (and in particular a high level of particles smaller than 200 nm), these particles having a form factor of the order of 2.
• B2 powder nanoscale boehmite powder
• Example 6 according to the invention The procedure was as in Example 4, replacing the B3 powder with the same level of another nanoscale boehmite powder (called B1 powder in the table), this time presenting particles in the form of platelets having (all) a smaller size. at 500 nm (and in particular a high level of particles smaller than 200 nm), these particles having a form factor of the order of 10.
• B1 powder nanoscale boehmite powder
• Example 4 The procedure was as in Example 4, replacing the B3 powder with the same level of the nanometric bohemite 'B1-sol' seen previously.
• Example 2 The procedure was as in Example 1, this time adding 2 parts by weight (instead of one part) of nanometric boehmite B1-sol, ie approximately 1 .9% by weight of nanometric boehmite with respect to the total dry mixture.
• Example 2 The procedure was as in Example 1, this time adding 3 parts by weight (instead of one part) of nanometric boehmite B1-sol, ie about 2.81% by weight of nanometric boehmite relative to the total dry mixture.
• Example 4 The procedure was as in Example 1, this time adding 5 parts by weight (instead of one part) of nanometric boehmite B1-sol and adding 0.6 parts by weight of the fluidizing agent (to adjust the viscosity) used. in Reference Example 4, all vermiculite being further removed from the composition, ie about 4.71% by weight of nanometric boehmite in the composition based on the total dry mix.
• Example 10 The procedure was as in Example 10, replacing the nanometric boehmite B1-sol by the same rate of a boehmite in the form of a powder (called B4 powder in the table) this time having a D50 of approximately 2.7 ⁇ , approximately 20. % by weight of the particles of this bohemite having a size of less than 750 nm (ie at least about 0.94% by weight of nanometric boehmite relative to the dry total mixture), the fluidizing agent having been removed as superfluous.
• B4 powder in the table this time having a D50 of approximately 2.7 ⁇ , approximately 20. % by weight of the particles of this bohemite having a size of less than 750 nm (ie at least about 0.94% by weight of nanometric boehmite relative to the dry total mixture), the fluidizing agent having been removed as superfluous.
• Reference Example 5 The procedure was as in Example 11, replacing the boehmite B4-powder with an aluminum trihydroxide AI (OH) 3 , sold under the reference SH500 by the company Alcan (and called ATH1 in Table 3), having a D50 of about 50 to 60 microns and having no particles smaller than 1 micron.
• OH aluminum trihydroxide AI
• Example 2 The procedure was as in Example 1, replacing the nano bohemite with a bohemite, sold under the reference PURAL NF by the company Sasol (and called B5 powder in Table 3), having a D50 of about 8-10 microns and not having particles smaller than 1 micron.
• plasterboards of 20 cm ⁇ 25 cm were prepared by mixing 100 parts by weight of a dry mixture comprising 71.1% by weight of plaster, 24.0% by weight of calcium carbonate, and 4.9% by weight of powder B3 (described in Example 4) with 48 parts of demineralized water to obtain plates having a density of 1 .12 ⁇ 0.02 after drying for 48 hours in the open air.
• composition according to the invention can in particular be used with advantages to obtain gypsum board fire resistant and intended for the formation and / or the cladding of the partitions or ceilings of buildings.

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• Ceramic Engineering (AREA)
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• Curing Cements, Concrete, And Artificial Stone (AREA)
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