EP3873866A1 - Procédé de fabrication d'un liant hydraulique - Google Patents
Procédé de fabrication d'un liant hydrauliqueInfo
- Publication number
- EP3873866A1 EP3873866A1 EP19829258.3A EP19829258A EP3873866A1 EP 3873866 A1 EP3873866 A1 EP 3873866A1 EP 19829258 A EP19829258 A EP 19829258A EP 3873866 A1 EP3873866 A1 EP 3873866A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- calcium
- hydrated
- alumina
- binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
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- 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
- C04B7/00—Hydraulic cements
- C04B7/32—Aluminous cements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/164—Calcium aluminates
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- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
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- 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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/44—Burning; Melting
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/008—Flocking or deflocking agents
- C04B2103/0081—Deflocking agents
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/0087—Ion-exchanging agents
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/54—Pigments; Dyes
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- 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
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00637—Uses not provided for elsewhere in C04B2111/00 as glue or binder for uniting building or structural materials
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- 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
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
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- 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
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
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- 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
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0087—Uses not provided for elsewhere in C04B2111/00 for metallurgical applications
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- 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
- C04B2111/60—Flooring materials
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- 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
- C04B2111/70—Grouts, e.g. injection mixtures for cables for prestressed concrete
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/72—Repairing or restoring existing buildings or building materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates generally to the field of methods for manufacturing hydraulic binders.
- It relates more particularly to a process for manufacturing a hydraulic binder comprising a calcium aluminate.
- the invention also relates to a calcium aluminate compound and a use of this calcium aluminate compound.
- Processes for the manufacture of hydraulic binders comprising a calcium aluminate are already known, in particular the processes by total fusion, implemented in electric ovens or reverberatory ovens, and the methods by sintering implemented in rotary ovens. These known methods include a high temperature cooking step, that is to say above 1300 ° C, allowing the raw materials to react with each other. However, this high temperature cooking step generates high energy consumption.
- the aforementioned manufacturing methods also include a final grinding step consisting of reducing the product, called clinker, obtained at the end of the high temperature cooking step to a fine powder.
- This grinding step also makes it possible to add other compounds to the cement in order to functionalize it, in particular to control its reactivity or delay its aging.
- the energy efficiency of grinding by a conventional ball mill is only around 5%, the vast majority of the energy used in this stage being dissipated in the form of heat.
- the present invention provides a method of manufacturing a more energy-efficient calcium aluminate.
- a method of manufacturing a hydraulic binder comprising a calcium aluminate according to which :
- composition comprising a lime source compound and an alumina source compound, said composition comprising a maximum of 95% lime and alumina , and a minimum of 23% alumina, by mass relative to the mass total dry matter of the composition;
- step b) the composition provided in step a) is placed in a medium saturated with humidity, at a hydration temperature of between 40 ° C. and 150 ° C., so as to precipitate hydrated phases comprising at least one oxide d aluminum combined with calcium oxide and water;
- step b) the precipitates obtained in step b) are placed at a baking temperature between 200 ° C and 1300 ° C, for at least 15 minutes.
- the process according to the invention is based on a reaction in two stages, a first hydration stage and a second stage of cooking at a lower temperature.
- step b This process generates a reasonable energy consumption, the compounds of the composition reacting, in step b), at a low temperature, between 40 ° C and 150 ° C only, and the precipitates thus obtained are then dehydrated at a temperature between 200 ° C and 1300 ° C.
- step c) the material obtained at the end of step c) is very friable, so that it is easily reduced to powder. Thus, only a small energy is necessary for the grinding of this material.
- the composition comprises a maximum of 95% of lime C and of alumina so that it comprises compounds which are naturally available and therefore less expensive than pure synthetic compounds.
- the invention also aims to produce hydraulic binders whose phases are rich in alumina.
- a composition comprising less than 23% of alumina tends to generate a significant amount of uncombined residual lime at the end of step c).
- the composition has a lime to alumina C / A ratio of between 0.5 and 3;
- the composition has a lime to alumina molar ratio tri-hydrated C / AH3 between 0.5 and 3;
- the composition is in the form of a set of particles whose particle size distribution is defined by a reference diameter d80 less than or equal to 100 micrometers;
- the composition comprises at least 5% of compounds chosen from the following list: the mono-hydrated alumina AH such as boehmite, iron oxides, silica S1O2, calcite CaCO3, titanium oxide T1O2, the hydrated salts or not combining as anion the sulfates, silicates, carbonates, nitrates, phosphates and as cation the calcium, magnesium, iron, in particular the calcium salts hydrated or not such as the calcium sulfates and the calcium carbonate, hydrated or non-hydrated aluminum salts such as aluminum silicates and in particular kaolin, aluminum sulfates, chlorine salts or chlorinated residues, magnesium salts, or even sodium salts such as sodium chloride available in particular in sea water ;
- the mono-hydrated alumina AH such as boehmite, iron oxides, silica S1O2, calcite CaCO3, titanium oxide T1O2, the hydrated salts or not combining as anion the sulfates, silicates,
- the composition does not comprise more than 20% of silica
- the composition does not comprise more than 15% of silica
- the composition does not comprise more than 10% of silica
- the composition does not comprise more than 8% of silica
- the composition does not comprise more than 6% of silica
- step b) the composition is placed in excess liquid water or in an atmosphere of saturated vapor;
- step b) the composition is placed in the medium saturated with humidity for a period of between 15 minutes and 48 hours;
- step c) the precipitates are placed at the cooking temperature for less than 240 minutes;
- the baking temperature is between 400 ° C and 1200 ° C, preferably between 900 ° C and 1000 ° C, more preferably between 930 ° C and 970 ° C;
- the cooking temperature is between 300 ° C and 750 ° C, preferably between 350 ° C and 700 ° C;
- the hydration temperature is less than 100 ° C;
- the alumina source compound of step a) is in dry form, preferably in crystallized form, that is to say is not in gel form.
- the alumina source compound from step a) is chosen from the list following: bauxite such as bauxite trihydrate (bauxite mainly comprising alumina in AH3 form), bauxite trihydrate white, bauxite trihydrate red, hydroxides, by-products of the aluminum industry and non-conforming manufacturing to high alumina content or a mixture thereof, iron-rich bauxite trihydrate, iron-poor bauxite trihydrate, hydrated aluminosilicates such as kaolin, or synthetic tri-hydrated alumina AH3;
- bauxite such as bauxite trihydrate (bauxite mainly comprising alumina in AH3 form), bauxite trihydrate white, bauxite trihydrate red, hydroxides, by-products of the aluminum industry and non-conforming manufacturing to high alumina content or a mixture thereof, iron-rich bauxite trihydrate, iron-poor bauxite trihydrate,
- the composition of step a) is formed by the mixture of at least two compounds chosen from the following list: bauxite trihydrate (bauxite mainly comprising alumina in AH3 form) rich in iron, bauxite trihydrate poor in iron, quicklime or hydrated lime, calcium sulphate, calcium carbonate, hydrated aluminosilicates such as kaolin, synthetic tri-hydrated alumina AH3, chlorinated salts or residues such as sodium chloride NaCl or sea water, or even nitrated salts or residues such as calcium nitrate CaNÜ3 or pig manure;
- the composition of step a) comprises at most 0.4% by weight of fluorinated compounds chosen from a source of CaF2 and / or the cryolite Na3AIF6, relative to the weight of the dry composition of step a); alternatively the composition of step a) comprises at most 0.3% by weight, for example at most 0.2% by weight of fluorinated compounds chosen from a source of CaF2 and / or the cryolite Na3AIF6, relative to the weight of the dry composition of step a); for example, the composition of step a) does not comprise fluorinated compounds chosen from a source of CaF2 and / or the cryolite Na3AIF6;
- the process according to the invention does not include the addition of fluorinated compounds chosen from a source of CaF2 and / or the cryolite Na3AIF6.
- the invention also provides a calcium aluminate compound obtained according to the process of the invention.
- the invention also provides a use of this calcium aluminate compound as a hydraulic binder, alone or combined with calcium sulphate and optionally portland cement, for example in the following applications:
- the invention finally proposes a use of this calcium aluminate compound, alone or combined with calcium sulphate and optionally portland cement, for example in the following applications:
- the term “calcium aluminate” means both an undoped calcium aluminate and a calcium aluminate doped with one or more compounds chosen from alumina.
- monohydrate AH such as boehmite, iron oxides, silica S1O2, calcite CaCO3, titanium oxide T1O2, salts, hydrated or not, combining as anion sulfates, silicates, carbonates, nitrates, phosphates and as cation calcium, magnesium, iron, in particular calcium salts, hydrated or not, such as calcium sulphates and calcium carbonate, aluminum salts, hydrated or not, such as aluminum silicates and in particular kaolin, aluminum sulphates, chlorine salts or chlorinated residues, magnesium salts, or even sodium salts such as sodium chloride available in particular in sea water.
- a calcium silicoaluminate is a particular example of calcium aluminate doped with silica.
- a calcium aluminate cement designates a powder essentially comprising one or more calcium aluminates, and forming a particular type of hydraulic binder.
- tri-hydrated alumina AH3 the compound comprising an alumina molecule AI 2 O3 for three molecules of water H 2 O
- mono-hydrated alumina AH the compound comprising a molecule alumina AI 2 O3 for a molecule of water H 2 O.
- the method according to the invention consists in manufacturing a hydraulic binder comprising a calcium aluminate, first by combining compounds by means of a hydration reaction leading to the formation of hydrated phases in the form of precipitates, then by calcining the hydrated phases obtained.
- the method according to the invention more precisely comprises steps according to which:
- composition comprising a lime source compound C and an alumina source compound, said composition comprising at most 95% lime C and alumina , and at least 23% alumina, by mass relative to the total mass of dry matter in the composition;
- step b) the composition provided in step a) is placed in a medium saturated with humidity, at a hydration temperature of between 40 ° C. and 150 ° C., so as to precipitate hydrated phases comprising at least one oxide d aluminum combined with calcium oxide and water; and, c) placing the precipitates obtained in step b) at a baking temperature between 200 ° C and 1300 ° C, for at least 15 minutes.
- step b the composition is placed in the medium saturated with moisture, so that the compounds of this composition release ions (we also say that they dissolve). These ions recombine in the form of hydrated phases comprising at least one aluminum oxide combined with a calcium oxide and with water. At saturation, the hydrated phases precipitate (we also say that they crystallize). The precipitation of the hydrated phases induces a drop in ionic concentrations in the medium saturated with humidity, which again causes the release of ions from the compounds of the composition. The dissolution / precipitation reactions continue until the compounds of the composition are used up. This is called the "hydration reaction" in step b).
- step c) of baking an objective is to break the atomic bonds between the calcium and aluminum ions and the water molecules of the hydrated crystallized phases formed in step b). These breaks in water molecule bonds lead to the formation of amorphous and / or crystalline calcium aluminates.
- Another objective may be to recombine dehydrated species in a controlled manner.
- Steps a), b) and c) are explained in more detail below.
- step c) of the hydraulic binder comprising at least one calcium aluminate
- the compounds of step a must be ) are capable of releasing at least ions comprising calcium and ions comprising aluminum.
- the compound releasing, in water, at least one ion comprising calcium is here the source compound of lime, while the compound releasing, in water, at least one ion comprising aluminum is the compound source alumina, for example a source compound of tri-hydrated alumina AH3.
- the composition of step a) comprises a maximum of 95% by mass of lime and alumina relative to the total mass of dry matter of the composition, that is to say that the compounds of this composition are not all pure. This rate is measured on the basis of the dry matter, that is to say in the absence of free water (after drying for 24 hours at 110 ° C. for example).
- the process makes it possible to use natural raw materials containing impurities, while limiting the negative effect of these impurities on the performance of the hydraulic binder (unlike the conventionally used processes).
- composition supplied in step a) to contain at least 23% of Al2O3 alumina because this makes it possible to limit the amount of residual lime not combined at the end of step c).
- the composition supplied in step a) contains at least 25% of alumina.
- the composition provided in step a) comprises at least 27% of alumina; alternatively, the composition supplied in step a) contains at least 30% of alumina.
- the composition supplied in step a) comprises at least 25% of tri-hydrated alumina AH3.
- the composition provided in step a) comprises at least 27% of tri-hydrated alumina AH3; alternatively, the composition supplied in step a) comprises at least 30% of tri-hydrated alumina AH 3 .
- the molar ratio of lime to trihydrated alumina "C / AH3" of the composition of step a) is between 0.5 and 3.
- the molar ratio of lime to alumina " C / A "of the composition of step a) is between 0.5 and 3.
- the choice of a value of ratio C / AH3 between 0.5 and 3 guarantees that is formed in step b) , the hydrated phase C3AH6 comprising one molecule of alumina for six molecules of water and three molecules of lime.
- This hydrated phase C3AH6 when it is dehydrated in step c), provides calcium aluminates generally having a chemistry with a C / A molar ratio of 3, and mineralogically several species can coexist, for example mainly calcium aluminate C12A7 and lime (hydrated or not).
- the composition supplied in step a) contains less than 20% of silica S1O2.
- the composition supplied in step a) contains less than 15% of silica S1O2.
- the composition supplied in step a) contains less than 10% of silica S1O2.
- the composition supplied in step a) contains less than 8% of silica S1O2.
- the composition supplied in step a) contains less than 6% of silica S1O2.
- a higher level of silica tends to favor the appearance of alumina-free phases, such as C2S and C3S, phases which are found for example in Portland cement. These phases are less reactive than the phases with alumina such as calcium aluminate compounds.
- the composition of step a) is here formed by the mixture of at least two compounds chosen from the following list: bauxite rich in iron, bauxite poor in iron, quicklime or hydrated lime, sulphate of calcium, calcium carbonate, hydrated aluminosilicates such as kaolin, synthetic tri-hydrated alumina AH3, chlorinated salts or residues such as sodium chloride NaCl or seawater, or even nitrated salts or residues such as calcium nitrate CaNÜ3 or pig manure.
- the majority of these compounds exist in their natural state, which is advantageous from an economic point of view.
- a source of tri-hydrated alumina is used, a bauxite comprising mainly tri-hydrated alumina. This is advantageous because the natural reserves of this bauxite are abundant.
- hydrated lime or quicklime is used as the source lime compound.
- hydrated lime is used as the source of lime. Using hydrated lime is easier to handle under safe conditions.
- the composition of step a) comprises at least 5% of compounds chosen from the following list: the mono-hydrated alumina AH such as boehmite, iron oxides, silica S1O2, calcite CaCO3, titanium oxide T1O2, the salts (hydrated or not) combining as anion the sulfates, silicates, carbonates, nitrates, phosphates and as cation the calcium, magnesium, iron, in particular the calcium salts, hydrated or not, such as the sulfates of calcium and calcium carbonate, aluminum salts, hydrated or not, such as aluminum silicates and in particular kaolin, sulfates aluminum, chlorine salts or chlorinated residues, magnesium salts, or even sodium salts such as sodium chloride available in particular in seawater.
- the mono-hydrated alumina AH such as boehmite, iron oxides, silica S1O2, calcite CaCO3, titanium oxide T1O2, the salts (hydrated or not) combining as anion the s
- the composition of step a) comprises at least 5% of chlorides.
- the composition of step a) comprises at least 5% of silicates, for example at least 5% of aluminum silicate, for example at least 5% of kaolin.
- the composition of step a) comprises at least 5% of calcium sulfates and / or aluminum sulfates.
- the at least 5% of precipitated compounds make it possible to provide functional characteristics to the hydraulic binder finally obtained.
- chlorides which form Friedel salts with calcium aluminates, make it possible to reduce the penetration of the salts within the medium.
- Silicates promote, with calcium aluminates, the formation of strattlingite, not subject to conversion.
- Sulfates promote the formation of ettringite or monosulfoaluminate, with good mechanical performance and / or shrinkage compensation, rapid drying, etc.
- the composition of step a) may be in the form of a dry, free or compacted powder, or alternatively may be in the form of a composition in an aqueous medium such as an aqueous suspension.
- step b) The particle size distribution of the compounds constituting the composition of step a) influences the speed of step b) of hydration.
- step b) the combination, by dissolution and then precipitation in the form of hydrates, of the compounds of the composition of step a), is facilitated and accelerated by an increase in the reactive surface of these compounds.
- all of the particles of the composition of step a) have a particle size distribution defined by a reference diameter d80 less than or equal to 100 micrometers.
- the reference diameter d80 of any set of particles is a quantity representative of the statistical distribution of the sizes of these particles, in other words of the particle size of this set of particles.
- the reference diameter d80 is a reference diameter defined as the diameter below which 80% of the particles used are located, by volume relative to the total volume of all of said particles.
- diameter is understood here to mean the largest dimension of the particle, whatever its shape.
- the reference diameter d80 of a set of particles is obtained from a particle size curve representing the statistical distribution of the size of each of the particles in this set.
- the reference diameter d80 of a set of particles can be determined by various techniques, such as the sedimentation method (detection by X-ray absorption) or the laser diffraction method (ISO 13320 standard).
- the particle size is measured according to ISO standard 13320 by the laser diffraction method with, for example, a particle size analyzer of the Mastersizer 2000 or 3000 laser type sold by the company Malvern, under a pressure of 3 bars.
- the compounds of the composition provided in step a) can be ground.
- This preliminary grinding or co-grinding can be carried out in a wet or dry environment. It is in particular possible to use for this purpose a turning jar with grinding balls, in which the mass of water introduced is such that it prevents clogging of the dry materials to be ground. This mass of water can for example be greater than or equal to the mass of dry matter introduced into the jar.
- the preliminary grinding of the compounds of the composition of step a), in aqueous media is generally accompanied by heating, natural or imposed, of the grinder used, so that the hydration reaction can begin as soon as the grinding takes place.
- steps a) and b) of the method are carried out partially simultaneously. This results in time savings and / or energy with respect to a process in which steps a) and b) are implemented in a completely sequential manner.
- steps a) and b) are carried out partially simultaneously, the water necessary for the hydration reaction is brought into contact with the composition of step a) upon grinding.
- the water used for grinding must be introduced in excess with respect to the composition to be ground, so that, as soon as it is ground, the medium in which the composition is placed is saturated with moisture.
- the medium saturated with moisture in which the composition is placed in step b) is formed by excess liquid water.
- the composition is placed in an amount of water at least equal to the amount of water necessary for the total hydration of the compounds of step a).
- Water can be supplied by the amount of water required for handling the products, for example during grinding in the wet phase or for transporting the products from step b) to step c).
- the amount of water required to obtain a paste which is sufficiently fluid to be handled in an industrial process is largely sufficient to also allow the hydration of the raw materials during step b).
- Those skilled in the art will know how to find the required amount of water, by checking that water is not a limiting factor in hydration, for example using a mineralogy measurement on the products obtained. from step b).
- the composition of step a) is placed with excess liquid water in a container, for example made of plastic or metal, in which it is heated.
- the composition is dispersed in liquid water, for example by means of a paddle stirrer when the composition is dry before being brought into contact with water, or by means of the jar when the composition is wet following wet grinding of the initial compounds.
- step a) mixed with liquid water is placed in an autoclave or any other industrial installation making it possible to meet the conditions of temperature and pressure.
- composition in a humid atmosphere, at the saturated vapor pressure of water. This atmosphere is then considered as a medium saturated with humidity.
- the moisture-saturated medium includes excess water.
- water should not be a factor limiting the hydration reaction.
- the presence of water after the hydration reaction of step b) facilitates the handling of the hydrated phases obtained.
- the ions capable of being obtained by placing the composition of step a) in the medium saturated with humidity are in particular the following: calcium ions Ca 2+ , aluminum hydroxide anions in basic medium AI (OH) 4 , sulfate ions S0 4 2 , anions of silicate in basic medium SiO (OH) 3 , carbonate ions CO3 2 ' , chloride ions Cl and nitrate ions NO3 2 " .
- the hydrated phases which can be obtained are then the following: CAH10, C2AH8, C3AH6, C 4 AH9-13, C2ASH8, C3A (CaS0 4 ) Hig, C3A (CaS0 4 ) 3H32, C3A (CaC03) Hi9, C3A (CaN03 ) Hi9, C3A (CaCl2) Hi9, in which CaS0 4 , CaC03, CaN03, and CaCl2 respectively represent calcium sulfate, calcium carbonate (or calcite), calcium nitrate, and calcium chloride.
- the composition is placed in this medium saturated with humidity for a period of between 15 minutes and 48 hours.
- This time is relatively short which is an advantage both for the speed of production and in terms of energy saving.
- step a) makes it possible to facilitate and / or accelerate the hydration reaction of step b).
- the hydration reaction of step b) can also be facilitated by an increase in the reaction temperature, or even in the pressure.
- the hydration temperature is chosen here in the range between 40 ° C and 150 ° C.
- any means to raise the temperature can be used to reach the desired hydration temperature in step b).
- traditional heating can be used (tunnel oven, electrical resistances, etc.).
- a temperature below 100 ° C, i.e. here between 40 ° C and 100 ° C, is particularly advantageous because it makes it possible to carry out step b) at atmospheric pressure, which is easy and advantageous from an economic and safety point of view in an industrial installation.
- Hydrothermal conditions are understood to mean a temperature above the boiling temperature and a pressure sufficient to guarantee a medium saturated with humidity (ie for example greater than 100 ° C. under a pressure of 1 atm). For a given temperature, the pressure must be higher than the saturated vapor pressure.
- a medium saturated with humidity ie for example greater than 100 ° C. under a pressure of 1 atm.
- the pressure must be higher than the saturated vapor pressure.
- the duration of step b) is chosen as a function of the hydration temperature. More specifically, the higher the hydration temperature, the shorter the duration of step b). Thus, for example, in the case of hydrated lime and bauxite trihydrate ground to a d80 of dqmiti, the rate of progress of the hydration reaction is close to 90% after 8 minutes at a hydration temperature of 150 ° C, this rate of progress being reached after 25 minutes at 100 ° C, after 90 minutes at 85 ° C, and after 20 hours at 40 ° C.
- a hydration temperature between 80 ° C and 90 ° C, for example 85 ° C, will be chosen.
- a hydration time between 15 minutes and 48 hours.
- the duration of hydration is between 18 hours and 30 hours, for example between 20 hours and 28 hours.
- the hydration time is between 22 hours and 26 hours.
- the hydration time is 24 hours.
- the hydrated phases resulting from the hydration reaction of step b) are in the form of precipitates. They are either in dry solid form, that is to say without free water, or in suspension. When they are in suspension, they should be separated from the free water around them because the evaporation of this free water later, during step c) of cooking, represents an additional energy cost. This separation can be done by various means, in particular filtration, pressing or even evaporation.
- Possible drying of the recovered precipitates is possible, without being necessary. This drying can be carried out between 80 ° C and 260 ° C approximately, under a dry atmosphere, for example by passing the precipitates in the oven at 85 ° C, for 24 hours. More generally, the drying is simultaneous with the implementation of step c) of cooking.
- step c) the precipitated hydrated phases are subjected to a baking treatment.
- the material obtained has a reactive capacity with water, which makes it a hydraulic binder.
- the cooking temperature chosen for the implementation of step c) depends, on the one hand, on the hydrated phases formed in step b), and, on the other hand, on the calcium aluminates that are desired. obtain at the end of step c).
- the CAH10 precipitate dehydrates at 200 ° C
- the C3AH6 precipitate dehydrates at 400 ° C.
- the dehydration temperatures of the usual hydrated phases are referenced in the FACTSage or GEMS thermodynamic data tables.
- the C3AH6 phase which is the most stable hydrated calcium aluminate phase obtained in step b), is completely dehydrated at 400 ° C. It may however be beneficial to use a baking temperature above 400 ° C to control the relative proportions of the other dehydrated phases and the overall reactivity of the hydraulic binder finally obtained.
- Both the mineralogy and the crystallinity of the calcium aluminates that can be obtained at the end of step c) depend on the duration and the temperature of cooking chosen. Likewise, the proportions of these different calcium aluminates in the final hydraulic binder depend on the duration and on the cooking temperature, also called dehydration temperature, chosen. For example, for an undoped calcium aluminate, the following phenomena will generally occur. For a cooking temperature between around 400 ° C and around 500 ° C, C3AH6 breaks down into C12A7 and hydrated lime Ca (OH) 2.
- the hydrated lime dehydrates, and the calcium aluminate therefore comprises a crystalline phase of C12A7 and dehydrated lime CaO.
- the species recrystallization occurs, mainly C12A7 and lime CaO.
- the recombination of the calcium aluminate and lime phases occurs, evolving towards the chemical equilibrium of the initial composition.
- the recombination of iron and silica occurs with the calcium aluminate phases, the amount of recombinant iron and silica increasing with temperature.
- the substances obtained are a more or less amorphous mixture.
- the degree of crystallinity, the relative proportion of the crystalline phases, and the residual crystallized water depend on the duration and on the temperature of step c) of dehydration.
- a higher cooking temperature has the effect of reducing the amorphous part and of developing the crystallized phases.
- the amount of residual crystallized water decreases as the dehydration temperature increases.
- Other phenomena such as recrystallization or recombination can also occur as the temperature increases, but these phenomena do not necessarily appear in sequential order.
- These dehydration, recrystallization or recombination phenomena each have their own kinetics, which also depend on the species considered.
- stage c) of cooking all the reactions which can occur at this temperature or else at a lower temperature can take place, and increasing the duration of stage c) allows the reactions to approach l state of equilibrium.
- the calcium aluminates which can be obtained in crystalline form are the following: C3A (3Ca0.Al203), C12A7 (1 2Ca0.7Al203), CA (CaO.A ⁇ Os), CA2 (Ca0.2Al203) or CA6 (Ca0 .6Al203) for phases containing only lime and alumina, but also C 4 A3 $ (4CaO.3AI2O3.SO3) or C2AS (2CaO.AI2O3.SiO2) for phases containing oxides of sulfur or silica.
- the hydraulic reactivity of these calcium aluminates that is to say their capacity and speed of reaction with water, is variable. In general, the hydraulic reactivity of the “pure” calcium aluminate phases decreases when the ratio C / A, that is to say the molar (or mass) ratio between lime and alumina, decreases.
- step c) the choice of a cooking temperature of 400 ° C. in step c) leads to obtaining the crystallized phase C12A7 and lime hydrated in the amorphous or poorly crystallized state, as well as any excess products which did not react in step b), namely Portlandite CH if excess of lime, and alumina monohydrate AH if excess of alumina.
- the relative proportions of the crystallized and amorphous phases obtained depend on the overall chemistry of the starting substances, in particular on the C / A ratio of the composition of step a).
- Treatment at higher temperatures induces a reduction in the amorphous part, an increase in the already crystallized phases as well as the appearance of new crystallized phases not observed at 400 ° C., such as the crystallized phases CA, CA2, C 4 A3 $, C2AS.
- step c) The duration and the cooking temperature of step c) are therefore to be defined according to the application and the reactivity targeted for the hydraulic binder produced.
- the cooking temperature is chosen within a range between 200 ° C and 1300 ° C.
- the baking temperature is preferably between 400 ° C and 1200 ° C, more preferably between 900 ° C and 1000 ° C, even more preferably between 930 ° C and 970 ° C.
- This baking temperature is significantly lower than the usual temperatures used in known calcium aluminate manufacturing processes, in particular those used in known sintering or melting processes.
- step c) When step c) is carried out at a pressure below atmospheric pressure, the baking temperature can optionally be lowered, for example for a baking temperature below 600 ° C., without changing the properties of the final hydraulic binder obtained.
- any means allowing the temperature to be raised can be used to reach the cooking temperature desired in step c).
- traditional heating or microwave heating can be used.
- cooking can be carried out in an electric oven, with a temperature ramp of 300 ° C per hour, until it reaches the desired cooking temperature, this cooking temperature being maintained for a desired cooking time.
- the cooling is then controlled by ventilation of the oven with a ramp of -300 ° C per hour, until reaching a temperature close to 110 ° C allowing the handling of the final product.
- the cooking time that is to say the time during which the hydrated phases are placed at the cooking temperature, is between 15 minutes and 240 minutes. This duration, less than or equal to 4 hours is very reasonable and makes it possible to limit energy consumption. Preferably, the cooking time is 3 hours or less.
- the C2F, C 4 AF ferrites and the C2AS Gehlenite lead to a hydraulic binder having a slower reactivity because their hydraulic potential is lower than that of pure calcium aluminates (CA or C12A7 phases), but may also have remarkable long-term mechanical resistance - especially C 4 AF.
- limiting the formation of the phases comprising ferrite and Gehlenite makes it possible to obtain a hydraulic binder with rapid reactivity at the end of step c), that is to say a hydraulic binder having a setting rapid and / or rapid increase in its initial resistance; but promoting their development leads to a hydraulic binder which will give a less reactive cement but having good mechanical resistance in the long term.
- step b) of the process according to the invention are such that they do not lead to the obtaining of new hydrated phases of calcium aluminates containing iron or silica.
- the iron, its oxides or the silica remain in free form and not recombined at the end of step b). It is thus possible, depending on the cooking temperature chosen in step c), to include or not, iron, its oxides or silica, in the final dehydrated phases.
- step c at a cooking temperature below 900 ° C., none of the crystalline phases C2F and / or C 4 AF, and / or C2AS is formed.
- all the residual lime present in the system following step b) remains in the form of hydrated lime or quicklime CaO, the latter having a high hygroscopy and too high reactivity, which are harmful to envisaged applications.
- step c) by placing in step c) at a cooking temperature between 930 ° C and 970 ° C, for example close to 950 ° C, for about 3 hours, the lime is found entirely combined in phases d aluminates of calcium, and iron and / or its oxides, just begin to react with the phases present to combine with crystalline phases of calcium aluminate and form the crystallized phases of C2F and / or C 4 AF.
- the ferrites seem to be formed in the form of C2F and / or C4AF, while the silica is just beginning to combine with phases of calcium aluminates in C2AS, but these phases are less reactive than calcium aluminates.
- the cooking temperature will be between 200 ° C and 750 ° C; alternatively, between 200 ° C and 700 ° C.
- the composition of step a) comprises at most 0.4% by weight of fluorinated compounds chosen from a source of CaF2 and / or the cryolite Na3AIF6, relative to the weight of the dry composition of step at) ; alternatively the composition of step a) comprises at most 0.3% by weight, for example at most 0.2% by weight of fluorinated compounds chosen from a source of CaF2 and / or the cryolite Na3AIF6, relative to the weight of the dry composition of step a); for example, the composition of step a) does not comprise fluorinated compounds chosen from a source of CaF2 and / or the cryolite Na3AIF6.
- the method according to the invention does not include the addition of fluorinated compounds chosen from a source of CaF2 and / or the cryolite Na3AIF6.
- the method according to the invention always leads to the production of a very crumbly calcium aluminate compound.
- the calcium aluminate compound can easily be reduced to a powder, for example by means of a mortar and pestle, or by means of a treatment of 5 to 10 minutes in a grinder such as 'a jar turner.
- the method according to the invention also always leads to the production of a calcium aluminate compound with a high specific surface (according to the BET method).
- the calcium aluminate compound obtained by the process according to the invention has for example a specific surface greater than 7 m 2 / g; or even more than 20 m 2 / g.
- the calcium aluminate compound obtained by the process according to the invention has a specific surface greater than 40 m 2 / g.
- the calcium aluminate compound obtained can be used as a hydraulic binder.
- the calcium aluminate compound obtained can be used alone or combined with calcium sulphate and optionally Portland cement to form a hydraulic binder.
- the hydraulic binder thus formed can for example be used in the following applications:
- mortars such as repair mortars, tile adhesives and joints, screeds and plasters, or even decorative plasters
- the calcium aluminate compound obtained can also be used in the following applications:
- the loss on ignition PF here mainly represents the humidity of the raw materials, measured by the relative weight loss after drying at 110 ° C for 24 hours.
- bauxite A (Australian) is poor in iron oxide and silica
- bauxite B or bauxite C are richer in iron oxides.
- Gypsum plaster is a semi-hydrated calcium sulphate
- gypsum is a di-hydrated calcium sulphate, knowing that everything will be found in di-hydrated form during step b).
- the calcium aluminate compounds LH2 to LH7 obtained according to the process of the invention are themselves used as hydraulic binders to form pure pastes denoted P1 to P10, and P * , and mortars M1, M11, M12 , M13 and M14, as well as comparative mortars MC1 and MC2.
- anhydrite FF® which is an anhydrous calcium sulphate marketed by the company Francis Flower, ordinary portland cement, abbreviated "OPC” which is the portland cement marketed by the company Milke (reference OPC 52.5R), NE14 sand (AFNOR standardized silica sand), citric and tartaric acids, sodium carbonate Na 2 C0 3 .
- Table 2 below groups together various initial compositions as well as the operating conditions of the process of the invention used to obtain the calcium aluminate compounds LH1 to LH 11.
- the mass% are given by mass either relative to the total mass of the wet composition, or relative to the total mass of materials dry composition.
- the fineness of the calcium aluminate compounds LH1 to LH11 is measured on an optical bench, by the laser diffraction method, according to standard IS0 13320, with a granulometer of the Mastersizer 2000 laser type, sold by the company Malvern, optical model. "Fraunhofer", under pressure of 3 bars.
- Table 3 summarizes the fineness of the calcium aluminate compounds LH2 to LH7 obtained according to the process of the invention, under the operating conditions of table 2. More specifically, this table 3 indicates the reference diameters d10, d50 , d80 and d90 of the different compounds obtained. These reference diameters define the particle size distribution of all the particles constituting each compound obtained.
- the reference diameter d10 is a reference diameter defined as the diameter below which 10% of the particles used are located, by mass relative to the total mass of all of said particles.
- the reference diameter d50 is a reference diameter defined as the diameter below which lies 50% of the particles used, by mass relative to the total mass of all of said particles.
- the reference diameter d90 is a reference diameter defined as the diameter below which lies 90% of the particles used, by mass relative to the total mass of all of said particles.
- the fineness is obtained after grinding the compounds obtained at the end of step c), with a pestle mortar for 5 minutes (LH3, LH4, LH5, LH6 and LH7), or for 10 minutes (LH2).
- the fineness of the calcium aluminate compounds LH2 to LH7 corresponds to that of a fine cement.
- a conventional commercial calcium aluminate manufactured by the melting process followed by grinding by a ball mill, for example of the Ternal® RG-S or Ternal® EP type sold by the company Kerneos, has a diameter d80 of around 65pm.
- the products obtained according to the process of the invention after light and rapid grinding, are as fine, even finer, than conventional hydraulic binders ground by conventional energy-consuming means such as ball or roller mills.
- the LH2 compound which is ground twice as long, is not particularly finer than the LH3 to LH7 compounds. This clearly shows that a light grinding is sufficient to obtain a fine cement by the process according to the invention.
- the products obtained by the process of the invention have the particularity of having a specific surface area according to the BET method higher than the cements existing on the market, which is particularly advantageous.
- the chemical composition of the calcium aluminate compounds LH1 to LH11 can be analyzed in an equivalent manner by different methods than a person skilled in the art will easily be able to choose, for example by X-ray diffraction, or even by a thermo-gravimetric (ATG) analysis method.
- X-ray fluorescence on pearl is chosen.
- the protocol is as follows: mix 0.85 g of calcined material and 5.15 g of lithium tetraborate; make the pearl on the Perl X3 device from the Panalytical brand (melting profile: 50s at 900 ° C, then 230s at 1050 ° C, then 230s at 1100 ° C and quenching); analyze the pearl using the XRF S4 Pioneer BRUKER brand device, via the Pearl program.
- Table 4 summarizes the mineralogical composition of the calcium aluminate compounds LH1 to LH11 obtained.
- the calcium aluminate compounds LH1 to LH11 obtained all comprise at least one calcium aluminate.
- binders very rich in C 12 A 7 are obtained, like Ternal® EP distributed by the company Kerneos, or binders very rich in CA phase, like Ternal® RG , or a new binder with a calcium sulfoaluminate phase C 4 A3 $, whose hydraulic potential is recognized.
- the calcium aluminate compounds LH1 to LH11 are used, in combination with calcium sulphate and / or Portland cement, as a hydraulic binder to form pastes numbered P1 to P10, as well as when sand is added to the binding phase, to form mortars numbered M1, M11, M12, M13 and M14, as well as comparative mortars MC1 and MC2 using commercial calcium aluminates.
- P * is a 100% LH6 test, that is to say without the addition of Portland cement or calcium sulphate.
- compositions are given in Tables 5 and 6 below.
- compositions are given by mass of each compound relative to the total mass of dough, while in Table 6, they are mass data of each compound relative to the total mass of mortar (% by mass).
- MC1 mortar is a comparative mortar made to compare the properties of M1 mortar to that of a mortar obtained from an existing aluminous cement, Ternal EP® cement (TEP * ) sold by the company Kerneos.
- TEP * Ternal EP® cement
- This cement obtained according to the fusion process from natural raw materials (bauxite monohydrate and limestone) contains mainly lime and alumina according to a C / A molar ratio of 1.77, approximately 8% of oxide of iron, and present as the main mineralogical phase C12A7. It is used as a binding phase in combination with calcium sulphate, for the production of mortars.
- MC2 mortar is obtained with the commercial product Ciment Fondu® (CF *), whose production is similar to that of Ternal EP, only has a C / A molar ratio around 1.73 and an iron oxide level around 15%, and presents as main mineralogical phase CA.
- CF * Ciment Fondu®
- MC2 are weighed and then homogenized for 15 minutes in a “Turbulat” type mixer.
- the mixed powders are then introduced into the bowl of a “Raynery” type mortar mixer, and after kneading, dry, for 30 seconds at 60 revolutions per minute (rpm), water, called water of mixing, is added all at once, then the mixing continues for 30 seconds at 60 rpm, then another 30 seconds at 120 rpm.
- rpm revolutions per minute
- the calcium aluminate compounds LH8 to LH11, respectively, are used alone as hydraulic binders to form mortars M11 to M14, according to the AFNOR standard.
- MC2 mortar is a comparative mortar formed according to this AFNOR standard, from Ciment Fondu® (CF * ) sold by the company Kerneos. Ciment Fondu® is obtained according to a conventional high-temperature melting process, from bauxite rich in mono-hydrated alumina and limestone.
- the open time of some of the mortars thus obtained is given in table 7.
- the open time corresponds to the time during which the mortar has a viscosity suitable for its handling and its positioning.
- the open time corresponds to the time elapsing between the moment when water is added to the hydraulic binder, and the moment when the setting of the binder begins, which is identified by an increase in temperature of the water-binder mixture. hydraulic.
- Table 7 shows that the open times of the mortars M1, respectively M11 to M14, obtained from hydraulic binders produced according to the process of the invention are equivalent to the open times of the comparative mortars MC1, respectively MC2.
- the mortars M1, M1 1 to M14, and MC1, and the pastes P1 to P10 are placed in a metal mold in which they are left for the time of their setting.
- the dimensions of the mold are as follows: 20 ⁇ 20 ⁇ 160mm 3 , so as to produce a mortar prism having the same dimensions as those of the mold.
- the mold is stored at 20 ° C, at a relative humidity of 80%, for 1 h, 2 h, 4 h, 5 h, 6 h or even 24 h before the hardened material is demolded and tested.
- Relative humidity also called humidity, is defined as the ratio of the partial pressure of water vapor in the air to the saturated vapor pressure (or vapor pressure) at the same temperature. In other words, relative humidity indicates the ratio between the water vapor content of the air in which is preserved the mold and the maximum capacity of this air to contain water under predetermined temperature conditions.
- the mechanical resistance to bending and compression are tested on prismatic test pieces of hardened material obtained at various times, 1 hour, 5 hours or even 24 hours after the contact of the powder (binder + additives + possible sand) with the 'water.
- the mechanical strengths are evaluated according to the NF EN 196-1 cement test standard, using a press known as the 3R press. More specifically, the mechanical resistance to bending (RF) is first evaluated, then the mechanical resistance to compression (RC) is evaluated from the two half-test pieces resulting from the bending test. The force applied to the specimen until failure allows the breaking stress to be calculated (in MegaPascal, denoted MPa), both in bending and in compression, according to standard NF EN 196-1.
- RF mechanical resistance to bending
- RC mechanical resistance to compression
- Tables 8 to 10 below summarize the different mechanical resistance values obtained for mortar prisms, at 20 ° C, after 2h, 6h or 24h of setting (M1 or MC1 mortars), after 1h, 5h or 24h of setting (pasta P1 to P10), or after 4h, 6h and 24h setting (mortars M11 to M14 and MC2).
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Abstract
Description
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Application Number | Priority Date | Filing Date | Title |
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FR1860094A FR3087769B1 (fr) | 2018-10-31 | 2018-10-31 | Procede de fabrication d'un liant hydraulique |
PCT/FR2019/052582 WO2020089564A1 (fr) | 2018-10-31 | 2019-10-30 | Procédé de fabrication d'un liant hydraulique |
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US (1) | US20220017414A1 (fr) |
EP (1) | EP3873866A1 (fr) |
JP (1) | JP2022510503A (fr) |
KR (1) | KR20210092729A (fr) |
CN (1) | CN113316562B (fr) |
BR (1) | BR112021008275A2 (fr) |
FR (1) | FR3087769B1 (fr) |
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US3156751A (en) * | 1961-12-06 | 1964-11-10 | Crane Co | Mold for forming a ceramic article and method of making the mold |
US3226240A (en) * | 1963-01-28 | 1965-12-28 | Standard Oil Co | Calcium aluminate cement composition |
JPS51111828A (en) * | 1975-03-27 | 1976-10-02 | Matsushita Electric Works Ltd | Production method of inorganic molded article |
JPS52101700A (en) * | 1976-02-21 | 1977-08-25 | Katsukawa Heitarou | Process for preparing calcium aluminate |
FR2470820A1 (fr) * | 1979-11-30 | 1981-06-12 | Lafarge Sa | Procede de fabrication de charges minerales contenant du monocarboaluminate de calcium hydrate |
US4410455A (en) * | 1980-10-22 | 1983-10-18 | Imperial Chemical Industries Plc | Process for producing a hydrogenation catalyst |
JPS62128919A (ja) * | 1985-11-26 | 1987-06-11 | Nippon Light Metal Co Ltd | カルシウムアルミネ−ト水和物の製造方法 |
US4710225A (en) * | 1986-05-23 | 1987-12-01 | Rucker Robert A | Refractory cement |
JPS6395114A (ja) * | 1986-10-06 | 1988-04-26 | Toubu Kagaku Kk | アルミン酸カルシウムの合成法 |
JP2779177B2 (ja) * | 1988-10-04 | 1998-07-23 | 電気化学工業株式会社 | 水硬性カルシウムアルミネートの風化防止方法 |
US5407459A (en) * | 1993-09-23 | 1995-04-18 | Alcan International Limited | Process for the preparation of calcium aluminates from aluminum dross residues |
JPH08119630A (ja) * | 1994-10-28 | 1996-05-14 | Sumitomo Chem Co Ltd | 水硬性カルシウムアルミネート水和物の製造方法 |
JPH10287420A (ja) * | 1997-04-11 | 1998-10-27 | Kawai Sekkai Kogyo Kk | カルシウムヘキサアルミネートの製造方法 |
JP3560580B2 (ja) * | 2001-10-18 | 2004-09-02 | 独立行政法人 科学技術振興機構 | 12CaO・7Al2O3化合物とその作成方法 |
FR2839066B1 (fr) * | 2002-04-24 | 2005-02-04 | Lafarge Aluminates | Liant ettringitique pour mortier dense, comprenant des sulfates de calcium et un compose mineral d'aluminates de calcium |
CN1405092A (zh) * | 2002-11-12 | 2003-03-26 | 中国铝业股份有限公司 | 拜尔法联合生产氧化铝和铝酸钙水泥的方法 |
EP2803649B1 (fr) * | 2013-05-15 | 2016-04-13 | Calucem GmbH | Ciment alumineux blanc |
JP2018002546A (ja) * | 2016-07-01 | 2018-01-11 | デンカ株式会社 | カルシウムアルミネートの製造方法 |
CN110028092B (zh) * | 2019-05-17 | 2020-06-09 | 中国科学院过程工程研究所 | 一种利用铝灰和电石渣制备铝酸钙的方法 |
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ZA202102822B (en) | 2022-07-27 |
US20220017414A1 (en) | 2022-01-20 |
CN113316562B (zh) | 2023-05-02 |
JP2022510503A (ja) | 2022-01-26 |
WO2020089564A1 (fr) | 2020-05-07 |
BR112021008275A2 (pt) | 2021-08-03 |
FR3087769A1 (fr) | 2020-05-01 |
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