• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    The present invention relates to a hydraulic binder comprising as a percentage by weight: from 17 to 55% of a Portland cement whose particles have a D50 of 2 μm to 11 μm; at least 5% silica fume; from 36 to 70% of an inorganic addition A1 whose particles have a D50 of between 15 and 150 μm; the sum of these percentages being from 80 to 100%; the sum of the percentages of cement and silica fume being greater than 28%.
    公开号:FR3022540A1
    申请号:FR1455728
    申请日:2014-06-20
    公开日:2015-12-25
    发明作者:Fabrice Toussaint；Gerard Molines；Remi Barbarulo
    申请人:Lafarge SA；
    IPC主号:
    专利说明:

    [0001] The invention relates to hydraulic binders which make it possible to obtain an ultra high performance concrete with a low cement content, as well as mixtures comprising this binder. BACKGROUND OF THE INVENTION
    [0002] Technological developments in recent years in the field of concrete have led to the development of hydraulic binders to obtain ultra-high performance concrete in terms in particular of compressive strength. These binders generally involve the use of additional materials in addition to cement and aggregates, which are for example fibers, organic adjuvants or so-called ultrafine particles. However, these conventional ultra high performance concretes have a relatively high cement content, generally from 700 kg of cement / m3 of concrete to 1000 kg of cement / m3 of concrete. However, the manufacture of cement, in particular the manufacture of clinker is at the origin of high carbon dioxide emissions. In fact, the production of clinker supposes: a) the preheating and decarbonation of the raw flour which is obtained by grinding of the raw materials, which are notably the limestone and the clay; and b) cooking the decarbonated flour at a temperature of about 1450 ° C, followed by a sudden cooling. These two steps produce CO2, on the one hand as a direct product of the decarbonation and on the other hand as a secondary product of the combustion which is carried out at the firing stage to provide the elevation in temperature. However, the high carbon dioxide emissions in conventional methods of producing cementitious compositions and concrete constitute a major environmental problem and, in the current context, are likely to be strongly penalized economically. There is therefore a strong need for a process for producing ultra-high performance concrete with associated reduced carbon dioxide emissions.
    [0003] For this purpose, the present invention provides a hydraulic binder comprising as a percentage by weight: from 17 to 55% of a Portland cement whose particles have a D50 of 2 el to 1 l; at least 5% silica fume; From 36 to 70% of an Al mineral addition whose particles have a D50 of from 15 to 150 μm; PA14009 EN 3022540 2 the sum of these percentages being from 80 to 100%; the sum of the percentages of cement and silica fume being greater than 28%. The present invention also relates to a mixture comprising in volume percentage, at least 45% of the hydraulic binder according to the invention and at least 30% of sand, the sum of these percentages being from 95 to 100%. The subject of the present invention is also a hydraulic composition comprising in a volume of 1 m3 excluding air entrapped and excluding fibers - from 155 to 195 liters of water; At least 770 liters of mixture according to the invention; the sum of the volumes of these 2 components ranging from 950 to 1000 liters. The invention also provides a shaped object for the field of construction comprising the hydraulic binder according to the invention or the mixture according to the invention. The invention seeks to provide at least one of the critical advantages described below. The invention makes it possible to meet the need for reducing emissions of O 2. In fact, the amount of cement (and in particular clinker) used in the context of the present invention is less than that which is traditionally necessary for ultra-fine concrete. high performance, up to 148 kg / m3 cement per m3 concrete. Advantageously, the hydraulic composition according to the invention has a high mechanical strength, generally greater than or equal to 90 MPa at 28 days. Other advantages and characteristics of the invention will become clear from reading the description and examples given by way of purely illustrative and nonlimiting that will follow. The subject of the invention is a hydraulic binder comprising as a percentage by weight: from 17 to 55% of a Portland cement whose particles have a D50 of from 2 el to 11 μm; at least 5% silica fume; from 36 to 70% of an Al mineral addition whose particles have a D50 of from 15 to 150 μm; the sum of these percentages being from 80 to 100%; the sum of the percentages of cement and silica fume being greater than 28%. PA14009 EN 3022540 3 A hydraulic binder is a material that picks up and hardens by hydration. The setting is generally the transition to the solid state of a hydraulic binder by hydration reaction. The setting is usually followed by a hardening period.
    [0004] Curing is usually the acquisition of the mechanical strengths of a hydraulic binder. Curing usually takes place after the end of the setting. The hydraulic binder according to the invention comprises a Portland cement. Portland cement within the meaning of the invention incorporates a Portland clinker. It is also conceivable to use a Portland cement clinker ground as Portland cement, provided further addition of calcium sulfate. The preferred Portland cements are those as defined in the European Standard NF EN 197-1 of April 2012 and those described in the ASTM C150-12 standard, more preferably it is the CEM I cements. Preferably, the hydraulic binder according to US Pat. The invention comprises from 17 to 50% of Portland cement, more preferably from 18 to 45%, expressed as a percentage by weight relative to the binder. The cements suitable for use according to the present invention are generally Portland cements with a BET surface area of from 1.20 to 3 m 2 / g, preferably from 1.20 to 2.5 m 2 / g.
    [0005] The BET surface area is a measure of the total real surface area of the particles, which takes into account the presence of reliefs, irregularities, superficial or internal cavities, porosity. The cements suitable for use according to the present invention are preferably the cements whose particles have a D10 of from 1 μm to 4 μm, more preferably from 1 μm to 3 μm, even more preferably from 1 μm to 1 μm. The cements suitable for use according to the present invention are preferably cements whose particles have a D50 of from 3 μm to 10 μm, more preferably from 4 μm to 9 μm.
    [0006] The cements suitable for use according to the present invention are preferably the cements whose particles have a D 90 of from 8 μm to 25 μm, more preferably 9 μm to 24 μm. D90, also denoted Dv90, is the 90th percentile of the particle size distribution, ie, 90% of the volume consists of 35 particles smaller than D90 and 10% larger. greater than D90. Similarly, the D50, also denoted Dv50, corresponds to the 50th percentile of the volume distribution of particle size, that is to say that 50% of the volume consists of particles whose size is less than D50 and 50% larger than the D50.
    [0007] Similarly, D10, also denoted Dv10, corresponds to the 10th percentile of the particle size volume distribution, i.e., 10% of the volume consists of particles smaller than D10 and 90 % larger than D10. The D10 or D90 of a set of particles may be generally determined by laser particle size for particles smaller than 800 μm, or by sieving for particles larger than 63 μm. Preferably, the Portland cement suitable for use according to the present invention has a Blaine specific surface greater than or equal to 5000 cm 2 / g, more preferably greater than or equal to 6500 cm 2 / g.
    [0008] The Portland cement that can be used according to the present invention can be milled and / or separated (by a dynamic separator) to obtain a cement having a Blaine surface area greater than or equal to 5000 cm 2 / g. This cement can be called ultrafine. The cement may for example be ground according to two methods. According to a first method, the cement or clinker can be milled to a Blaine surface area of 5000 to 9000 cm 2 / g. A high efficiency separator, second generation or third generation, or a very high efficiency separator, can be used in this first step to separate the cement having the desired fineness and remove the cement not having the desired fineness. This cement is then returned to the mill.
    [0009] According to a second method, a Portland cement can pass into a very high efficiency separator, called THF (very high fineness), in order to separate the cement particles having a Blaine surface area greater than or equal to the target fineness (the target fineness). being greater than 5000 cm2 / g) and the cement particles having a Blaine specific surface area less than the target fineness. Cement particles having a Blaine surface area greater than or equal to the target fineness can be used as is. The cement particles having a Blaine specific surface area less than the target fineness can be separated or ground separately until the desired Blaine surface area is obtained. The mills which can be used in both methods are for example a ball mill, a vertical mill, a roller press, a horizontal mill (for example of the Horomill® type) or a vertical agitated mill (for example Tower type). Mill). The hydraulic binder according to the invention comprises silica fume. The silica fume suitable according to the invention may be a by-product of metallurgy and silicon production. The silica fume is generally formed of spherical particles comprising at least 85% by mass of amorphous silica.
    [0010] Preferably, the silica fume used according to the present invention may be chosen from silica fumes according to the European Standard NF EN 197-1 of February 2001, paragraph 5.2.7. Preferably, the hydraulic binder according to the invention comprises from 5 to 45% silica fume, more preferably from 5 to 40%, even more preferably from 6 to 30%, expressed as a percentage by weight relative to the binder. The hydraulic binder according to the invention comprises a mineral addition Al. The mineral addition Al is chosen from pozzolanic additions or siliceous additions such as quartz, calcium-limestone mineral additions, calcareous additions such as calcium carbonate or their mixtures.
    [0011] The mineral additions Al which are also suitable according to the invention may be chosen from slags, optionally milled, calcined schists, materials containing calcium carbonate, fly ash, zeolites, ash from the combustion of plants, calcined clays and mixtures thereof. Preferably, the inorganic additions Al which are suitable according to the invention may be fines of silica and / or calcium carbonate. The mineral additions Al are, for example calcined schists (for example as defined in the standard NF EN 197-1, paragraph 5.2.5), mineral additions comprising calcium carbonate, for example limestone (for example such as defined in the standard NF EN 197-1, paragraph 5.2.6), mineral additions comprising silica, for example siliceous fines or mixtures thereof. Preferably, the hydraulic binder according to the invention comprises from 36 to 68%, addition A1, more preferably from 36 to 66%, expressed as a percentage by weight relative to the binder. The hydraulic binder according to the invention may further comprise calcium sulphate. Preferably, the hydraulic binder according to the invention further comprises from 0.01 to 8% of calcium sulphate, expressed as a percentage by weight relative to the binder. Calcium sulphate exists in its natural state. It is also possible to use a calcium sulphate which is a by-product of certain industrial processes. The calcium sulfate may be anhydrous or not. Preferably, when the fineness of the cement increases, it is possible to also increase the amount of calcium sulphate to obtain optimal mechanical strengths. The skilled person will know by his knowledge optimize the amount of calcium sulfate using known methods. This optimization will be based on the fineness of the cement particles. The hydraulic binder according to the invention may furthermore comprise from 0 to 20%, expressed as a percentage by weight relative to the binder, of pozzolanic materials (for example as defined in the European standard NF EN 197-1 of February 2001, paragraph 5.2 .3), slags (for example as defined in the European standard 10 NF EN 197-1 of February 2001 paragraph 5.2.2), calcined schists (for example as defined in the European standard NF EN 197-1 of February 2001 paragraph 5.2.5), materials containing calcium carbonate, for example limestone (for example as defined in the European Standard NF EN 197-1 of February 2001 paragraph 5.2.6), of siliceous additions (for example as defined in the French standard 15 NF P 18-509 of December 1998 paragraph 5), fly ash (for example as defined in the European standard NF EN 197-1 of February 2001 paragraph 5.2.4) or their mixtures. Another object of the invention is a mixture comprising, in percentage by volume, at least 45% of the hydraulic binder according to the invention and at least 30% of sand, the sum of these percentages being between 95 and 100%. The mixture according to the invention comprises a sand. Preferably, the sand of the mixture according to the invention is a siliceous sand, calcined bauxite sand, sand-lime sand, calcareous sand or mixtures thereof. The particle size of the sands is generally determined by sieving.
    [0012] Preferably, the mixture according to the invention comprises a sand whose particles have a D10 of from 100 μm to 1 mm. Preferably, the mixture according to the invention comprises a sand whose particles have a D50 of from 200 to 3 mm, more preferably from 250 to 1000 μm.
    [0013] Preferably, the mixture according to the invention comprises a sand whose particles have a D90 of less than or equal to 5 mm, more preferably a D90 of from 300 μm to 5 mm, even more preferably a D90 of from 350 μm to 1,000! Am. The mixture according to the invention preferably comprises a sand whose particles have a D10 of from 100 μm to 1 mm and a D50 of from 200 μm to 3 mm and a D90 of 300 μm to 5 μm. mm. Another object of the invention is a hydraulic composition comprising 5 in a volume of 1 m 3 excluding occluded air and excluding fibers - from 155 to 195 liters of water; at least 770 liters of mixture according to the invention; the sum of the volumes of these 2 components ranging from 950 to 1000 liters.
    [0014] In general, the water comprises the added water for the mixing and the water of the adjuvants, also called total water. The hydraulic composition according to the invention includes both the compositions in the fresh state and in the cured state, for example a cement slurry, a mortar or a concrete. The hydraulic composition according to the invention may also comprise an adjuvant, for example one of those described in standards EN 934-2 of September 2002, EN 934-3 of November 2009 or EN 934-4 of August 2009, and optionally mineral additions. Preferably, the hydraulic compositions according to the invention also comprise an adjuvant for hydraulic composition, for example an accelerator, a viscosifying agent, an antifoaming agent, a retarder, an inerting clays, a reducing agent for shrinkage, a plasticizer and / or or a superplasticizer. In particular, it is useful to include a polycarboxylate superplasticizer, in particular from 0.01 to 5%, preferably from 0.1 to 3%, expressed as a mass of dry extract, relative to the mass of cement.
    [0015] It should be noted that these adjuvants can be added to the binder or the mixture according to the invention. The hydraulic composition according to the invention may further comprise a fluidizing agent or a superplasticizer. The term "superplasticizer" as used in this specification and accompanying claims is to be understood to include both water reducers and superplasticizers as described in the book entitled "Concrete Admixtures Handbook, Properties". Science and Technology, "VS Ramachandran, Noyes Publications, 1984. A water reducer is defined as an adjuvant which typically reduces the amount of mixing water of a concrete for a given workability from typically 10 to 35%. Water reducers include, for example, lignosulfonates, hydroxycarboxylic acids, carbohydrates and other specialized organic compounds, for example glycerol, polyvinyl alcohol, sodium aluminoxymethyl siliconate, sulfanilic acid and casein. Superplasticizers belong to a new class of water reducers, chemically different from normal water reducers and able to reduce water amounts by about 30%. Superplasticizers have been broadly classified into four groups: sulfonated condensates of naphthalene formaldehyde (SNF) (usually a sodium salt); sulphonated condensates of melamine formaldehyde (SMF); modified lignosulfonates (MLS); And the others. More recent superplasticizers include polycarboxylic compounds such as polycarboxylates, for example polyacrylates. A superplasticizer is preferably a new generation superplasticizer, for example a copolymer containing a polyethylene glycol as a grafted chain and carboxylic functions in the main chain as a polycarboxylic ether. Sodium polycarboxylate polysulfonates and sodium polyacrylates may also be used. Phosphonic acid derivatives can also be used. The required amount of superplasticizer usually depends on the reactivity of the cement. The lower the reactivity, the lower the required amount of superplasticizer. To reduce the total amount of alkaline salts, the superplasticizer can be used as a calcium salt rather than as a sodium salt. Phosphonic acid derivatives can also be used. Sodium polycarboxylate polysulfonates and sodium polyacrylates may also be used. The amount of superplasticizer required generally depends on the reactivity of the cement. The lower the reactivity, the lower the amount of superplasticizer required. In order to reduce the total content of alkaline salts, the superplasticizer can be used in the form of calcium salt rather than sodium salt. The hydraulic composition according to the invention may further comprise an anti-foaming agent, for example polydimethylsiloxane. Anti-foaming agents also include silicones in the form of a solution, solid or preferably in the form of a resin, an oil or an emulsion, preferably in water. More particularly suitable are silicones comprising (RSiO0.5) and (R2SiO) groups. In these formulas, the R radicals, which may be the same or different, are preferably a hydrogen atom or an alkyl group of 1 to 8 carbon atoms, the methyl group being preferred. The number of patterns is preferably from 30 to 120.
    [0016] The hydraulic composition according to the invention may further comprise a viscosifying agent and / or a flow limit modifier (generally for increasing the viscosity and / or the flow limit). Such agents include: cellulose derivatives, for example, water-soluble cellulose ethers, such as carboxymethyl, methyl, ethyl, hydroxyethyl and sodium hydroxypropyl ethers; alginates; and xanthan, carrageenan or guar gum. A mixture of these agents can be used. The hydraulic composition according to the invention may further comprise an accelerator and / or a retarder. The hydraulic composition according to the invention may further comprise fibers, for example mineral fibers (for example glass, basalt), organic fibers (for example plastic type APV), metal fibers (for example steel) or a mixture of these. The organic fibers may especially be chosen from polyvinyl alcohol (PVA) fibers, poly-acrylonitrile (PAN) fibers, high density polyethylene (HDPE) fibers, polyamide or polyimide fibers, polypropylene fibers. , aramid fibers or carbon fibers. Mixtures of these fibers can also be used. These organic fibers may be in the form of an object consisting of either single-strand or multi-strand, the diameter of the object ranging from 25 microns to 800 microns. The individual length of the organic fibers is preferably between 10 and 50 mm. The metal fibers may be metal fibers selected from steel fibers such as high strength steel fibers, amorphous steel fibers, or stainless steel fibers. . Optionally, the steel fibers may be coated with a non-ferrous metal such as copper, zinc, nickel (or their alloys). The individual length of the metal fibers is preferably at least 2 mm and is even more preferably in the range 10-30 mm. Crenellated, corrugated or crocheted fibers may be used at the ends. Preferably, the amount of fiber is from 0.1 to 6 (:) / 0, still more preferably from 1 to 5% of the volume of the hydraulic composition. The use of fiber mixtures with different characteristics makes it possible to adapt the properties of the concrete to the desired characteristics. It should be noted that the fibers can be added to the binder or to the mixture according to the invention.
    [0017] The hydraulic composition according to the invention can be prepared by mixing the mixture according to the invention or the hydraulic binder according to the invention with water. According to an advantageous embodiment of the process for preparing a hydraulic composition according to the invention, the amount of water used is from 160 to 195 μm 3 and preferably from 160 to 185 μm 3. The hydraulic composition can be reinforced, for example by metal reinforcements. The hydraulic composition can be prestressed, by cables or tendons adhering, or post-stretched, by cables or tendons or sheaths or non-adherent bars. Prestressing, in the form of pre-tension or post-tension, is particularly suitable for compositions made according to the present invention.
    [0018] Advantageously, the hydraulic compositions obtained according to the invention have a compressive strength greater than or equal to 90 MPa at 28 days after mixing and / or greater than or equal to 120 MPa after heat treatment, for example after a heat treatment of 2 days at 90 ° C, performed after 2 days at 20 ° C. The hydraulic composition according to the invention may be prepared according to methods known to those skilled in the art, including the mixing of solid components and water, shaping (eg casting, spraying, spraying or calendering) and hardening. The hydraulic composition according to the invention may be subjected to a heat treatment after setting to improve its mechanical properties. The post-curing treatment, also called the thermal cure of the concrete, is generally carried out at a temperature of 60 ° C to 90 ° C. The temperature of the heat treatment must be lower than the boiling temperature of the water at ambient pressure. The heat treatment temperature after setting is generally less than 100 ° C. The duration of the heat treatment after setting can be, for example, 6 hours to 4 days, preferably about 2 days. The heat treatment can begin, generally at least one day after the start of the setting and preferably on concrete aged 1 to 12 days at 20 ° C. The heat treatment can be carried out in dry or wet environments or in cycles that alternate the two environments, for example, a 24-hour treatment in a humid environment followed by a 24-hour treatment in a dry environment. The invention also relates to a shaped object for the field of construction comprising the hydraulic binder according to the invention or the mixture according to the invention.
    [0019] The following measuring methods were used: Laser particle size distribution The particle size curves of the various powders are obtained from a Malvern MS2000 laser particle size analyzer. The measurement is carried out in a suitable medium (for example, in an aqueous medium); the particle size should be from 0.02 μm to 2 mm. The light source consists of a red He-Ne laser (632 nm) and a blue diode (466 nm). The optical model is that of Fraunhofer, the calculation matrix is of polydisperse type. A background measurement is first performed with a pump speed of 2000 rpm, an agitator speed of 800 rpm and a noise measurement over 10 s, in the absence of ultrasound. It is then verified that the laser light intensity is at least 80%, and that a decreasing exponential curve is obtained for the background noise. If this is not the case, the lenses of the cell should be cleaned. A first measurement is then carried out on the sample with the following parameters: pump speed of 2000 rpm, stirrer speed of 800 rpm, absence of ultrasound, obscuration limit between 10 and 20%. The sample is introduced to have a darkness slightly above 10%. After darkening stabilization, the measurement is made with a time between immersion and the measurement set at 10 s. The measurement time is 30 s (30,000 diffraction images analyzed). In the granulogram obtained, it must be taken into account that part of the population of the powder can be agglomerated. Then a second measurement (without draining the tank) with ultrasound. The pump speed is raised to 2500 rpm, agitation at 1000 rpm, ultrasound is emitted at 100% (30 watts). This regime is maintained for 3 minutes, then the initial parameters are returned: pump speed 2000 rpm, stirrer speed 800 rpm, absence of ultrasound. After 10 s (to evacuate the possible air bubbles), a measurement of 30 s (30,000 images analyzed) is carried out. This second measurement corresponds to a deagglomerate powder by ultrasonic dispersion. Each measurement is repeated at least twice to check the stability of the result. The apparatus is calibrated before each work session by means of a standard sample (silica Sifraco C10) whose particle size curve is known. All the measurements presented in the description and the ranges announced correspond to the values obtained with ultrasound. BET surface area measurement method The specific surface area of the different powders is measured as follows. A sample of powder of the following mass is taken: 0.1 to 0.2 g for a specific surface area estimated at more than 30 m 2 / g; 0.3 g for a specific surface area estimated at 30 m2 / g; 1 g for a specific surface area estimated at 3-10 m 2 / g; 1.5 g for a specific surface area estimated at 2-3 m2 / g; 2 g for a specific surface area estimated at 1.5-2 m2 / g; 3 g for a specific surface area estimated at 1-1.5 m2 / g. A cell of 3 cm3 or 9 cm3 is used depending on the volume of the sample. The entire measuring cell (cell + glass rod) is weighed. Then the sample is added to the cell: the product should not be less than one millimeter from the top of the cell throat. The whole is weighed (cell + glass rod + sample). The measuring cell is placed on a degassing station and the sample is degassed. Degassing parameters are 30 min / 45 ° C for Portland cement, gypsum, pozzolans; 3 hours / 200 ° C for slags, fly ash, aluminous cement, limestone; and 4 h / 300 ° C for control alumina. The cell is quickly plugged with a plug after degassing. We weigh the whole and we note the result. All weighings are done without the cap, which is temporarily removed for measurement. The mass of the sample is obtained by subtracting the mass of the cell from the sum of the masses of the cell and the degassed sample. The sample is then analyzed after it has been placed on the measuring station. The analyzer is the Beckman Coulter SA 3100. The measurement is based on nitrogen adsorption by the sample at a given temperature, here the temperature of the liquid nitrogen is about -196 ° C. The apparatus measures the pressure of the reference cell in which the adsorbate is at its saturation vapor pressure and that of the sample cell in which known volumes of adsorbate are injected. The curve resulting from these measurements is the adsorption isotherm. In the measurement process, knowledge of the dead volume of the cell is necessary: a measurement of this volume is therefore made with helium before analysis. The mass of the previously calculated sample is entered as a parameter. The BET surface is determined by the software by linear regression from the experimental curve. The reproducibility standard deviation obtained from 10 measurements on a surface-area silica 21.4 m 2 / g is 0.07. The reproducibility standard deviation obtained from 10 measurements on a specific surface cement 0.9 m2 / g is 0.02. Once every two weeks a check is made on a reference product. Twice a year, a check is made with the reference alumina supplied by the manufacturer. Measurement method of compressive strength PA14009 EN 3022540 13 Whatever the deadline, the compressive strength is measured on a cylindrical sample having a diameter of 7 cm and a height of 14 cm, the surfaces on which the compressive force is applied to the sample are smoothed out. The applied compressive force is increased at a rate of 3.85 kN / sec during the compression test. Examples The present invention is described by Examples A, B, C, D, E, F, G, H which follow, without limitation. 10 - Raw materials: / Ciment 52.5N PMES Teil Lafarge France / Millisil C6 Sibelco, France / Silica fume MSTO2 Le Pontet SEPR, France / Micro Anhydrite A Maxit, France 15 / Sand BE01 Sibelco, France / Superplasticizer F2 Chryso, France The cement was prepared by grinding and separation of Portland CEM I 52.5N PMES cement from the Lafarge Le Teil cement plant. This grinding was carried out using an air jet mill associated with a very high efficiency separator. The ground cement obtained had a 1.7 μm D10, a 5.3 μm D50, and a 10.6 μm D90. Its Blaine surface is 6950cm2 / g and its BET surface is 1.65m2 / g. Millisil C6 is a siliceous filler (quartz) from Sibelco. It corresponds to addition Al. It has a D10 of 2.9 pm, a D50 of 28.9 pm, and a D90 of 95.6 pm. The silica fume MST 02 from the company SEPR is characterized by a BET surface area of 12 m 2 / g. Micro A anhydrite is a micronized anhydrous calcium sulfate from the company Maxit. It has a D10 of 1.6 μm, a D50 of 12.3 μm, and a D90 of 17.0 μm.
    [0020] BE01 is a siliceous sand from Sibelco. It has a D10 of about 210 μm and a D50 of about 310 μm, a D90 of about 400 μm. Superplasticizer F2 is a new generation superplasticizer based on modified polycarboxylate.
    [0021] Materials: - A RAYNERI R601 kneader mixer, which was supplied by the company VMI with a tank of 10 liters. This mixer performs a planetary rotation movement; cylindrical cardboard molds with a diameter of 7 cm and a height of 14 cm; a climatic chamber at 95-100% relative humidity and 90 ° C. +/- 1 ° C. supplied by Verre Labo Mula; a humid chamber at 95-100% relative humidity and 20 +/- 1 ° C. Protocol for the preparation of the hydraulic composition according to the invention: The concrete (hydraulic composition) was manufactured according to the protocol described below. : 1) introduction of dry materials (sand, Al, cement, calcium sulphate and silica fume) into the bowl of the Rayneri kneader; 2) kneading for 3 minutes at a speed of 15 rpm to homogenize the solids; 3) introducing the mixing water and half of the superplasticizer for 30 seconds, at the speed of rotation of 35 rpm; 4) kneading for 4 minutes and 30 seconds at the speed of 35 rpm; 5) introducing the other half of the superplasticizer for 30 seconds, at a speed of rotation of 50 rpm; 6) kneading for 2 minutes and 30 seconds at a speed of 50 rpm; 7) Stopping the mixer. Fresh concrete has been obtained. The concrete was poured into the cylindrical molds.
    [0022] The molded test pieces obtained are sealed and put on hold for 24 hours at 20 ° C. Then, the test pieces are demolded and are placed either: in a humid chamber for 28 days at 20 ° C. and 100% relative humidity; either in a humid chamber for 7 days at 20 ° C. and 100% relative humidity, then in a climatic chamber for 48 hours at 90 ° C. and 100% relative humidity (heat treatment). Then the mechanical strengths were measured. 35 - Hydraulic binders according to the invention, in% by mass: PA14009 FR 3022540 15% Cement% Al% Silica fume% calcium sulphate A 18.2% 40.7% 40.3% 0.8% B 42.0 % 37.5% 18.6% 1.9% C 17.7% 61.9% 19.6% 0.8% D 48.7% 43.1% 6.0% 2.2% E 25, 6% 66.9% 6.3% 1.2% F 26.3% 46.6% 25.9% 1.2% G 33.9% 52.1% 12.5% 1.5% H 34 , 0% 48.0% 16.5% 1.5% - Composition of the mixtures according to the invention, in% by volume:% Binder% Hydraulic Sand A 50.8% 49.2% B 51.0% 49.0 % C 50.8% 49.2% D 51.1% 48.9% E 50.8% 49.2% F 50.8% 49.2% G 50.9% 49.1% H 50.9 % 49.1% - Hydraulic compositions according to the invention, in liters for 1 m3 of concrete: The hydraulic compositions according to the invention are described below in liters 1m3 of concrete, excluding occluded air and excluding fibers. Adjuvant Mixture Water Added Total Water A 828.9 18.7 152.4 166.8 B 821.6 12.2 166.2 175.5 C 833.0 12.2 154.8 164.2 D 804.1 10 , 3 185.6 193.5 E 808.2 9.4 182.4 189.6 F 832.0 13.1 154.9 165.0 G 832.0 11.2 156.8 165.5 H 829, 8 11,7 158,5 167,5 PA14009 EN 5 3022540 16 - Performance of hydraulic compositions: The mechanical compressive strengths are measured on cylinders with a diameter of 70 mm and a height of 140 mm. The results are expressed in MPa. Rc Rc 28days / Treatment 20 ° C heat A 135.6 199.4 B 187.2 239.1 C 134.8 196.2 D 164.9 202.4 E 128.9 169.1 F 154.9 219 G 181.4 225.2 H 176 235.7 PA14009 EN 17
    权利要求:
    Claims (12)
    [0001]
    CLAIMS1- Hydraulic binder comprising in percentage by weight: - from 17 to 55% of a Portland cement whose particles have a D50 of 2μm to 11 μm - at least 5% of silica fume; from 36 to 70% of an Al mineral addition whose particles have a D50 of from 15 to 150 Fini; the sum of these percentages being from 80 to 100%; the sum of the percentages of cement and silica fume being greater than 28%.
    [0002]
    2- hydraulic binder according to claim 1 characterized in that the cement is a cement CEM I.
    [0003]
    3- hydraulic binder according to claim 1 or 2 characterized in that it further comprises calcium sulfate.
    [0004]
    4. Hydraulic binder according to any one of the preceding claims, characterized in that the mineral addition Al is selected from pozzolanic additions or siliceous additions such as quartz, mineral additions silico-limestone, calcareous additions such as carbonate calcium or their mixtures.
    [0005]
    5- hydraulic binder according to any one of the preceding claims characterized in that the particles of the cement have a D90 of 8μm to 251.1m.
    [0006]
    6. Blend comprising in volume percentage, at least 45% of the hydraulic binder according to any one of claims 1 to 5 and at least 30% of sand, the sum of these percentages being from 95 to 100%.
    [0007]
    7- The mixture of claim 6 characterized in that it comprises a sand whose particles have a D10 of 100 microns to 1 mm and a D50 of 200 prn to 3 mm and a D90 of 3001.irn to 5 mm.
    [0008]
    8- Mixture according to claim 6 or 7 characterized in that the sand is siliceous sand, calcined bauxite sand, sand-lime sand, calcareous sand or mixtures thereof.
    [0009]
    9- Hydraulic composition comprising in a volume of 1 m3 outside occluded air and excluding fibers 18 3022540 from 155 to 195 liters of water; at least 770 liters of mixture according to one of claims 6 to 8; the sum of the volumes of these 2 components ranging from 950 to 1000 liters.
    [0010]
    10- The hydraulic composition of claim 9 comprising an anti-foaming agent.
    [0011]
    11- hydraulic composition according to any one of claims 9 to 10 characterized in that it further comprises inorganic fibers, organic or metal or a mixture thereof.
    [0012]
    12- shaped object for the field of construction comprising the hydraulic binder according to any one of claims 1 to 5 or the mixture according to any one of claims 6 to 8.
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    同族专利:
    公开号 | 公开日
    ES2732211T3|2019-11-21|
    US20170152183A1|2017-06-01|
    US9926234B2|2018-03-27|
    RU2683295C2|2019-03-27|
    CN106470956B|2019-04-02|
    PH12017500021A1|2017-05-15|
    AU2015276145A1|2017-01-12|
    RU2016152490A|2018-07-23|
    CN106470956A|2017-03-01|
    MX370872B|2020-01-08|
    MX2016016616A|2017-03-20|
    WO2015193420A1|2015-12-23|
    SG11201610642TA|2017-02-27|
    EP3157886B1|2019-04-03|
    CA2952106A1|2015-12-23|
    BR112016029620A2|2017-08-22|
    CO2017000417A2|2017-06-09|
    MY179002A|2020-10-26|
    RU2016152490A3|2019-01-14|
    EP3157886A1|2017-04-26|
    SA516380523B1|2021-01-05|
    FR3022540B1|2021-05-14|
    AU2015276145B2|2019-02-14|
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    法律状态:
    2015-05-26| PLFP| Fee payment|Year of fee payment: 2 |
    2015-12-25| PLSC| Publication of the preliminary search report|Effective date: 20151225 |
    2016-06-13| PLFP| Fee payment|Year of fee payment: 3 |
    2017-06-15| PLFP| Fee payment|Year of fee payment: 4 |
    2018-06-13| PLFP| Fee payment|Year of fee payment: 5 |
    2020-05-29| PLFP| Fee payment|Year of fee payment: 7 |
    2021-05-27| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1455728A|FR3022540B1|2014-06-20|2014-06-20|ULTRA HIGH PERFORMANCE CONCRETE WITH LOW CEMENT CONTENT|FR1455728A| FR3022540B1|2014-06-20|2014-06-20|ULTRA HIGH PERFORMANCE CONCRETE WITH LOW CEMENT CONTENT|
    US15/320,157| US9926234B2|2014-06-20|2015-06-18|Ultra-high performance concretes having a low cement content|
    EP15728908.3A| EP3157886B1|2014-06-20|2015-06-18|Ultra-high performance concretes having a low cement content|
    MX2016016616A| MX370872B|2014-06-20|2015-06-18|Ultra-high performance concretes having a low cement content.|
    AU2015276145A| AU2015276145B2|2014-06-20|2015-06-18|Ultra-high performance concretes having a low cement content|
    RU2016152490A| RU2683295C2|2014-06-20|2015-06-18|Ultra-high performance concrete having a low cement content|
    PCT/EP2015/063684| WO2015193420A1|2014-06-20|2015-06-18|Ultra-high performance concretes having a low cement content|
    ES15728908T| ES2732211T3|2014-06-20|2015-06-18|Ultra high performance concrete with low cement content|
    CN201580036753.0A| CN106470956B|2014-06-20|2015-06-18|Ultra-high performance concrete with low cement|
    SG11201610642TA| SG11201610642TA|2014-06-20|2015-06-18|Ultra-high performance concretes having a low cement content|
    BR112016029620A| BR112016029620A2|2014-06-20|2015-06-18|ultra high performance concrete with low cement content|
    CA2952106A| CA2952106A1|2014-06-20|2015-06-18|Ultra-high performance concretes having a low cement content|
    MYPI2016002191A| MY179002A|2014-06-20|2015-06-18|Ultra-high performance concretes having a low cement content|
    SA516380523A| SA516380523B1|2014-06-20|2016-12-19|Ultra–High Performance Concretes Having A Low Cement Content|
    PH12017500021A| PH12017500021A1|2014-06-20|2017-01-03|Ultra-high performance concretes having a low cement content|
    CONC2017/0000417A| CO2017000417A2|2014-06-20|2017-01-19|Ultra-high performance concretes that have low cement content|
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