EP3365301A1 - Hydraulic composition having improved carbonation resistance - Google Patents

Hydraulic composition having improved carbonation resistance

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Publication number
EP3365301A1
EP3365301A1 EP16809907.5A EP16809907A EP3365301A1 EP 3365301 A1 EP3365301 A1 EP 3365301A1 EP 16809907 A EP16809907 A EP 16809907A EP 3365301 A1 EP3365301 A1 EP 3365301A1
Authority
EP
European Patent Office
Prior art keywords
polyalkyleneimine
binder
hydraulic
composition
composition according
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.)
Withdrawn
Application number
EP16809907.5A
Other languages
German (de)
French (fr)
Inventor
Alexandre JACQUEMIN
Lê-Chiên HOANG
Rémi BARBARULO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Holcim Technology Ltd
Original Assignee
Holcim Technology Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Holcim Technology Ltd filed Critical Holcim Technology Ltd
Publication of EP3365301A1 publication Critical patent/EP3365301A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/26—Carbonates
    • C04B14/28—Carbonates of calcium
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/34—Metals, e.g. ferro-silicon
    • 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
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/22—Carbonation resistance
    • 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 to the field of construction materials, and more particularly to a new composition, in particular hydraulic, having improved durability, in particular a better resistance to carbonation.
  • the durability of concrete or mortar structures obtained by hardening a hydraulic composition is a major concern. Indeed, a work must withstand over time to the various aggressions or solicitations (physical, mechanical, chemical, ...), that is to say to the loads to which it is subjected, as well as wind, to the rain, cold, heat or environment. However exposure to the ambient atmosphere can cause the carbonation of the material resulting from the hardening of a hydraulic composition. Indeed, the amount of water introduced into the hydraulic composition in the fresh state is often greater than the stoichiometric amount, which leads to a porous medium whose pores are first filled with water. When the cementitious material dries, it becomes desaturated in water and the pores partially fill with air.
  • the atmospheric CO 2 thus diffuses into the hydraulic composition hydrated by its porosity and reacts with the hydrates of the cement, in particular with portlandite, to form calcium carbonate. This results in a drop in pH which generally goes from a value of 13 in the non-carbonated zone to a value generally less than 9 in the carbonated zone.
  • the pH of the degraded zone of the hardened hydraulic composition decreases and initiates the corrosion of the steels in a humid medium and in the presence of oxygen.
  • Carbonation is a major problem for hydraulic compositions with low clinker content. Indeed, during hardening, these hydraulic compositions are very sensitive to carbonation because of their low rate of Portlandite (phase created during the hydration of a clinker, especially Portland), this phase playing a buffer role in the progression carbonation.
  • the problem to be solved by the invention is to provide a means for reducing or preventing carbonation, and thus the corrosion of metal elements when present, in the hydraulic compositions in the cured state, in particular the compositions hydraulic systems with low clinker content and mineral additions.
  • the present invention seeks to reduce or prevent carbonation at a given stage of the hydration, which is characterized by the same mechanical resistance in compression (iso-resistance). Without being bound by theory, it would seem that carbonation is strongly linked to the progress of hydration.
  • composition comprising at least:
  • a hydraulic binder comprising at least one clinker
  • the hydraulic composition has improved resistance to carbonation
  • the metal reinforcements present in the hydraulic composition are not or only slightly corroded
  • the coating (as defined in standard NF EN 1992-1-1 of October 2005, paragraph 4.4.1.1) of the reinforcements becomes less critical and the positioning of the reinforcements in the thickness of the hydraulic composition is facilitated;
  • the hydraulic composition may comprise a reduced rate of clinker, without this promoting the corrosion of the metal reinforcements;
  • the hydraulic composition makes it possible to form a barrier to gases other than CO 2 (for example radon, chlorine, and oxygen), as well as a liquid barrier.
  • gases other than CO 2 for example radon, chlorine, and oxygen
  • the present invention is particularly applicable to reinforced concretes, in particular reinforced concrete based on hydraulic composition having a low level of clinker.
  • the composition of the invention is such that it consists of said hydraulic binder and one or more polyalkyleneimine (s).
  • a composition according to the invention more specifically designates a so-called hydraulic binder composition.
  • hydroaulic binder means a dry material that takes and hardens by hydration.
  • the setting is the transition from liquid or pasty state to solid state.
  • the setting is followed or accompanied by a curing phenomenon during which the material acquires mechanical properties. Hardening usually occurs after the end of setting, especially for cements.
  • a hydraulic binder generally comprises a clinker, calcium sulfate, and one or more mineral additions, in particular as detailed below.
  • the invention thus more particularly relates to a hydraulic binder comprising in addition to a clinker, at least one polyalkyleneimine according to the invention, and where appropriate one or more mineral additions.
  • a composition according to the invention further comprises water.
  • composition of the invention more specifically designates a so-called hydraulic composition.
  • hydraulic composition a composition comprising a hydraulic binder, water, optionally in the cured state of the metal elements, optionally aggregates and optionally adjuvants.
  • the hydraulic composition of the invention is a concrete, more particularly an reinforced concrete.
  • the amount of water is such that the water / binder mass ratio is preferably from 0.3 to 0.8 and preferably from 0.4 to 0.7.
  • a hydraulic composition according to the invention includes both the compositions in the fresh state, for example a cement slurry, and in the cured state, for example a mortar or a concrete.
  • the fresh hydraulic composition comprises water for hydration of the binder, while the cured hydraulic composition is obtained after hydration to give concrete or mortar.
  • composition according to the invention comprises at least one branched polyalkyleneimine.
  • the hydraulic composition of the invention which incorporates at least one polyalkyleneimine, has a greater resistance to carbonation than a reference hydraulic composition free of polyalkyleneimine, which makes it possible to improve the durability of said hydraulic composition and reduce corrosion of any metal reinforcements.
  • the polyalkyleneimine (s) of the hydraulic composition of the invention has (s) a molecular weight of from 400 g / mol to 1,000,000 g / mol, preferably from 600 g / mol to 200,000 g / mol preferably from 800 g / mol to 50,000 g / mol, for example from 1,000 g / mol to 5,000 g / mol.
  • molecular weight is meant a weight average molecular weight (Mw).
  • the polyalkyleneimine (s) is (are) present in the composition in a weight ratio of 0.05% to 5.0% relative to the weight of the binder.
  • the weight ratio of polyalkyleneimine (s) relative to the binder is from 0.1% to 4.0%, preferably from 0.15% to 3.0%, or from 0.2% to 1%, 5%.
  • the nitrogen content (% dry) of the polyalkyleneimines is advantageously from 15% to 33%.
  • composition of the invention may comprise a mixture of several polyalkyleneimines.
  • polyalkyleneimine mention may be made of polyethyleneimine or polypropyleneimine.
  • the composition according to the invention comprises at least one polyethyleneimine, preferably a branched polyethyleneimine.
  • the composition of the invention comprises at least one branched polyalkyleneimine.
  • the branched polyalkyleneimines contain primary, secondary and tertiary amines.
  • It may be in particular a branched polyethyleneimine or a branched polypropyleneimine.
  • Branched polyethyleneimines are generally obtained by polymerization of ethyleneimine (also known as aziridine).
  • PEI dendrimer polyethyleneimines dendrimer
  • PPI dendrimer polypropyleneimines dendrimer
  • These compounds have an alkylenediamine-type nucleus and are generated in a tree ("star") structure around this nucleus, by stacking successive generation layers.
  • These compounds mainly comprise primary amines (at the periphery) and tertiary amines (at the heart).
  • the polyalkyleneimine (s) (s) are present in the composition of the invention in a free form, for example in aqueous solution.
  • the clinker used according to the present invention may be a Portland clinker, a sulfo-aluminous clinker, an aluminous clinker, a belitic clinker, a sulpho-belitic clinker and mixtures thereof, preferably a Portland clinker.
  • a Portland clinker is obtained by high temperature clinkerisation of a mixture comprising in particular limestone and clay.
  • a Portland clinker is a clinker as defined in standard NF EN 197-1 of February 2001.
  • the mass proportion of clinker in the hydraulic binder may be from 0% to
  • 100% relative to the mass of the binder preferably from 5% to 95%, more preferably from 30% to 85%.
  • the invention is particularly advantageous for hydraulic compositions having a low clinker content.
  • a low clinker ratio means a clinker mass content in the hydraulic binder less than 85%.
  • the reduced amount of clinker is usually compensated in the hydraulic binder by mineral additions, such as a limestone filler described below.
  • mineral additions such as a limestone filler described below.
  • Mineral additions are generally materials that can be used as a partial substitution for clinker.
  • the mineral additives suitable for the hydraulic binder according to the invention may be chosen from slags (for example as defined in standard NF EN 197-1 of February 2001, paragraph 5.2.2), natural or artificial pozzolans (for example such as defined in standard NF EN 197-1 of February 2001, paragraph 5.2.3), fly ash (for example as defined in standard NF EN 197-1 of February 2001, paragraph 5.2.4), calcined schists (For example as defined in standard NF EN 197-1 of February 2001, paragraph 5.2.5), mineral additions based on calcium carbonate, for example limestone (for example as defined in standard NF EN 197 - 1 February 2001, paragraph 5.2.6), silica fumes (for example as defined in standard NF EN 197-1 of February 2001, paragraph 5.2.7), metakaolins, biomass ash (for example ashes of rice husks) and mixtures thereof.
  • slags for example as defined in standard NF EN 197-1 of February 2001, paragraph 5.2.2
  • natural or artificial pozzolans for example such as defined in standard
  • the mineral additions used according to the invention may also be ash from the combustion of plants, such as for example the ashes from the combustion of rice balls.
  • the mineral additions used according to the invention may also be zeolites.
  • Flying ash is usually a powdery particle in the flue gases of coal-fired power plants. It is usually recovered by electrostatic or mechanical precipitation.
  • the chemical composition of a fly ash depends mainly on the chemical composition of the burned coal and the process used in the thermal power plant from which it originated. It is the same for its mineralogical composition.
  • the fly ash used according to the invention may be of siliceous or calcic nature.
  • the fly ash used according to the present invention is chosen from those as described in European Standard NF EN 197-1 of February 2001.
  • Slags are generally obtained by rapidly cooling the molten slag from the smelting of iron ore in a blast furnace.
  • the slags used according to the present invention may be chosen from granulated blast furnace slags according to the European Standard NF EN 197-1 of February 2001, paragraph 5.2.2.
  • the silica fumes used according to the present invention can be a material obtained by reducing high-purity quartz by charcoal in electric arc furnaces. used for the production of silicon and ferrosilicon alloys.
  • the silica fumes are generally formed of spherical particles comprising at least 85% by mass of amorphous silica.
  • the silica fumes used according to the present invention are chosen from silica fumes according to the European standard NF EN 197-1 of February 2001, paragraph 5.2.7.
  • the pozzolanic materials used according to the present invention may be natural siliceous or silico-aluminous substances, or a combination thereof.
  • Pozzolanic materials include natural pozzolans, which are generally materials of volcanic origin or sedimentary rocks, and calcined natural pozzolans, which are materials of volcanic origin, clays, shales or rocks. sedimentary, thermally activated.
  • the pozzolanic materials used according to the invention may be chosen from pumice, tuffs, slag or mixtures thereof.
  • the pozzolanic materials used according to the present invention are chosen from pozzolanic materials according to European Standard NF EN 197-1 of February 2001, section 5.2.3.
  • the mineral additives used according to the invention are materials containing calcium carbonate, for example limestone (also called limestone filler).
  • the calcined clays used according to the present invention can result from the calcination of a clay, kaolinite, associated with different minerals (phyllosilicates, quartz, iron oxides) in varying proportions depending on the deposits. They can be obtained either by grinding calcination or by grinding calcination in production units with rotary kilns, trays or so-called “flash” calcination, for example. They are essentially composed of amorphous alumina silicate particles.
  • the calcined clays used according to the present invention may be chosen from metakaolins according to the preliminary draft standard PR NF P 18-513 of December 2011.
  • the hydraulic binder of the invention may further comprise calcium sulphate.
  • the calcium sulphate used includes gypsum (calcium sulphate dihydrate, CaSO 4 .2H 2 O), hemihydrate (CaSO 4 .1 / 2H 2 O), anhydrite (anhydrous calcium sulphate, CaSO 4 ) or one of their mixtures. Gypsum and anhydrite exist in their natural state. It is also possible to use a calcium sulphate which is a by-product of certain industrial processes.
  • the hydraulic binder of the invention comprises from 3% to 28% by weight of calcium sulphate relative to the weight of clinker.
  • a high content of calcium sulphate is generally adopted for aluminous and sulphoaluminous cements.
  • the chemical nature (gypsum, hemihydrate or anhydrite) and the calcium sulphate dosage are advantageously adjusted depending on the cement to prevent swelling of the hydrates.
  • the hydraulic binder of the invention comprises from 1% to 8%, preferably from 2% to 5% by mass of calcium sulphate relative to the mass of clinker.
  • a binder according to the invention is generally obtained by co-grinding a clinker and calcium sulphate.
  • composition of the invention in particular the hydraulic composition of the invention, may comprise, in the cured state, metallic elements, for example reinforcements, in particular reinforced concrete reinforcements according to the European standard NF EN 1992-1- 1 of October 2005.
  • the frames can be in the form of bars, welded mesh or assembly of bars, reinforcement.
  • the junctions of the bars may be provided by overlapping, splicing, soldering, ligation, crimping or any other means.
  • the metal elements are drawn steel fibers completely or partially replacing ordinary metal reinforcements in certain applications (pavements, shotcrete or repair concrete).
  • composition of the invention in particular the hydraulic composition of the invention, may comprise aggregates.
  • the aggregates optionally used in the composition according to the invention include sand (whose particles generally have a maximum size (Dmax) less than or equal to 4 mm), and possibly chippings (whose particles generally have a minimum size (Dmin) greater than 4 mm and preferably a Dmax less than or equal to 20 mm).
  • the aggregates used in the composition according to the invention are generally conform to the European standard NF EN 12620 of August 2003, and are of natural or artificial origin. Aggregates can also be wood.
  • composition of the invention in particular the hydraulic composition of the invention, may comprise conventional adjuvants subject to their compatibility with the polyalkyleneimine (s) required according to the invention.
  • the hydraulic composition according to the invention comprises at least one adjuvant for hydraulic composition: an accelerator, an air-entraining agent, a viscosifying agent, a retarder, an inerting clays, an antifoaming agent, a plasticizer and / or a superplasticizer.
  • the hydraulic composition according to the invention comprises at least one antifoam agent avoiding the entrainment of air in the composition.
  • Inerting clays are compounds that reduce or prevent the harmful effects of clays on the properties of hydraulic binders. Inerting clays include those described in WO 2006/032785 and WO 2006/032786.
  • 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 15%.
  • Water reducers include, for example, lignosulfonates, hydroxycarboxylic acids, carbohydrates and other specialized organic compounds, for example glycerol, polyvinyl alcohol, sodium alumino-methyl-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 were 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 as polycarboxylates, for example polyacrylates.
  • SNF naphthalene formaldehyde
  • SMF sulphonated condensates of melamine formaldehyde
  • MLS modified lignosulfonates
  • More recent superplasticizers include polycarboxylic compounds 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 can also be used. Phosphonic acid derivatives, sodium polycarboxylate polysulfonates and sodium polyacrylates may 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.
  • Antifoam agents also include silicones in the form of a solution of. solid or preferably in the form of resin, oil or emulsion, preferably in water. More particularly suitable are silicones comprising (RSiOo, 5) and (R 2 SiO) groups.
  • 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.
  • the amount of such an agent in the final cement is generally at most 5 parts by weight relative to the cement.
  • composition according to the invention can comprise:
  • a hydraulic binder comprising a Portland clinker, calcium sulphate and a calcined filler or other mineral addition, the mass proportion of clinker in the binder being from 30% to 85%,
  • At least one branched polyalkyleneimine with a molecular weight of from 400 g / mol to 1,000,000 g / mol, preferably from 600 g / mol to 200,000 g / mol, preferably from 800 g / mol to 50,000 g / mol, for example from 1,000 g / mol to 5,000 g / mol, in a proportion by weight of between 0.05% and 5.0% relative to the weight of said hydraulic binder,
  • the weight ratio water / binder is from 0.3 to 0.8 and preferably from 0.4 to 0.7
  • a granulate such as sand, and optionally an antifoaming agent.
  • the present invention also relates to a method for manufacturing a composition according to the invention, comprising a step of contacting at least one hydraulic binder, comprising at least one clinker, with at least one branched polyalkyleneimine, having a a molecular weight of 400 g / mol to 1,000,000 g / mol, in a polyalkyleneimine (s) / binder weight ratio of from 0.05% to 5.0%.
  • the composition prepared is a hydraulic composition
  • the hydraulic binder and the polyalkyleneimine (s) are contacted in the presence of water.
  • the hydraulic composition according to the invention can be used directly on site in the fresh state and cast in a formwork adapted to the intended application, or used in prefabrication plant.
  • the mixing of the hydraulic composition can be carried out according to methods known to those skilled in the art.
  • polyalkyleneimine (s) can be added to the water or to one of the components of the hydraulic composition according to the present invention, for example to hydraulic binder or aggregates.
  • the polyalkyleneimine (s) may be added at any time during the manufacture of the fresh hydraulic composition according to the invention, in solid or liquid form.
  • the polyalkyleneimine (s) is (are) implemented in the form of an aqueous solution.
  • This embodiment is particularly suitable for the case of polyalkyleneimine (s) soluble in water at basic pH, as is the case of branched polyalkyleneimines.
  • the present invention also relates to the use of at least one branched polyalkyleneimine having a molecular weight of from 400 g / mol to 1,000,000 g / mol to reduce and / or prevent carbonation in a composition hydraulic system comprising a hydraulic binder, said at least one polyalkyleneimine (s) being present in the hydraulic composition in a polyalkyleneimine (s) / binder weight ratio of from 0.05% to 5.0%.
  • the present invention relates more particularly to the use of at least one branched polyalkyleneimine, having a molecular weight of from 400 g / mol to 1 000 000 g / mol, in combination with a hydraulic binder in a hydraulic composition at the a fresh state, said at least one polyalkyleneimine (s) being present in the hydraulic composition in a polyalkyleneimine (s) / binder weight ratio of from 0.05% to 5.0%, for reducing and / or preventing carbonation at within said hydraulic composition in the cured state.
  • composition according to the present invention can be shaped to produce, after hydration and hardening, a shaped object for the field of construction.
  • the invention also relates to such a shaped object, obtained from a composition according to the present invention, in particular a hydraulic composition according to the present invention.
  • Objects shaped for the field of construction include, for example, a floor, a screed, a foundation, a wall, a partition, a ceiling, a beam, a worktop, a pillar, a bridge stack, a cinder block, a pipe, a pole, a staircase, a panel, a cornice, a mold, a road element (for example a curb), or a covering (for example road or wall).
  • Mortar specimens were prepared from a hydraulic composition comprising a low clinker hydraulic binder (substituted by 35% of a limestone filler).
  • the water / binder ratio is equal to 0.55 and the TiBP TrilsoButyl Phosphate (antifoam) dosage is 0.09% / binder.
  • Table 1 The composition of the specimens is shown in Table 1 and the characteristics of the cement and sand are shown in Tables 2 and 3. Table 1
  • the branched polyethyleneimines (PEI) of Table 4 were used in various proportions (by weight) relative to the hydraulic binder. Table 4
  • the sand was put into the bowl of a Perrier type 32 mixer with prewetting water. Mixing started and was maintained at low speed for 1 minute.
  • the kneading was then stopped for 4 minutes.
  • the hydraulic binder (clinker + filler) was added and kneading was resumed at low speed for 1 minute.
  • the mixing water comprising the adjuvants (branched polyethylenimine and antifoam), was then added in 30 seconds while mixing at low speed.
  • the adjuvants branched polyethylenimine and antifoam
  • the mixture was kneaded at high speed for 1 minute to obtain a mortar.
  • the mortar was then poured into polystyrene molds measuring 4 cm x 4 cm x 16 cm (without vibration) to obtain 6 concrete specimens (demolded after 24 h at 20 ° C at 100% relative humidity). ).
  • the mortar specimens were then placed under accelerated carbonation conditions. After 6 days of curing in a wet cabinet at 100% relative humidity and 20 ° C., the test pieces were placed in a carbonation box (rectangular HDPE tank, with a capacity of 576 liters, equipped with a tight-fitting lid). whose atmosphere has been enriched with CO 2 (10% +/- 0.5% C0 2 in the air volume of the chamber), 20 ° C +/- 1 ° C and 65% +/- 5% relative humidity.
  • a carbonation box rectangular HDPE tank, with a capacity of 576 liters, equipped with a tight-fitting lid.
  • the temperature regulation was ensured by the fact that the box is placed in a laboratory regulated at 20 +/- 1 ° C.
  • the relative humidity was regulated by a tray filled with ammonium nitrate salt saturated with water, this tray being positioned at the bottom of the box, over the entire available surface.
  • the box was connected to a network fed by bottles filled with a mixture of 50% CO 2 /50% nitrogen under pressure.
  • An expansion unit has enabled the mixture to be delivered at 1 bar of relative pressure in the network.
  • the introduction of the gas was managed automatically by a CO 2 gas analyzer which continuously analyzed the atmosphere of the box (ABISS wall scanner, model LMP 320, supplied by the company PBI Datasensor). At each introduction of gas, another electro valve was opened to evacuate excess gas to a crawl space outside the laboratory, this to prevent overpressure in the box.
  • a fan operated continuously to have a homogeneous distribution of CO 2 gas in the atmosphere of the box.
  • Resistance to carbonation was estimated by measuring the carbonation rate of the specimens. The higher this speed, the less resistant the concrete is to carbonation, and the greater the risk of structural reinforcement corrosion. This speed was measured by determining the depth of carbonated concrete after different periods of exposure of the specimens in the box enriched in gaseous CO 2 .
  • the material is said to be carbonated when its pH is less than or equal to 9. This was visualized by spraying a solution of 0.5% phenolphthalein diluted in a mixture composed of 50% demineralized water and 50% ethanol. Phenolphthalein is a colored indicator that changes to purple pink when the pH is above 9 and remains colorless when the pH is below 9. The carbonated concrete zones are therefore those that remain colorless after spraying the phenolphthalein suspension.
  • the depths of carbonate concrete and mortar were measured in several zones. The arithmetic mean of the values obtained was calculated. The carbonation rate is expressed in mm / day. This is the slope of the line obtained when we represent the evolution of the carbonation depth (in mm) as a function of the square root of time (in days).

Abstract

The present invention relates to a composition including: at least one hydraulic binder, containing at least one clinker, and at least one branched polyalkyleneimine having a molecular weight of from 400 g/mol to 1000000 g/mol in a weight ratio of the polyalkyleneimine(s)/binder of from 0.05% to 5.0%.

Description

COMPOSITION HYDRAULIQUE PRESENTANT UNE RESISTANCE A LA  HYDRAULIC COMPOSITION HAVING RESISTANCE TO
CARBONATATION AMELIOREE  IMPROVED CARBONATION
La présente invention se rapporte au domaine des matériaux de construction, et plus particulièrement à une nouvelle composition, en particulier hydraulique, présentant une durabilité améliorée, en particulier une meilleure résistance à la carbonatation. The present invention relates to the field of construction materials, and more particularly to a new composition, in particular hydraulic, having improved durability, in particular a better resistance to carbonation.
La durabilité des ouvrages en béton ou en mortier obtenus par durcissement d'une composition hydraulique est une préoccupation majeure. En effet, un ouvrage doit résister au cours du temps aux diverses agressions ou sollicitations (physiques, mécaniques, chimiques, ...), c'est-à-dire aux charges auxquelles il est soumis, ainsi qu'au vent, à la pluie, au froid, à la chaleur ou au milieu ambiant. Or l'exposition à l'atmosphère ambiante peut provoquer la carbonatation du matériau issu du durcissement d'une composition hydraulique. En effet, la quantité d'eau introduite dans la composition hydraulique à l'état frais est souvent supérieure à la quantité stœchiométrique, ce qui amène à un milieu poreux dont les pores sont d'abord remplis d'eau. Lorsque le matériau cimentaire sèche, il se désature en eau et les pores se remplissent partiellement d'air. Le CO2 atmosphérique diffuse ainsi dans la composition hydraulique hydratée par sa porosité et vient réagir avec les hydrates du ciment, en particulier avec la portlandite, pour former du carbonate de calcium. Il en résulte une baisse du pH qui passe généralement d'une valeur de 13 dans la zone non carbonatée à une valeur généralement inférieure à 9 dans la zone carbonatée. Le pH de la zone dégradée de la composition hydraulique durcie baisse et initie la corrosion des aciers en milieu humide et en présence d'oxygène. The durability of concrete or mortar structures obtained by hardening a hydraulic composition is a major concern. Indeed, a work must withstand over time to the various aggressions or solicitations (physical, mechanical, chemical, ...), that is to say to the loads to which it is subjected, as well as wind, to the rain, cold, heat or environment. However exposure to the ambient atmosphere can cause the carbonation of the material resulting from the hardening of a hydraulic composition. Indeed, the amount of water introduced into the hydraulic composition in the fresh state is often greater than the stoichiometric amount, which leads to a porous medium whose pores are first filled with water. When the cementitious material dries, it becomes desaturated in water and the pores partially fill with air. The atmospheric CO 2 thus diffuses into the hydraulic composition hydrated by its porosity and reacts with the hydrates of the cement, in particular with portlandite, to form calcium carbonate. This results in a drop in pH which generally goes from a value of 13 in the non-carbonated zone to a value generally less than 9 in the carbonated zone. The pH of the degraded zone of the hardened hydraulic composition decreases and initiates the corrosion of the steels in a humid medium and in the presence of oxygen.
En cas de corrosion, la rouille se développe autour des barres d'acier et fait éclater la composition d'enrobage, ce qui pose problème. Le béton issu de la composition hydraulique s'en trouve endommagé et la corrosion est d'autant plus accélérée que les armatures métalliques sont mises à nues.  In case of corrosion, the rust develops around the steel bars and burst the coating composition, which is a problem. The concrete resulting from the hydraulic composition is damaged and the corrosion is all the more accelerated as the metal frames are exposed.
La carbonatation est notamment un problème majeur pour les compositions hydrauliques à faible taux de clinker. En effet, lors du durcissement, ces compositions hydrauliques sont très sensibles à la carbonatation du fait de leur faible taux de Portlandite (phase créée lors de l'hydratation d'un clinker, notamment Portland), cette phase jouant un rôle tampon dans la progression de la carbonatation.  Carbonation is a major problem for hydraulic compositions with low clinker content. Indeed, during hardening, these hydraulic compositions are very sensitive to carbonation because of their low rate of Portlandite (phase created during the hydration of a clinker, especially Portland), this phase playing a buffer role in the progression carbonation.
Afin de répondre aux exigences des utilisateurs, il est devenu nécessaire de trouver un moyen pour réduire ou prévenir la carbonatation, et ainsi la corrosion d'éléments métalliques quand ils sont présents, dans les compositions hydrauliques à l'état durci, en particulier les compositions hydrauliques ayant un faible taux de clinker et comprenant des additions minérales. In order to meet the requirements of users, it has become necessary to find a way to reduce or prevent carbonation, and thus the corrosion of metal elements when present, in the hydraulic compositions in the cured state, in particular the hydraulic compositions having a low clinker content and comprising mineral additions.
Aussi le problème que se propose de résoudre l'invention est de fournir un moyen pour réduire ou prévenir la carbonatation, et ainsi la corrosion d'éléments métalliques quand ils sont présents, dans les compositions hydrauliques à l'état durci, en particulier les compositions hydrauliques ayant un faible taux de clinker et comprenant des additions minérales. Il est à noter que la présente invention cherche à réduire ou prévenir la carbonatation à un degré d'avancement de l'hydratation donné, qui est caractérisé par une même résistance mécanique en compression (iso-résistance). Sans être lié par la théorie, il semblerait en effet que la carbonatation soit fortement liée à l'avancement de l'hydratation.  Also the problem to be solved by the invention is to provide a means for reducing or preventing carbonation, and thus the corrosion of metal elements when present, in the hydraulic compositions in the cured state, in particular the compositions hydraulic systems with low clinker content and mineral additions. It should be noted that the present invention seeks to reduce or prevent carbonation at a given stage of the hydration, which is characterized by the same mechanical resistance in compression (iso-resistance). Without being bound by theory, it would seem that carbonation is strongly linked to the progress of hydration.
Plus précisément, la présente invention se rapporte à une composition comprenant au moins : More specifically, the present invention relates to a composition comprising at least:
- un liant hydraulique comprenant au moins un clinker, et  a hydraulic binder comprising at least one clinker, and
au moins une polyalkylèneimine ramifiée, ayant un poids moléculaire compris de 400 g/mol à 1 000 000 g/mol, selon un rapport pondéral polyalkylèneimine(s)/liant compris de 0,05 % à 5 %. Ainsi, de manière inattendue, les inventeurs ont mis en évidence qu'il est possible d'utiliser une (ou plusieurs) polyalkylèneimine ajoutée directement dans la masse de la composition hydraulique pour réduire et/ou prévenir la carbonatation de la composition à l'état durci, et ainsi améliorer la durabilité de la composition hydraulique et diminuer la corrosion des armatures métalliques.  at least one branched polyalkyleneimine having a molecular weight of from 400 g / mol to 1 000 000 g / mol, in a polyalkyleneimine (s) / binder weight ratio of from 0.05% to 5%. Thus, unexpectedly, the inventors have demonstrated that it is possible to use one (or more) polyalkyleneimine added directly to the mass of the hydraulic composition in order to reduce and / or prevent the carbonation of the composition in its state. hardened, and thus improve the durability of the hydraulic composition and reduce the corrosion of the reinforcements.
La présente invention permet d'accéder à une composition hydraulique à durabilité améliorée qui a une ou plusieurs des caractéristiques suivantes :  The present invention provides access to an improved durability hydraulic composition that has one or more of the following characteristics:
- la composition hydraulique présente une résistance améliorée à la carbonatation ;  the hydraulic composition has improved resistance to carbonation;
- les armatures métalliques présentes dans la composition hydraulique ne sont pas ou peu corrodées ;  the metal reinforcements present in the hydraulic composition are not or only slightly corroded;
- la corrosion des armatures métalliques peut être retardée lorsque celle-ci se produit ; - the corrosion of metal reinforcements can be delayed when this occurs;
- l'enrobage (tel que défini dans la norme NF EN 1992-1-1 d'octobre 2005, paragraphe 4.4.1.1) des armatures devient moins critique et le positionnement des armatures dans l'épaisseur de la composition hydraulique est facilité ; - la composition hydraulique peut comprendre un taux réduit de clinker, sans que cela ne favorise la corrosion des armatures métalliques ; the coating (as defined in standard NF EN 1992-1-1 of October 2005, paragraph 4.4.1.1) of the reinforcements becomes less critical and the positioning of the reinforcements in the thickness of the hydraulic composition is facilitated; the hydraulic composition may comprise a reduced rate of clinker, without this promoting the corrosion of the metal reinforcements;
- la composition hydraulique permet de former une barrière à d'autres gaz que le CO2 (par exemple radon, chlore, et oxygène), ainsi qu'une barrière aux liquides. the hydraulic composition makes it possible to form a barrier to gases other than CO 2 (for example radon, chlorine, and oxygen), as well as a liquid barrier.
La présente invention trouve particulièrement à s'appliquer pour les bétons armés, en particulier les bétons armés à base de composition hydraulique ayant un faible taux de clinker.  The present invention is particularly applicable to reinforced concretes, in particular reinforced concrete based on hydraulic composition having a low level of clinker.
Selon une variante de l'invention, la composition de l'invention est telle qu'elle est constituée dudit liant hydraulique et d'une ou plusieurs polyalkylèneimine(s). According to a variant of the invention, the composition of the invention is such that it consists of said hydraulic binder and one or more polyalkyleneimine (s).
Selon cette variante, une composition selon l'invention désigne plus précisément une composition dite de liant hydraulique.  According to this variant, a composition according to the invention more specifically designates a so-called hydraulic binder composition.
Conventionnellement, on entend par « liant hydraulique » un matériau sec qui prend et durcit par hydratation. La prise est le passage de l'état liquide ou pâteux à l'état solide. La prise est suivie ou accompagnée d'un phénomène de durcissement pendant lequel le matériau acquiert des propriétés mécaniques. Le durcissement a généralement lieu après la fin de la prise, particulièrement pour les ciments.  Conventionally, the term "hydraulic binder" means a dry material that takes and hardens by hydration. The setting is the transition from liquid or pasty state to solid state. The setting is followed or accompanied by a curing phenomenon during which the material acquires mechanical properties. Hardening usually occurs after the end of setting, especially for cements.
Un liant hydraulique comprend généralement un clinker, du sulfate de calcium, et une ou plusieurs addition(s) minérale(s), notamment tels que détaillés ci-après.  A hydraulic binder generally comprises a clinker, calcium sulfate, and one or more mineral additions, in particular as detailed below.
L'invention vise ainsi plus particulièrement un liant hydraulique comprenant outre un clinker, au moins une polyalkylèneimine conforme à l'invention, et le cas échéant une ou plusieurs addition(s) minérale(s).  The invention thus more particularly relates to a hydraulic binder comprising in addition to a clinker, at least one polyalkyleneimine according to the invention, and where appropriate one or more mineral additions.
Selon une autre variante de l'invention, une composition selon l'invention comprend en outre de l'eau. According to another variant of the invention, a composition according to the invention further comprises water.
Selon cette variante, la composition de l'invention désigne plus précisément une composition dite hydraulique.  According to this variant, the composition of the invention more specifically designates a so-called hydraulic composition.
Conventionnellement, on entend par « composition hydraulique » une composition comprenant un liant hydraulique, de l'eau, éventuellement à l'état durci des éléments métalliques, éventuellement des granulats et éventuellement des adjuvants. De préférence, la composition hydraulique de l'invention est un béton, plus particulièrement un béton armé.  Conventionally, the term "hydraulic composition" a composition comprising a hydraulic binder, water, optionally in the cured state of the metal elements, optionally aggregates and optionally adjuvants. Preferably, the hydraulic composition of the invention is a concrete, more particularly an reinforced concrete.
La quantité d'eau est telle que le rapport massique eau/liant est de préférence de 0,3 à 0,8 et préférentiellement de 0,4 à 0,7.  The amount of water is such that the water / binder mass ratio is preferably from 0.3 to 0.8 and preferably from 0.4 to 0.7.
Une composition hydraulique selon l'invention inclut à la fois les compositions à l'état frais, par exemple un coulis de ciment, et à l'état durci, par exemple un mortier ou un béton. L'homme du métier comprend que la composition hydraulique à l'état frais comprend de l'eau servant à l'hydratation du liant, tandis que la composition hydraulique à l'état durci est obtenue après hydratation pour donner du béton ou du mortier. Polyalkylèneimines A hydraulic composition according to the invention includes both the compositions in the fresh state, for example a cement slurry, and in the cured state, for example a mortar or a concrete. Those skilled in the art understand that the fresh hydraulic composition comprises water for hydration of the binder, while the cured hydraulic composition is obtained after hydration to give concrete or mortar. polyalkyleneimines
La composition selon l'invention comprend au moins une polyalkylèneimine ramifiée. The composition according to the invention comprises at least one branched polyalkyleneimine.
De manière inattendue, la composition hydraulique de l'invention, qui incorpore au moins une polyalkylèneimine, présente une résistance à la carbonatation supérieure à une composition hydraulique de référence dépourvue de polyalkylèneimine, ce qui permet d'améliorer la durabilité de ladite composition hydraulique et diminuer la corrosion d'éventuelles armatures métalliques. Unexpectedly, the hydraulic composition of the invention, which incorporates at least one polyalkyleneimine, has a greater resistance to carbonation than a reference hydraulic composition free of polyalkyleneimine, which makes it possible to improve the durability of said hydraulic composition and reduce corrosion of any metal reinforcements.
En effet, comme il ressort clairement des exemples décrits ci-après, la présence d'une ou plusieurs polyalkylèneimine(s) dans une composition hydraulique s'avère contre attente tout particulièrement bénéfique pour diminuer la vitesse de carbonatation dans ladite composition.  Indeed, as is clear from the examples described below, the presence of one or more polyalkyleneimine (s) in a hydraulic composition proves against waiting particularly beneficial to reduce the carbonation rate in said composition.
La ou les polyalkylèneimine(s) de la composition hydraulique de l'invention possède(nt) un poids moléculaire compris de 400 g/mol à 1 000 000 g/mol, de préférence compris de 600 g/mol à 200 000 g/mol, préférentiellement de 800 g/mol à 50 000 g/mol, par exemple de 1 000 g/mol à 5 000 g/mol. Par « poids moléculaire », on entend un poids moléculaire moyen en poids (Mw). The polyalkyleneimine (s) of the hydraulic composition of the invention has (s) a molecular weight of from 400 g / mol to 1,000,000 g / mol, preferably from 600 g / mol to 200,000 g / mol preferably from 800 g / mol to 50,000 g / mol, for example from 1,000 g / mol to 5,000 g / mol. By "molecular weight" is meant a weight average molecular weight (Mw).
La ou les polyalkylèneimine(s) est (sont) présente(s) dans la composition selon un rapport massique compris de 0,05 % à 5,0 % par rapport à la masse du liant. The polyalkyleneimine (s) is (are) present in the composition in a weight ratio of 0.05% to 5.0% relative to the weight of the binder.
De préférence, le rapport massique de polyalkylèneimine(s) par rapport au liant est compris de 0,1 % à 4,0 %, préférentiellement de 0,15 % à 3,0 %, ou encore de 0,2 % à 1,5 %.  Preferably, the weight ratio of polyalkyleneimine (s) relative to the binder is from 0.1% to 4.0%, preferably from 0.15% to 3.0%, or from 0.2% to 1%, 5%.
La teneur en azote ( %sec) des polyalkylèneimines est avantageusement comprise de 15 % à 33 %.  The nitrogen content (% dry) of the polyalkyleneimines is advantageously from 15% to 33%.
La composition de l'invention peut comprendre un mélange de plusieurs polyalkylèneimines,. The composition of the invention may comprise a mixture of several polyalkyleneimines.
A titre de polyalkylèneimine, on peut citer la polyéthylèneimine ou la polypropylèneimine.  As polyalkyleneimine, mention may be made of polyethyleneimine or polypropyleneimine.
De préférence, la composition selon l'invention comprend au moins une polyéthylèneimine, préférentiellement une polyéthylèneimine ramifiée. Selon un mode de réalisation, la composition de l'invention comprend au moins une polyalkylèneimine ramifiée. Preferably, the composition according to the invention comprises at least one polyethyleneimine, preferably a branched polyethyleneimine. According to one embodiment, the composition of the invention comprises at least one branched polyalkyleneimine.
Les polyalkylèneimines ramifiées contiennent des aminés primaires, secondaires et tertiaires.  The branched polyalkyleneimines contain primary, secondary and tertiary amines.
II peut s'agir notamment d'une polyéthylèneimine ramifiée ou d'une polypropylèneimine ramifiée.  It may be in particular a branched polyethyleneimine or a branched polypropyleneimine.
Les polyéthylèneimines ramifiées sont généralement obtenues par polymérisation d'éthylèneimine (aussi appelée aziridine).  Branched polyethyleneimines are generally obtained by polymerization of ethyleneimine (also known as aziridine).
A titre de polyalkylèneimine ramifiée, on peut également citer les polyéthylèneimines dendrimère (dendrimère PEI) et les polypropylèneimines dendrimère (dendrimère PPI). Ces composés possèdent un noyau de type alkylènediamine et sont générés en arborescence (« en étoile ») autour de ce noyau, par empilement de couches de génération successives. Ces composés comprennent principalement des aminés primaires (en périphérie) et des aminés tertiaires (au cœur).  As branched polyalkyleneimine, mention may also be made of polyethyleneimines dendrimer (PEI dendrimer) and polypropyleneimines dendrimer (PPI dendrimer). These compounds have an alkylenediamine-type nucleus and are generated in a tree ("star") structure around this nucleus, by stacking successive generation layers. These compounds mainly comprise primary amines (at the periphery) and tertiary amines (at the heart).
Selon un mode de réalisation, la ou les polyalkylèneimine(s) (sont) présente(s) dans la composition de l'invention sous une forme libre, par exemple en solution aqueuse.  According to one embodiment, the polyalkyleneimine (s) (s) are present in the composition of the invention in a free form, for example in aqueous solution.
Clinker clinker
Le clinker utilisé selon la présente invention peut être un clinker Portland, un clinker sulfo-alumineux, un clinker alumineux, un clinker bélitique, un clinker sulfo-bélitique et leurs mélanges, de préférence un clinker Portland.  The clinker used according to the present invention may be a Portland clinker, a sulfo-aluminous clinker, an aluminous clinker, a belitic clinker, a sulpho-belitic clinker and mixtures thereof, preferably a Portland clinker.
Un clinker Portland est obtenu par clinkérisation à haute température d'un mélange comprenant notamment du calcaire et de l'argile. Par exemple, un clinker Portland est un clinker tel que défini dans la norme NF EN 197- 1 de février 2001.  A Portland clinker is obtained by high temperature clinkerisation of a mixture comprising in particular limestone and clay. For example, a Portland clinker is a clinker as defined in standard NF EN 197-1 of February 2001.
La proportion massique en clinker dans le liant hydraulique peut-être comprise de 0 % à The mass proportion of clinker in the hydraulic binder may be from 0% to
100 % par rapport à la masse du liant, de préférence de 5 % à 95 %, plus préférentiellement de 30 % à 85 %. 100% relative to the mass of the binder, preferably from 5% to 95%, more preferably from 30% to 85%.
Comme évoqué précédemment, l'invention est particulièrement intéressante pour des compositions hydrauliques possédant un faible taux en clinker.  As mentioned above, the invention is particularly advantageous for hydraulic compositions having a low clinker content.
Au sens de l'invention, un faible taux de clinker signifie une teneur massique en clinker dans le liant hydraulique inférieure à 85 %.  For the purposes of the invention, a low clinker ratio means a clinker mass content in the hydraulic binder less than 85%.
Ainsi, la quantité réduite en clinker est usuellement compensée dans le liant hydraulique par des additions minérales, comme par exemple un filler calcaire décrit ci-après. Addition minérale Thus, the reduced amount of clinker is usually compensated in the hydraulic binder by mineral additions, such as a limestone filler described below. Mineral addition
Les additions minérales sont généralement des matériaux utilisables en substitution partielle du clinker.  Mineral additions are generally materials that can be used as a partial substitution for clinker.
Les additions minérales convenant au liant hydraulique selon l'invention peuvent être choisies parmi les laitiers (par exemple tels que définis dans la norme NF EN 197-1 de février 2001, paragraphe 5.2.2), les pouzzolanes naturelles ou artificielles (par exemple telles que définies dans la norme NF EN 197-1 de février 2001, paragraphe 5.2.3), les cendres volantes (par exemple telles que définies dans la norme NF EN 197-1 de février 2001, paragraphe 5.2.4), les schistes calcinés (par exemple tels que définis dans la norme NF EN 197-1 de février 2001, paragraphe 5.2.5), les additions minérales à base de carbonate de calcium, par exemple le calcaire (par exemple tel que défini dans la norme NF EN 197- 1 de février 2001 , paragraphe 5.2.6), les fumées de silice (par exemple telles que définies dans la norme NF EN 197-1 de février 2001, paragraphe 5.2.7), les métakaolins, les cendres de biomasses (par exemple les cendres de cosses de riz) et leurs mélanges.  The mineral additives suitable for the hydraulic binder according to the invention may be chosen from slags (for example as defined in standard NF EN 197-1 of February 2001, paragraph 5.2.2), natural or artificial pozzolans (for example such as defined in standard NF EN 197-1 of February 2001, paragraph 5.2.3), fly ash (for example as defined in standard NF EN 197-1 of February 2001, paragraph 5.2.4), calcined schists (For example as defined in standard NF EN 197-1 of February 2001, paragraph 5.2.5), mineral additions based on calcium carbonate, for example limestone (for example as defined in standard NF EN 197 - 1 February 2001, paragraph 5.2.6), silica fumes (for example as defined in standard NF EN 197-1 of February 2001, paragraph 5.2.7), metakaolins, biomass ash (for example ashes of rice husks) and mixtures thereof.
Les additions minérales utilisées selon l'invention peuvent être également les cendres issues de la combustion de végétaux, comme par exemple les cendres issues de la combustion des balles de riz.  The mineral additions used according to the invention may also be ash from the combustion of plants, such as for example the ashes from the combustion of rice balls.
Les additions minérales utilisées selon l'invention peuvent être également des zéolithes. The mineral additions used according to the invention may also be zeolites.
Une cendre volante est généralement une particule pulvérulente comprise dans les fumées des centrales thermiques alimentées au charbon. Elle est généralement récupérée par précipitation électrostatique ou mécanique. Flying ash is usually a powdery particle in the flue gases of coal-fired power plants. It is usually recovered by electrostatic or mechanical precipitation.
La composition chimique d'une cendre volante dépend principalement de la composition chimique du charbon brûlé et du procédé utilisé dans la centrale thermique dont elle est issue. Il en est de même pour sa composition minéralogique. Les cendres volantes utilisées selon l'invention peuvent être de nature siliceuse ou calcique.  The chemical composition of a fly ash depends mainly on the chemical composition of the burned coal and the process used in the thermal power plant from which it originated. It is the same for its mineralogical composition. The fly ash used according to the invention may be of siliceous or calcic nature.
De préférence, la cendre volante utilisée selon la présente invention est choisie parmi celles telles que décrites dans la norme Européenne NF EN 197-1 de février 2001.  Preferably, the fly ash used according to the present invention is chosen from those as described in European Standard NF EN 197-1 of February 2001.
Les laitiers sont généralement obtenus par refroidissement rapide du laitier fondu provenant de la fusion du minerai de fer dans un haut fourneau.  Slags are generally obtained by rapidly cooling the molten slag from the smelting of iron ore in a blast furnace.
Les laitiers utilisés selon la présente invention peuvent être choisi parmi les laitiers granulés de haut fourneau selon la norme Européenne NF EN 197-1 de février 2001 paragraphe 5.2.2.  The slags used according to the present invention may be chosen from granulated blast furnace slags according to the European Standard NF EN 197-1 of February 2001, paragraph 5.2.2.
Les fumées de silice utilisées selon la présente invention peuvent être un matériau obtenu par réduction de quartz de grande pureté par du charbon dans des fours à arcs électriques utilisés pour la production de silicium et d'alliages de ferrosilicium. Les fumées de silice sont généralement formées de particules sphériques comprenant au moins 85 % en masse de silice amorphe. The silica fumes used according to the present invention can be a material obtained by reducing high-purity quartz by charcoal in electric arc furnaces. used for the production of silicon and ferrosilicon alloys. The silica fumes are generally formed of spherical particles comprising at least 85% by mass of amorphous silica.
De préférence, les fumées de silice utilisées selon la présente invention sont choisies parmi les fumées de silice selon la norme Européenne NF EN 197-1 de février 2001 paragraphe 5.2.7.  Preferably, the silica fumes used according to the present invention are chosen from silica fumes according to the European standard NF EN 197-1 of February 2001, paragraph 5.2.7.
Les matériaux pouzzolaniques utilisés selon la présente invention peuvent être des substances naturelles siliceuses ou silico-alumineuses, ou une combinaison de celles-ci. Parmi les matériaux pouzzolaniques, on peut citer les pouzzolanes naturelles, qui sont en général des matériaux d'origine volcanique ou des roches sédimentaires, et les pouzzolanes naturelles calcinées, qui sont des matériaux d'origine volcanique, des argiles, des schistes ou des roches sédimentaires, activés thermiquement. Les matériaux pouzzolaniques utilisés selon l'invention peuvent être choisis parmi les ponces, les tuffs, les scories ou leurs mélanges.  The pozzolanic materials used according to the present invention may be natural siliceous or silico-aluminous substances, or a combination thereof. Pozzolanic materials include natural pozzolans, which are generally materials of volcanic origin or sedimentary rocks, and calcined natural pozzolans, which are materials of volcanic origin, clays, shales or rocks. sedimentary, thermally activated. The pozzolanic materials used according to the invention may be chosen from pumice, tuffs, slag or mixtures thereof.
De préférence, les matériaux pouzzolaniques utilisés selon la présente invention sont choisis parmi les matériaux pouzzolaniques selon la norme Européenne NF EN 197-1 de février 2001 paragraphe 5.2.3.  Preferably, the pozzolanic materials used according to the present invention are chosen from pozzolanic materials according to European Standard NF EN 197-1 of February 2001, section 5.2.3.
De préférence, les additions minérales utilisées selon l'invention sont des matériaux contenant du carbonate de calcium, par exemple du calcaire (aussi appelé filler calcaire).  Preferably, the mineral additives used according to the invention are materials containing calcium carbonate, for example limestone (also called limestone filler).
Les argiles calcinées utilisées selon la présente invention peuvent résulter de la calcination d'une argile, la kaolinite, associée à différents minéraux (phyllosilicates, quartz, oxydes de fer) en proportions variables suivant les gisements. Ils peuvent être obtenus soit par calcination broyage soit par broyage calcination dans des unités de production à fours rotatifs, à plateaux ou par calcination dite « flash », par exemple. Ils sont essentiellement composés de particules de silicate d'alumine amorphe.  The calcined clays used according to the present invention can result from the calcination of a clay, kaolinite, associated with different minerals (phyllosilicates, quartz, iron oxides) in varying proportions depending on the deposits. They can be obtained either by grinding calcination or by grinding calcination in production units with rotary kilns, trays or so-called "flash" calcination, for example. They are essentially composed of amorphous alumina silicate particles.
De préférence, les argiles calcinées utilisés selon la présente invention peuvent être choisis parmi les métakaolins selon l'avant-projet de norme PR NF P 18-513 de décembre 2011.  Preferably, the calcined clays used according to the present invention may be chosen from metakaolins according to the preliminary draft standard PR NF P 18-513 of December 2011.
Selon une variante, le liant hydraulique de l'invention peut en outre comprendre du sulfate de calcium. According to one variant, the hydraulic binder of the invention may further comprise calcium sulphate.
Le sulfate de calcium utilisé inclut le gypse (sulfate de calcium dihydraté, CaS04.2H20), le semi-hydrate (CaS04.1/2H20), l'anhydrite (sulfate de calcium anhydre, CaS04) ou un de leurs mélanges. Le gypse et l'anhydrite existent à l'état naturel. Il est également possible d'utiliser un sulfate de calcium qui est un sous-produit de certains procédés industriels. En général, le liant hydraulique de l'invention comprend de 3 % à 28 % de sulfate de calcium en masse par rapport à la masse de clinker. The calcium sulphate used includes gypsum (calcium sulphate dihydrate, CaSO 4 .2H 2 O), hemihydrate (CaSO 4 .1 / 2H 2 O), anhydrite (anhydrous calcium sulphate, CaSO 4 ) or one of their mixtures. Gypsum and anhydrite exist in their natural state. It is also possible to use a calcium sulphate which is a by-product of certain industrial processes. In general, the hydraulic binder of the invention comprises from 3% to 28% by weight of calcium sulphate relative to the weight of clinker.
Une teneur élevée en sulfate de calcium est généralement adoptée pour les ciments alumineux et sulfoalumineux. La nature chimique (gypse, semi-hydrate ou anhydrite) et le dosage en sulfate de calcium sont avantageusement ajustés en fonction du ciment pour éviter le gonflement des hydrates.  A high content of calcium sulphate is generally adopted for aluminous and sulphoaluminous cements. The chemical nature (gypsum, hemihydrate or anhydrite) and the calcium sulphate dosage are advantageously adjusted depending on the cement to prevent swelling of the hydrates.
Dans le cas où le clinker est un clinker Portland, le liant hydraulique de l'invention comprend de 1 % à 8 %, de préférence de 2 % à 5 % de sulfate de calcium en masse par rapport à la masse de clinker.  In the case where the clinker is a Portland clinker, the hydraulic binder of the invention comprises from 1% to 8%, preferably from 2% to 5% by mass of calcium sulphate relative to the mass of clinker.
Un liant selon l'invention est généralement obtenu par co-broyage d'un clinker et de sulfate de calcium.  A binder according to the invention is generally obtained by co-grinding a clinker and calcium sulphate.
Eléments métalliques Metallic elements
La composition de l'invention, en particulier la composition hydraulique de l'invention, peut comprendre à l'état durci des éléments métalliques, comme par exemple des armatures, notamment des armatures pour béton armé selon la norme européenne NF EN 1992-1-1 d'octobre 2005.  The composition of the invention, in particular the hydraulic composition of the invention, may comprise, in the cured state, metallic elements, for example reinforcements, in particular reinforced concrete reinforcements according to the European standard NF EN 1992-1- 1 of October 2005.
Les armatures peuvent se présenter sous forme de barres, de treillis soudés ou assemblage de barres, de ferraillages. Les jonctions des barres peuvent être assurées par recouvrement, par dispositif de raboutage, par soudure, par ligature, par sertissage ou tout autre moyen.  The frames can be in the form of bars, welded mesh or assembly of bars, reinforcement. The junctions of the bars may be provided by overlapping, splicing, soldering, ligation, crimping or any other means.
Selon une variante de l'invention, les éléments métalliques sont des fibres d'acier tréfilé remplaçant complètement ou partiellement des armatures métalliques ordinaires dans certaines applications (dallages, béton projeté ou béton de réparation).  According to a variant of the invention, the metal elements are drawn steel fibers completely or partially replacing ordinary metal reinforcements in certain applications (pavements, shotcrete or repair concrete).
Granulats aggregates
La composition de l'invention, en particulier la composition hydraulique de l'invention, peut comprendre des granulats.  The composition of the invention, in particular the hydraulic composition of the invention, may comprise aggregates.
Les granulats éventuellement utilisés dans la composition selon l'invention incluent du sable (dont les particules ont généralement une taille maximale (Dmax) inférieure ou égale à 4 mm), et éventuellement des gravillons (dont les particules ont généralement une taille minimale (Dmin) supérieure à 4 mm et de préférence une Dmax inférieure ou égale à 20 mm). Les granulats utilisés dans la composition selon l'invention sont généralement conformes à la norme européenne NF EN 12620 d'août 2003, et sont d'origine naturelle ou artificielle. Les granulats peuvent être également du bois. The aggregates optionally used in the composition according to the invention include sand (whose particles generally have a maximum size (Dmax) less than or equal to 4 mm), and possibly chippings (whose particles generally have a minimum size (Dmin) greater than 4 mm and preferably a Dmax less than or equal to 20 mm). The aggregates used in the composition according to the invention are generally conform to the European standard NF EN 12620 of August 2003, and are of natural or artificial origin. Aggregates can also be wood.
Adjuvants admixtures
La composition de l'invention, en particulier la composition hydraulique de l'invention, peut comprendre des adjuvants conventionnels sous réserve de leur compatibilité avec la ou les polyalkylèneimines requises selon l'invention.  The composition of the invention, in particular the hydraulic composition of the invention, may comprise conventional adjuvants subject to their compatibility with the polyalkyleneimine (s) required according to the invention.
Les adjuvants utilisables dans la composition hydraulique selon l'invention peuvent par exemple être un de ceux décrits dans les normes européennes NF EN 934-2 de septembre 2002, NF EN 934-3 de novembre 2009 ou NF EN 934-4 d'août 2009. Avantageusement, la composition hydraulique selon l'invention comprend au moins un adjuvant pour composition hydraulique : un accélérateur, un agent entraîneur d'air, un agent viscosant, un retardateur, un inertant des argiles, un agent antimousse, un plastifiant et/ou un superplastifiant.  The adjuvants that can be used in the hydraulic composition according to the invention can for example be one of those described in European standards NF EN 934-2 of September 2002, NF EN 934-3 of November 2009 or NF EN 934-4 of August 2009. Advantageously, the hydraulic composition according to the invention comprises at least one adjuvant for hydraulic composition: an accelerator, an air-entraining agent, a viscosifying agent, a retarder, an inerting clays, an antifoaming agent, a plasticizer and / or a superplasticizer.
De préférence, la composition hydraulique selon l'invention comprend au moins un agent antimousse évitant l'entraînement d'air dans la composition.  Preferably, the hydraulic composition according to the invention comprises at least one antifoam agent avoiding the entrainment of air in the composition.
Les inertants des argiles sont des composés qui permettent de réduire ou de prévenir les effets néfastes des argiles sur les propriétés des liants hydrauliques. Les inertants des argiles incluent ceux décrits dans WO 2006/032785 et WO 2006/032786.  Inerting clays are compounds that reduce or prevent the harmful effects of clays on the properties of hydraulic binders. Inerting clays include those described in WO 2006/032785 and WO 2006/032786.
Le terme "superplastifiant" tel qu'utilisé dans la présente description et les revendications qui l'accompagnent est à comprendre comme incluant à la fois les réducteurs d'eau et les superplastifiants tels que décrits dans le livre intitulé « Concrète Admixtures Handbook, Properties Science and Technology », V.S. Ramachandran, Noyés Publications, 1984.  The term "superplasticizer" as used in the present 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.
Un réducteur d'eau est défini comme un adjuvant qui réduit de typiquement 10 % à 15 % la quantité d'eau de gâchage d'un béton pour une ouvrabilité donnée. Les réducteurs d'eau incluent, par exemple les lignosulfonates, les acides hydroxycarboxyliques, les glucides et d'autres composés organiques spécialisés, par exemple le glycérol, l'alcool polyvinylique, l'alumino-méthyl-siliconate de sodium, l'acide sulfanilique et la caséine.  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 15%. Water reducers include, for example, lignosulfonates, hydroxycarboxylic acids, carbohydrates and other specialized organic compounds, for example glycerol, polyvinyl alcohol, sodium alumino-methyl-siliconate, sulfanilic acid and casein.
Les superplastifiants appartiennent à une nouvelle classe de réducteurs d'eau, chimiquement différents des réducteurs d'eau normaux et capables de réduire les quantités d'eau d'environ 30 %. Les superplastifiants ont été globalement classés en quatre groupes : les condensais sulfonés de naphtalène formaldéhyde (SNF) (généralement un sel de sodium) ; les condensais sulfonés de mélamine formaldéhyde (SMF) ; les lignosulfonates modifiés (MLS) ; et les autres. Des superplastifiants plus récents incluent des composés polycarboxyliques comme les polycarboxylates, par exemple les polyacrylates. Un superplastifiant est de préférence un superplastifiant nouvelle génération, par exemple un copolymère contenant un polyéthylène glycol comme chaîne greffée et des fonctions carboxyliques dans la chaîne principale comme un éther polycarboxylique. Les polycarboxylates-polysulfonates de sodium et les polyacrylates de sodium peuvent aussi être utilisés. Les dérivés d'acide phosphonique, les polycarboxylate-polysulfonates de sodium et les polyacrylates de sodium peuvent aussi être utilisés. La quantité nécessaire de superplastifiant dépend généralement de la réactivité du ciment. Plus la réactivité est faible, plus la quantité nécessaire de superplastifiant est faible. Pour réduire la quantité totale de sels alcalins, le superplastifiant peut être utilisé sous forme de sel de calcium plutôt que sous forme de sel de sodium. 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 were 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 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 can also be used. Phosphonic acid derivatives, sodium polycarboxylate polysulfonates and sodium polyacrylates may 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.
D'autres additifs peuvent être incorporés dans la composition selon l'invention, par exemple, un agent antimousse (par exemple polydiméthylsiloxane ; le triisobutylphosphonate). Les agents antimousses comprennent également les silicones sous forme de solution, de. solide ou de préférence sous forme de résine, d'huile ou d'émulsion, de préférence dans l'eau. Plus particulièrement adaptés sont les silicones comprenant des groupements (RSiOo,5) et (R2SiO). Other additives may be incorporated in the composition according to the invention, for example an antifoaming agent (for example polydimethylsiloxane, triisobutylphosphonate). Antifoam agents also include silicones in the form of a solution of. solid or preferably in the form of resin, oil or emulsion, preferably in water. More particularly suitable are silicones comprising (RSiOo, 5) and (R 2 SiO) groups.
Dans ces formules, les radicaux R, qui peuvent être identiques ou différents, sont de préférence un atome d'hydrogène ou un groupe alkyle de 1 à 8 atomes de carbone, le groupe méthyle étant préféré. Le nombre de motifs est de préférence de 30 à 120.  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.
La quantité d'un tel agent dans le ciment final est généralement d'au plus 5 parties en poids par rapport au ciment.  The amount of such an agent in the final cement is generally at most 5 parts by weight relative to the cement.
Selon un mode de réalisation préféré, une composition selon l'invention peut comprendre : According to a preferred embodiment, a composition according to the invention can comprise:
un liant hydraulique comprenant un clinker Portland, du sulfate de calcium et un filler calcaire ou une autre addition minérale, la proportion massique de clinker dans le liant étant comprise de 30 % à 85 %,  a hydraulic binder comprising a Portland clinker, calcium sulphate and a calcined filler or other mineral addition, the mass proportion of clinker in the binder being from 30% to 85%,
au moins une polyalkylèneimine ramifiée de poids moléculaire compris de 400 g/mol à 1 000 000 g/mol, de préférence compris de 600 g/mol à 200 000 g/mol, préférentiellement de 800 g/mol à 50 000 g/mol, par exemple de 1 000 g/mol à 5 000 g/mol, selon une proportion massique comprise de 0,05 % à 5,0 % par rapport à la masse dudit liant hydraulique,  at least one branched polyalkyleneimine with a molecular weight of from 400 g / mol to 1,000,000 g / mol, preferably from 600 g / mol to 200,000 g / mol, preferably from 800 g / mol to 50,000 g / mol, for example from 1,000 g / mol to 5,000 g / mol, in a proportion by weight of between 0.05% and 5.0% relative to the weight of said hydraulic binder,
de l'eau, selon une proportion telle que le rapport massique eau/liant est compris de 0,3 à 0,8 et préférentiellement de 0,4 à 0,7,  water, in a proportion such that the weight ratio water / binder is from 0.3 to 0.8 and preferably from 0.4 to 0.7,
éventuellement un granulat tel qu'un sable, et éventuellement un agent antimousse. optionally a granulate such as sand, and optionally an antifoaming agent.
La présente invention se rapporte également à un procédé de fabrication d'une composition selon l'invention, comprenant une étape de mise en contact d'au moins un liant hydraulique, comprenant au moins un clinker, avec au moins une polyalkylèneimine ramifiée, ayant un poids moléculaire de 400 g/mol à 1 000 000 g/mol, selon un rapport pondéral polyalkylèneimine(s)/liant compris de 0,05 % à 5,0 %. The present invention also relates to a method for manufacturing a composition according to the invention, comprising a step of contacting at least one hydraulic binder, comprising at least one clinker, with at least one branched polyalkyleneimine, having a a molecular weight of 400 g / mol to 1,000,000 g / mol, in a polyalkyleneimine (s) / binder weight ratio of from 0.05% to 5.0%.
De préférence, notamment lorsque la composition préparée est une composition hydraulique, le liant hydraulique et la ou les polyalkylèneimine(s) sont mis en contact en présence d'eau.  Preferably, especially when the composition prepared is a hydraulic composition, the hydraulic binder and the polyalkyleneimine (s) are contacted in the presence of water.
La composition hydraulique selon l'invention peut être utilisée directement sur chantier à l'état frais et coulée dans un coffrage adapté à l'application visée, ou utilisée en usine de préfabrication.  The hydraulic composition according to the invention can be used directly on site in the fresh state and cast in a formwork adapted to the intended application, or used in prefabrication plant.
Le gâchage de la composition hydraulique peut être effectué selon des méthodes connues de l'homme du métier.  The mixing of the hydraulic composition can be carried out according to methods known to those skilled in the art.
Ainsi, la ou les polyalkylèneimine(s) peu(ven)t être ajoutée(s) à l'eau ou à un des composants de la composition hydraulique selon la présente invention, par exemple au liant hydraulique ou aux granulats.  Thus, the polyalkyleneimine (s) can be added to the water or to one of the components of the hydraulic composition according to the present invention, for example to hydraulic binder or aggregates.
La ou les polyalkylèneimine(s) peu(ven)t être ajoutée(s) à n'importe quel moment de la fabrication de la composition hydraulique à l'état frais selon l'invention, sous forme de solide ou de liquide.  The polyalkyleneimine (s) may be added at any time during the manufacture of the fresh hydraulic composition according to the invention, in solid or liquid form.
Selon un mode de réalisation préféré, la ou les polyalkylèneimine(s) est (sont) mise(s) en œuvre sous la forme d'une solution aqueuse.  According to a preferred embodiment, the polyalkyleneimine (s) is (are) implemented in the form of an aqueous solution.
Ce mode de réalisation est particulièrement adapté au cas de polyalkylèneimine(s) soluble(s) dans l'eau à pH basique, comme c'est le cas des polyalkylèneimines ramifiées.  This embodiment is particularly suitable for the case of polyalkyleneimine (s) soluble in water at basic pH, as is the case of branched polyalkyleneimines.
Utilisation use
La présente invention se rapporte également à l'utilisation d'au moins une polyalkylèneimine ramifiée, ayant un poids moléculaire compris de 400 g/mol à 1 000 000 g/mol, pour réduire et/ou prévenir la carbonatation au sein d'une composition hydraulique comprenant un liant hydraulique, ladite ou lesdites polyalkylèneimine(s) étant présente(s) dans la composition hydraulique selon un rapport pondéral polyalkylèneimine(s)/liant compris de 0,05 % à 5,0 %. La présente invention se rapporte plus particulièrement à l'utilisation d'au moins une polyalkylèneimine ramifiée, ayant un poids moléculaire compris de 400 g/mol à 1 000 000 g/mol, en association avec un liant hydraulique dans une composition hydraulique à l'état frais, ladite ou lesdites polyalkylèneimine(s) étant présente(s) dans la composition hydraulique selon un rapport pondéral polyalkylèneimine(s)/liant compris de 0,05 % à 5,0 %, pour réduire et/ou prévenir la carbonatation au sein de ladite composition hydraulique à l'état durci. The present invention also relates to the use of at least one branched polyalkyleneimine having a molecular weight of from 400 g / mol to 1,000,000 g / mol to reduce and / or prevent carbonation in a composition hydraulic system comprising a hydraulic binder, said at least one polyalkyleneimine (s) being present in the hydraulic composition in a polyalkyleneimine (s) / binder weight ratio of from 0.05% to 5.0%. The present invention relates more particularly to the use of at least one branched polyalkyleneimine, having a molecular weight of from 400 g / mol to 1 000 000 g / mol, in combination with a hydraulic binder in a hydraulic composition at the a fresh state, said at least one polyalkyleneimine (s) being present in the hydraulic composition in a polyalkyleneimine (s) / binder weight ratio of from 0.05% to 5.0%, for reducing and / or preventing carbonation at within said hydraulic composition in the cured state.
Objet mis en forme Shaped object
La composition selon la présente invention peut être mise en forme pour produire, après hydratation et durcissement, un objet mis en forme pour le domaine de la construction.  The composition according to the present invention can be shaped to produce, after hydration and hardening, a shaped object for the field of construction.
L'invention se rapporte également à un tel objet mis en forme, obtenu à partir d'une composition selon la présente invention, en particulier d'une composition hydraulique selon la présente invention.  The invention also relates to such a shaped object, obtained from a composition according to the present invention, in particular a hydraulic composition according to the present invention.
Les objets mis en forme pour le domaine de la construction incluent, par exemple, un sol, une chape, une fondation, un mur, une cloison, un plafond, une poutre, un plan de travail, un pilier, une pile de pont, un parpaing, une canalisation, un poteau, un escalier, un panneau, une corniche, un moule, un élément de voirie (par exemple une bordure de trottoir), ou un revêtement (par exemple de route ou de mur).  Objects shaped for the field of construction include, for example, a floor, a screed, a foundation, a wall, a partition, a ceiling, a beam, a worktop, a pillar, a bridge stack, a cinder block, a pipe, a pole, a staircase, a panel, a cornice, a mold, a road element (for example a curb), or a covering (for example road or wall).
Dans la présente description, y compris les revendications qui l'accompagnent, les pourcentages sont exprimés par masse, sauf quand il en est autrement spécifié.  In the present description, including the accompanying claims, the percentages are by mass unless otherwise specified.
Les exemples suivants illustrent la réalisation de l'invention.  The following examples illustrate the embodiment of the invention.
EXEMPLES EXAMPLES
Exemple 1 - Préparation des éprouvettes de mortier Example 1 - Preparation of mortar specimens
Des éprouvettes de mortier ont été préparées à partir d'une composition hydraulique comprenant un liant hydraulique à faible taux de clinker (substitué par 35 % d'un filler calcaire). Le ratio eau/liant est égal à 0,55 et le dosage en TiBP, TrilsoButyl Phosphate (agent antimousse) est de 0,09 %/liant.  Mortar specimens were prepared from a hydraulic composition comprising a low clinker hydraulic binder (substituted by 35% of a limestone filler). The water / binder ratio is equal to 0.55 and the TiBP TrilsoButyl Phosphate (antifoam) dosage is 0.09% / binder.
La composition des éprouvettes est indiquée dans le Tableau 1 et les caractéristiques du ciment et du sable sont indiquées dans les Tableaux 2 et 3. Tableau 1 The composition of the specimens is shown in Table 1 and the characteristics of the cement and sand are shown in Tables 2 and 3. Table 1
Tableau 2 : Caractéristiques du CEM I 52.5 N CE CP2 NF, Saint Pierre La Cour Table 2: Characteristics of the CEM I 52.5 N CE CP2 NF, Saint Pierre The Court
Tableau 3 : Caractéristi ues du sable norma isé (EN 12620) Table 3: Characteristics of standardized sand (EN 12620)
Les polyéthylèneimines (PEI) ramifiées du Tableau 4 ont été utilisées, en diverses proportions (en masse) par rapport au liant hydraulique. Tableau 4 The branched polyethyleneimines (PEI) of Table 4 were used in various proportions (by weight) relative to the hydraulic binder. Table 4
Protocole de préparation Protocol of preparation
Le sable a été mis dans le bol d'un malaxeur Perrier type 32 avec l'eau de prémouillage. Le malaxage a débuté et a été maintenu à petite vitesse pendant 1 minute.  The sand was put into the bowl of a Perrier type 32 mixer with prewetting water. Mixing started and was maintained at low speed for 1 minute.
Le malaxage a ensuite été stoppé pendant 4 minutes.  The kneading was then stopped for 4 minutes.
Le liant hydraulique (clinker+filler) a été ajouté et le malaxage a repris à petite vitesse pendant 1 minute.  The hydraulic binder (clinker + filler) was added and kneading was resumed at low speed for 1 minute.
L'eau de gâchage, comprenant les adjuvants (polyéthylèmeneimine ramifiée et antimousse), a ensuite été ajoutée en 30 secondes tout en malaxant à petite vitesse.  The mixing water, comprising the adjuvants (branched polyethylenimine and antifoam), was then added in 30 seconds while mixing at low speed.
Le mélange a été malaxé à grande vitesse pendant 1 minute, pour obtenir un mortier.  The mixture was kneaded at high speed for 1 minute to obtain a mortar.
Le mortier a ensuite été coulé dans des moules en polystyrène de dimensions 4 cm x 4 cm x 16 cm (sans vibration), afin d'obtenir 6 éprouvettes de béton (démoulées après 24 h à 20 °C à 100 % d'humidité relative). The mortar was then poured into polystyrene molds measuring 4 cm x 4 cm x 16 cm (without vibration) to obtain 6 concrete specimens (demolded after 24 h at 20 ° C at 100% relative humidity). ).
Exemple 2 - Mesure de la carbonatation des éprouvettes de mortierExample 2 - Measurement of carbonation of the mortar specimens
Protocole de mesure Measurement protocol
Les éprouvettes de mortier ont ensuite été placées dans des conditions de carbonatation accélérée. Après 6 jours de cure en armoire humide à 100 % d'humidité relative et 20 °C, les éprouvettes ont été placées dans un caisson de carbonatation (cuve rectangulaire en PEHD, de 576 litres de capacité, muni d'un couvercle étanche), dont l'atmosphère a été enrichie en CO2 (10 % +/- 0,5 % de C02 dans le volume d'air du caisson), 20 °C +/-1 °C et 65 % +/- 5 % d'humidité relative. The mortar specimens were then placed under accelerated carbonation conditions. After 6 days of curing in a wet cabinet at 100% relative humidity and 20 ° C., the test pieces were placed in a carbonation box (rectangular HDPE tank, with a capacity of 576 liters, equipped with a tight-fitting lid). whose atmosphere has been enriched with CO 2 (10% +/- 0.5% C0 2 in the air volume of the chamber), 20 ° C +/- 1 ° C and 65% +/- 5% relative humidity.
La régulation en température a été assurée par le fait que le caisson est disposé dans un laboratoire régulé à 20 +/-1 °C. Le taux d'humidité relative a été régulé par un bac rempli de sel de nitrate d'ammonium saturé d'eau, ce bac étant positionné au fond du caisson, sur toute la surface disponible. Pour le CO2, le caisson a été connecté à un réseau alimenté par des bouteilles remplies d'un mélange 50 % CO2 / 50 % d'azote sous pression. Une centrale de détente a permis de délivrer le mélange à 1 bar de pression relative dans le réseau. L'introduction du gaz a été gérée de façon automatique par un analyseur de CO2 gazeux qui a analysé en continu l'atmosphère du caisson (analyseur mural, de la marque ABISS, modèle LMP 320, fourni par la société PBI Datasensor). A chaque introduction de gaz, une autre électro vanne s'ouvrait pour évacuer le surplus de gaz vers un vide sanitaire extérieur au laboratoire, ceci afin d'éviter toute surpression dans le caisson. Un ventilateur a fonctionné en continu pour avoir une répartition homogène du CO2 gazeux dans l'atmosphère du caisson. The temperature regulation was ensured by the fact that the box is placed in a laboratory regulated at 20 +/- 1 ° C. The relative humidity was regulated by a tray filled with ammonium nitrate salt saturated with water, this tray being positioned at the bottom of the box, over the entire available surface. For CO 2 , the box was connected to a network fed by bottles filled with a mixture of 50% CO 2 /50% nitrogen under pressure. An expansion unit has enabled the mixture to be delivered at 1 bar of relative pressure in the network. The introduction of the gas was managed automatically by a CO 2 gas analyzer which continuously analyzed the atmosphere of the box (ABISS wall scanner, model LMP 320, supplied by the company PBI Datasensor). At each introduction of gas, another electro valve was opened to evacuate excess gas to a crawl space outside the laboratory, this to prevent overpressure in the box. A fan operated continuously to have a homogeneous distribution of CO 2 gas in the atmosphere of the box.
A différentes échéances (à 2, 3, 4, 7, 13, 14, 28, et à 35 jours), les éprouvettes ont été sorties du caisson de carbonatation et fendues à l'aide d'un coupe-pavé hydraulique pour déterminer la profondeur de carbonatation.  At different deadlines (at 2, 3, 4, 7, 13, 14, 28, and 35 days), the specimens were taken out of the carbonation box and split with a hydraulic cutter to determine depth of carbonation.
La résistance à la carbonatation a été estimée en mesurant la vitesse de carbonatation des éprouvettes. Plus cette vitesse est élevée, moins le béton est résistant à la carbonatation, et plus le risque de corrosion des armatures de structure est élevé. Cette vitesse a été mesurée en déterminant la profondeur de béton carbonaté après différentes périodes d'exposition des éprouvettes dans le caisson enrichi en CO2 gazeux. Le matériau est dit carbonaté lorsque son pH est inférieur ou égal à 9. Ceci a été visualisé en pulvérisant une solution de phénolphtaléine à 0,5 % diluée dans un mélange composé à 50 % d'eau déminéralisée et 50 % d'éthanol. La phénolphtaléine est un indicateur coloré qui vire au rose pourpre lorsque le pH est supérieur à 9 et reste incolore lorsque le pH est inférieur à 9. Les zones de béton carbonatées sont donc celles qui restent incolores après pulvérisation de la suspension de phénolphtaléine. Les profondeurs de béton et mortier carbonatés ont été mesurées en plusieurs zones. La moyenne arithmétique des valeurs obtenues a été calculée. La vitesse de la carbonatation est exprimée en mm/jour . Il s'agit de la pente de la droite obtenue lorsque l'on représente l'évolution de la profondeur de carbonatation (en mm) en fonction de la racine carrée du temps (en jour). Resistance to carbonation was estimated by measuring the carbonation rate of the specimens. The higher this speed, the less resistant the concrete is to carbonation, and the greater the risk of structural reinforcement corrosion. This speed was measured by determining the depth of carbonated concrete after different periods of exposure of the specimens in the box enriched in gaseous CO 2 . The material is said to be carbonated when its pH is less than or equal to 9. This was visualized by spraying a solution of 0.5% phenolphthalein diluted in a mixture composed of 50% demineralized water and 50% ethanol. Phenolphthalein is a colored indicator that changes to purple pink when the pH is above 9 and remains colorless when the pH is below 9. The carbonated concrete zones are therefore those that remain colorless after spraying the phenolphthalein suspension. The depths of carbonate concrete and mortar were measured in several zones. The arithmetic mean of the values obtained was calculated. The carbonation rate is expressed in mm / day. This is the slope of the line obtained when we represent the evolution of the carbonation depth (in mm) as a function of the square root of time (in days).
Résultats  Results
Les résultats de la mesure de la vitesse de carbonatation (mm/jour1/2) en fonction de la proportion (%/liant) et du poids moléculaire (g/mol) du PEI sont indiqués dans le Tableau 5 : The results of the measurement of the carbonation rate (mm / day 1/2 ) as a function of the proportion (% / binder) and the molecular weight (g / mol) of the PEI are indicated in Table 5:
Tableau 5 Table 5
Toutes les PEI et tous les dosages par rapport au liant ont conduit à des vitesses de carbonatation réduites par rapport à la référence sans PEI. All PEI and all binder based assays resulted in reduced carbonation rates compared to the reference without PEI.
Il est observé que la vitesse de carbonatation diminue quand la proportion massique de PEI par rapport au liant augmente.  It is observed that the carbonation rate decreases when the mass proportion of PEI relative to the binder increases.

Claims

REVENDICATIONS
1. Composition comprenant au moins : 1. Composition comprising at least:
un liant hydraulique comprenant au moins un clinker, et  a hydraulic binder comprising at least one clinker, and
au moins une polyalkylèneimine ramifiée, ayant un poids moléculaire compris de 400 g/mol à 1 000 000 g/mol, selon un rapport pondéral polyalkylèneimine(s)/liant compris de 0,05 % à 5,0 %.  at least one branched polyalkyleneimine having a molecular weight of from 400 g / mol to 1,000,000 g / mol, in a polyalkyleneimine (s) / binder weight ratio of from 0.05% to 5.0%.
2. Composition selon la revendication 1, caractérisée en ce qu'elle est constituée dudit liant hydraulique et d'une ou plusieurs polyalkylèneimine(s). 2. Composition according to claim 1, characterized in that it consists of said hydraulic binder and one or more polyalkyleneimine (s).
3. Composition selon la revendication 1, comprenant en outre de l'eau, de préférence selon un rapport massique eau/liant compris de 0,3 à 0,8. 3. Composition according to claim 1, further comprising water, preferably in a weight ratio water / binder of 0.3 to 0.8.
4. Composition selon la revendication 1 ou 3, comprenant en outre des éléments métalliques, de préférence des armatures. 4. Composition according to claim 1 or 3, further comprising metal elements, preferably reinforcements.
5. Composition selon l'une quelconque des revendications précédentes, dans laquelle la polyalkylèneimine est une polyéthylèneimine ou une polypropylèneimine, de préférence une polyéthylèneimine. 5. A composition according to any one of the preceding claims, wherein the polyalkyleneimine is a polyethyleneimine or a polypropyleneimine, preferably a polyethyleneimine.
6. Composition selon l'une quelconque des revendications précédentes, dans lequel le clinker est un clinker Portland. 6. Composition according to any one of the preceding claims, wherein the clinker is a Portland clinker.
7. Composition selon l'une quelconque des revendications précédentes, dans laquelle la proportion massique en clinker dans le liant hydraulique est comprise de 5 % à 95 %, de préférence de 30 % à 85 %, par rapport à la masse dudit liant. 7. Composition according to any one of the preceding claims, wherein the mass proportion of clinker in the hydraulic binder is from 5% to 95%, preferably from 30% to 85%, relative to the mass of said binder.
8. Composition selon l'une quelconque des revendications précédentes, dans laquelle le rapport pondéral polyalkylèneimine(s)/liant est compris de 0,1 % à 4,0 %, préférentiellement de 0,15 % à 3,0 %, ou encore de 0,2 % à 1,5 %. 8. Composition according to any one of the preceding claims, wherein the polyalkyleneimine (s) / binder weight ratio is from 0.1% to 4.0%, preferably from 0.15% to 3.0%, or from 0.2% to 1.5%.
9. Composition selon l'une quelconque des revendications précédentes, dans laquelle le liant hydraulique comprend en outre au moins une addition minérale, qui est de préférence choisie dans le groupe constitué par les laitiers, les pouzzolanes, les cendres volantes, les schistes calcinés, les matériaux à base de carbonate de calcium, les fumées de silice, les métakaolins, les cendres de biomasse et leurs mélanges. 9. Composition according to any one of the preceding claims, wherein the hydraulic binder further comprises at least one mineral addition, which is preferably selected from the group consisting of slags, pozzolans, ashes. calcined schists, calcium carbonate materials, silica fumes, metakaolins, biomass ashes and mixtures thereof.
10. Procédé de fabrication d'une composition selon l'une quelconque des revendications 1 à 10, comprenant une étape de mise en contact d'au moins un liant hydraulique, comprenant au moins un clinker, avec au moins une polyalkylèneimine ramifiée, ayant un poids moléculaire de 400 g/mol à 1 000 000 g/mol, selon un rapport pondéral polyalkylèneimine(s)/liant compris de 0,05 % à 5,0 %. 10. A method of manufacturing a composition according to any one of claims 1 to 10, comprising a step of contacting at least one hydraulic binder, comprising at least one clinker, with at least one branched polyalkyleneimine having a a molecular weight of 400 g / mol to 1,000,000 g / mol, in a polyalkyleneimine (s) / binder weight ratio of from 0.05% to 5.0%.
11. Procédé de fabrication d'une composition selon la revendication 1 ou 3, dans lequel la ou les polyalkylèneimine(s) est (sont) mise(s) en œuvre sous la forme d'une solution aqueuse. 11. The method of manufacturing a composition according to claim 1 or 3, wherein the one or more polyalkyleneimine (s) is (are) implemented in the form of an aqueous solution.
12. Utilisation d'au moins une polyalkylèneimine ramifiée, ayant un poids moléculaire compris de 400 g/mol à 1 000 000 g/mol, pour réduire et/ou prévenir la carbonatation au sein d'une composition hydraulique comprenant au moins un liant hydraulique, ladite ou lesdites polyalkylèneimine(s) étant présente(s) dans la composition hydraulique selon un rapport pondéral polyalkylèneimine(s)/liant compris de 0,05 % à 5,0 %. Use of at least one branched polyalkyleneimine having a molecular weight of from 400 g / mol to 1,000,000 g / mol to reduce and / or prevent carbonation in a hydraulic composition comprising at least one hydraulic binder said at least one polyalkyleneimine (s) being present in the hydraulic composition in a polyalkyleneimine (s) / binder weight ratio of from 0.05% to 5.0%.
13. Objet mis en forme pour le domaine de la construction obtenu à partir d'une composition selon l'une quelconque des revendications 1 à -9. 13. Object shaped for the field of construction obtained from a composition according to any one of claims 1 to -9.
EP16809907.5A 2015-10-20 2016-10-20 Hydraulic composition having improved carbonation resistance Withdrawn EP3365301A1 (en)

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