Novel accelerators for hydraulic compositions based on granulated blast furnace slag

Abstract

The present invention relates to an adjuvant composition comprising, relative to the total weight of the adjuvant composition: - 1% to 60% by weight of an aluminum salt, and - a calcium salt and / or crystallized blast furnace slag. The present invention also relates to an adjuvanted hydraulic binder composition and to a hydraulic composition comprising such an adjuvant composition.

Description

[0001] New accelerators for hydraulic compositions based on granulated blast furnace slag

[0002] The present invention relates to an admixture composition for hydraulic binders based on granulated blast furnace slag comprising a specific combination of admixtures.

[0003] The present invention also relates to a hydraulic binder composition and a hydraulic binder-based hydraulic composition comprising granulated blast furnace slag and comprising said combination of admixtures.

[0004] The present invention further relates to the use of said combination of adjuvants for improving the compressive mechanical strengths of a hydraulic or hydraulic binder composition based on granulated blast furnace slag.

[0005] Common cement compositions contain a significant proportion of clinker. For example, most common cements defined in EN 197-1:201 1 “Composition, specifications and conformity criteria for common cements” contain at least 65% clinker by weight.

[0006] We are seeking to lower the clinker content of cement compositions in order to reduce greenhouse gas emissions linked to their production (carbon footprint), while maintaining their mechanical and rheological properties.

[0007] However, the high presence of granulated blast furnace slag and the decrease in clinker content induces a decrease in short-term compressive strengths, particularly 24-hour compressive strengths. However, the admixtures known to improve the compressive strengths of a hydraulic composition based on a hydraulic binder composition with a high clinker content are not effective enough to improve the compressive strengths of a hydraulic composition with a high content of granulated blast furnace slag.

[0008] There is therefore a need for new admixtures to improve the compressive strength, preferably in the short term (e.g. 24 hours), of hydraulic compositions based on granulated blast furnace slag, which do not deteriorate the other properties of these hydraulic compositions, in particular their workability over time. For example, for ready-mix concrete (RMC) type applications, the workability maintenance usually required is 2 hours. For specific applications on large construction sites (e.g. diaphragm walls), the required workability maintenance can be up to 8 hours.

[0009] The present invention therefore relates to an adjuvant composition comprising, relative to the total mass of the adjuvant composition:

[0010] - from 1% to 60% by mass of an aluminum salt, and

[0011] - a calcium salt and / or crystallized blast furnace slag.

[0012] Indeed, the inventors surprisingly discovered that the combination of a calcium salt and / or a crystallized blast furnace slag with an aluminum salt improves the effect of the aluminum salt on the compressive strengths, in particular the short-term compressive strengths. They therefore discovered a synergy between these compounds, which makes it possible to significantly increase the compressive strength, in particular in the short term, of hydraulic compositions based on granulated blast furnace slag.

[0013] In particular, if the contents are expressed in mass relative to the total dry mass of active ingredients in the adjuvant composition, the adjuvant composition comprises:

[0014] - from 40% to 98% by mass of an aluminum salt, and

[0015] - a calcium salt and / or crystallized blast furnace slag.

[0016] Adjuvant composition

[0017] Preferably, the aluminum salt is selected from aluminum carbonate, aluminum chloride, aluminum nitrate, aluminum trihydroxide, aluminum sulfate, aluminum oxalate, aluminum acetate, aluminum thiocyanate, preferably the aluminum salt is aluminum trihydroxide.

[0018] Preferably, the calcium salt is chosen from calcium chloride, calcium nitrate, calcium dihydroxide, calcium sulfate, calcium oxalate, calcium acetate, calcium thiocyanate, preferably the calcium salt is calcium nitrate.

[0019] For the purposes of the present invention, crystallized blast furnace slag is understood to mean a by-product of the steel industry during the production of cast iron in blast furnaces, formed from non-ferrous constituents, fluxes and coke ash, and which has been slowly cooled in order to be crystallized. Crystallized blast furnace slag, due to its low amorphous phase content (less than two-thirds by mass), is not considered to be a hydraulic binder.

[0020] Depending on the cooling process of the molten slag, we therefore distinguish two families:

[0021] - crystallized slag, obtained by slow cooling which transforms it into a hard artificial and chemically stable rock; and

[0022] - vitrified slag (granulated) obtained by sudden cooling in water, which gives it a vitreous structure allowing it to develop hydraulic binder properties.

[0023] Typically, the crystallized blast furnace slag comprises (or consists of) 0% to 40% by mass of amorphous phase and 60% to 100% by mass of crystalline phase, relative to the total mass of crystallized blast furnace slag, preferably 0% to 20% by mass of amorphous phase and 80% to 100% by mass of crystalline phase, preferably 0% to 15% by mass of amorphous phase and 85% to 100% by mass of crystalline phase, preferably 1% to 10% by mass of amorphous phase and 90% to 99% by mass of crystalline phase.

[0024] The contents of amorphous phase and crystalline phase are determined by the X-ray diffraction technique. This technique makes it possible to determine the nature and proportion of crystalline phases and the proportion of amorphous phase by X-ray diffraction and RIETVELD refinement.

[0025] In contrast, granulated blast furnace slag is obtained by sudden cooling in order to vitrify it; it is overwhelmingly amorphous.

[0026] The crystallized blast furnace slag is preferably as defined in the French experimental standard P18-302 published by AFNOR in December 1991.

[0027] Typically, a crystallized blast furnace slag is composed primarily of lime (CaO) between 35% and 50% by mass, silica (SiC>2) between 27% and 39% by mass, alumina (AI2O3) between 8% and 24% by mass, and magnesia (MgO) less than 12% by mass. It also contains 5% or less by mass of iron oxide (Fe20s) and 2% or less by mass of sulfur S.

[0028] Preferably, the particle size of crystallized blast furnace slag is between 10 nm and 500 pm, preferably between 0.2 pm and 400 pm. The particle size of crystallized blast furnace slag is determined by laser granulometry, a method based on the principle of diffraction of a laser beam by particles suspended in a carrier medium.

[0029] Preferably, the crystallized blast furnace slag is ground.

[0030] The specific surface area of ​​the ground crystallized blast furnace slag particles is preferably between 2000 and 10000 cm 2 / g, preferably between 4000 and 9000 cm 2 / g, more preferably between 4000 and 6000 cm 2 / g, measured using the air permeability method (Blaine method) according to EN 196-6.

[0031] Preferably, the aluminum salt content is between 5% and 50% by mass, preferably between 10% and 45% by mass, preferably between 15% and 40% by mass, preferably between 20% and 35% by mass, relative to the total mass of the adjuvant composition.

[0032] Expressed relative to the total dry mass of active materials in the adjuvant composition, the aluminum salt content is preferably between 45% and 95% by mass, preferably between 50% and 85% by mass, preferably between 50% and 80% by mass, preferably between 50% and 75% by mass.

[0033] Preferably, the content of calcium salt and / or crystallized blast furnace slag is between 1% and 40% by mass, preferably between 2% and 30% by mass, preferably between 5% and 25% by mass, preferably between 8% and 15% by mass, relative to the total mass of the adjuvant composition.

[0034] Expressed relative to the total dry mass of active materials in the adjuvant composition, the content of calcium salt and / or crystallized blast furnace slag is preferably between 1% and 60% by mass, preferably between 2% and 60% by mass, preferably between 2.5% and 55% by mass, preferably between 5% and 55% by mass, preferably between 5% and 50% by mass, preferably between 10% and 50% by mass, preferably between 15% and 45% by mass, preferably between 20% and 40% by mass.

[0035] Preferably, the mass ratio between the mass content of aluminum salt and the mass content of calcium salt and / or crystallized blast furnace slag is between 0.1 and 15, preferably between 0.5 and 10, preferably between 1 and 8, preferably between 1.5 and 6, preferably between 2 and 5.

[0036] Preferably, the adjuvant composition comprises, relative to the total mass of the adjuvant composition, between 1% and 60% by mass of an aluminum salt, and a calcium salt.

[0037] Preferably, the adjuvant composition further comprises an alkali or alkaline earth salt selected from alkali or alkaline earth salts of formate, carbonate, chloride, hydroxide, oxalate, thiocyanate, silicate, sulfate or nitrate or a mixture thereof, preferably comprises an alkali or alkaline earth salt of thiocyanate, preferably comprises sodium or calcium thiocyanate.

[0038] It is understood that this alkali or alkaline-earth salt, when present, is different from the possible calcium salt of the adjuvant composition. Preferably, the content of alkali or alkaline-earth salt as defined above, preferably the content of alkali or alkaline-earth thiocyanate salt, is between 0.5% and 30% by mass, preferably between 1% and 20% by mass, preferably between 5% and 15% by mass, relative to the total mass of the adjuvant composition.

[0039] Expressed relative to the total dry mass of active materials in the adjuvant composition, the content of alkali or alkaline-earth salt as defined above, preferably the content of alkali or alkaline-earth thiocyanate salt, is preferably between 3% and 30% by mass, preferably between 5% and 25% by mass, preferably between 7% and 20% by mass, preferably between 8% and 15% by mass.

[0040] Preferably, the adjuvant composition further comprises an alkanolamine, preferably selected from diethanolisopropanolamine (DEIPA), triisopropanolamine (TIPA), N,N-bis(2-hydroxypropyl)-N-(hydroxyethyl)amine (EDIPA), triethanolamine (TEA), N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (THEED), methyldiethanolamine (MDEA), bis-(2-hydroxypropyl)-amine (DIPA) and diethanolamine (DEA), preferably the alkanolamine is diethanolisopropanolamine (DEIPA).

[0041] Preferably, the alkanolamine content is between 0.5% and 30% by mass, preferably between 1% and 20% by mass, preferably between 5% and 15% by mass, relative to the total mass of the adjuvant composition.

[0042] Expressed relative to the total dry mass of active materials in the adjuvant composition, the alkanolamine content is preferably between 3% and 30% by mass, preferably between 5% and 25% by mass, preferably between 7% and 20% by mass, preferably between 8% and 15% by mass.

[0043] Preferably, the adjuvant composition is in the form of a suspension, preferably aqueous, or a powder, and preferably is in the form of an aqueous suspension.

[0044] When the admixture composition is in the form of a powder, it may further comprise an additional compound in powder form. This additional compound is preferably selected from ground calcium carbonate, precipitated calcium carbonate, silica, precipitated silica, calcium sulfate (anhydrous or hemihydrate or dihydrate), barium sulfate, granulated blast furnace slag, ground calcined or uncalcined clays, ground zeolite, silicates and aluminosilicates, talc, chalk, ground dolomite, ground expanded perlite, ground diatomite, ground calcined diatomite, ground recycled hardened cementitious materials (including foam concretes) and mixtures thereof. The composition may also comprise colorants and antifoaming agents.This additional compound is inert or has very low reactivity, that is to say it does not react in the presence of water, or significantly more slowly than a hydraulic binder, such as crystallized blast furnace slag.

[0045] When the adjuvant composition is in the form of a suspension, it may comprise a dispersing agent and a stabilizing agent. The dispersing agent is preferably selected from polyalkoxylated polycarboxylate polymers, polyalkoxylated phosphonate polymers, polyacids or surfactants or mixtures thereof. The stabilizing agent is preferably selected from cellulose or cellulose derivatives (preferably cellulose ethers or cellulose esters or mixtures thereof), polysaccharides (preferably guar gum and its derivatives, welan gum, xanthan gum, diutan gum or gellan gum or any of their mixtures), crosslinked polyvinyl alcohol, latexes and derivatives, high molar mass polyethylene glycols (preferably Mw > 50,000 g / mol), sodium alginate, and clays (preferably sepiolite or bentonite), or mixtures thereof.The suspension may also include biocides, colorants and antifoam agents.

[0046] Other additives may be present in the adjuvant composition of the present invention.

[0047] These additives may be chosen by a person skilled in the art from the typical additives of hydraulic binder compositions and hydraulic compositions. Mention may in particular be made of alkanolamines, glycols, glycerols, water-reducing and high-water-reducing adjuvants, surfactants, carboxylic acids or their salts such as acetic, adipic, gluconic, formic, oxalic, citric, maleic, lactic, tartaric, malonic acids and mixtures thereof, anti-foam additives, air-entraining additives and / or grinding agents, setting retarders.

[0048] The adjuvant composition according to the invention may further comprise a reducing or high water reducing adjuvant chosen from polyalkoxylated polycarboxylate polymers and polyalkoxylated phosphonate polymers, and any of their mixtures.

[0049] Preferably, the polyalkoxylated polycarboxylate polymers comprise units of the following formulas (I) and (II): in which

[0050] - “R2” and “R3” independently represent hydrogen or methyl,

[0051] - “M” represents independently of each other H + or a cation of valence v chosen from an alkali metal cation, an alkaline earth metal cation, a bi- or trivalent metal cation, an ammonium cation or an organic ammonium cation,

[0052] - when “M” represents H, “v” represents 1, and when “M” represents a cation (as defined above), “v” is the valence of the cation M,

[0053] - “R7” and “R8” independently represent hydrogen, methyl or a group of formula -COO(M)i / v with M and v as defined above,

[0054] - “m” represents 0, 1 or 2,

[0055] - “p” represents 0 or 1,

[0056] - “X” is O or NR9, “R9” representing H, a C1-C20 alkyl group, a cycloalkyl group or an alkylaryl group, and

[0057] - “R1” represents a C1-C20 alkyl group, a cycloalkyl group, an alkylaryl group, or -[Alkyl-O] z -R6, in which the “Alkyl” of each Alkyl-0 unit of the group — [Alkyl-O] z - independently represents a linear or branched alkylene comprising from 2 to 4 carbon atoms, and “R6” represents H, a C1 to C20 alkyl group, a cyclohexyl group or an alkylaryl group, and “z” is an integer ranging from 2 to 250,

[0058] - “a” is a number ranging from 0.05 to 0.95, “a” being the mole fraction of units of formula (I) in the polymer, and

[0059] - “b” is a number ranging from 0.05 to 0.95, “b” being the mole fraction of units of formula (II) in the polymer.

[0060] Preferably, the polyalkoxylated phosphonate polymers are of the following formula (III): in which

[0061] “R5” is a hydrogen atom or a monovalent hydrocarbon group containing from 1 to 18 carbon atoms and optionally one or more heteroatoms; the “Ri” are similar to or different from each other and represent an alkylene such as ethylene, propylene, butylene, amylene, octylene or cyclohexene, or an arylene such as styrene or methylstyrene, the “Ri” optionally containing one or more heteroatoms;

[0062] “Q” is a hydrocarbon group containing from 2 to 18 carbon atoms and optionally one or more heteroatoms;

[0063] “A” is an alkylene group containing from 1 to 5 carbon atoms; the “Rj” are similar or different from each other and can be chosen from:

[0064] - the group A-PO3H2, A having the aforementioned meaning,

[0065] - the alkyl group comprising from 1 to 18 carbon atoms and which may carry [R5-0(Ri-0)m] groups, R5 and Ri having the aforementioned meanings,

[0066] "m" is a number greater than or equal to 0,

[0067] "r" is the number of [R5-O(Ri-O)m] groups carried by all Rj, "q" is the number of [R5-O(Ri-O)m] groups carried by Q, the sum "r+q" is between 1 and 10,

[0068] “y” is an integer between 1 and 3,

[0069] “Q”, “N” and “Rj” may together form one or more cycles, this or these cycles being able to further contain one or more other heteroatoms.

[0070] According to a first embodiment, the adjuvant composition comprises, relative to the total mass of the adjuvant composition, from 1% to 60% by mass (or from 40 to 98% by mass if the content is expressed relative to the total dry mass of active materials of the adjuvant composition) of an aluminum salt, and a calcium salt.

[0071] According to a second embodiment, the adjuvant composition comprises, relative to the total mass of the adjuvant composition, from 1% to 60% by mass (or from 40 to 98% by mass if the content is expressed relative to the total dry mass of active materials of the adjuvant composition) of an aluminum salt, and crystallized blast furnace slag. According to a third embodiment, the adjuvant composition comprises, relative to the total mass of the adjuvant composition, from 1% to 60% by mass (or from 40 to 98% by mass if the content is expressed relative to the total dry mass of active materials of the adjuvant composition) of an aluminum salt, and a mixture of calcium salt and crystallized blast furnace slag.

[0072] All characteristics of the adjuvant composition apply independently to any of these three embodiments. In particular, the contents and ratios of the above description defined in relation to the calcium salt and the crystallized blast furnace slag apply independently to the calcium salt and the crystallized blast furnace slag.

[0073] Thus, for example, in the first embodiment, the calcium salt content is preferably between 1% and 40% by mass, preferably between 2% and 30% by mass, preferably between 5% and 25% by mass, preferably between 8% and 15% by mass, relative to the total mass of the adjuvant composition (or preferably between 1% and 60% by mass, preferably between 2% and 60% by mass, preferably between 2.5% and 55% by mass, preferably between 5% and 55% by mass, preferably between 5% and 50% by mass, preferably between 10% and 50% by mass, preferably between 15% and 45% by mass, preferably between 20% and 40% by mass when the content is expressed relative to the total dry mass of active ingredients in the adjuvant composition);in the second embodiment, the content of crystallized blast furnace slag is preferably between 1% and 40% by mass, preferably between 2% and 30% by mass, preferably between 5% and 25% by mass, preferably between 8% and 15% by mass, relative to the total mass of the adjuvant composition (or preferably between 1% and 60% by mass, preferably between 2% and 60% by mass, preferably between 2.5% and 55% by mass, preferably between 5% and 55% by mass, preferably between 5% and 50% by mass, preferably between 10% and 50% by mass, preferably between 15% and 45% by mass, preferably between 20% and 40% by mass when the content is expressed relative to the total dry mass of active ingredients in the adjuvant composition);and for example, in the third embodiment, each of the calcium salt and the crystallized blast furnace slag is independently present in a content preferably of between 1% and 40% by mass, preferably between 2% and 30% by mass, preferably between 5% and 25% by mass, preferably between 8% and 15% by mass, relative to the total mass of the adjuvant composition (or preferably of between 1% and 60% by mass, preferably between 2% and 60% by mass, preferably between 2.5% and 55% by mass, preferably between 5% and 55% by mass, preferably between 5% and 50% by mass, preferably between 10% and 50% by mass, preferably between 15% and 45% by mass, preferably between 20% and 40% by mass when the content is expressed relative to the total dry mass of active ingredients in the composition adjuvant).;

[0074] Throughout the description, the contents in the adjuvant composition are indicated relative to the total dry mass of active materials in the adjuvant composition. "In active materials" means that only compounds that have an effect on a property of a hydraulic composition comprising them are taken into account. Active materials or active compounds are to be contrasted with materials (powder or liquid) that are present in the adjuvant composition only as a diluent, but do not have a notable effect on a property of a hydraulic composition comprising them; they are therefore inert compounds. In particular, a content relative to the total dry mass of active materials means that water is not taken into account in the case of a composition in the form of a suspension or liquid solution, and that the additional compound(s) in powder form are not taken into account in the case of a composition in powder form.

[0075] In particular, the contents relative to the total dry mass of active materials of the adjuvant composition are expressed relative to the total mass content of aluminum salt, calcium salt and / or crystallized blast furnace slag, and optionally alkali or alkaline-earth salt (preferably the content of alkali or alkaline-earth salt of thiocyanate), and / or alkanolamine(s). For example, in the first embodiment above, the contents relative to the total dry mass of active materials of the adjuvant composition may be expressed relative to the total mass content of aluminum salt and calcium salt, and optionally alkali or alkaline-earth salt (preferably the content of alkali or alkaline-earth salt of thiocyanate), and / or alkanolamine(s).In the second embodiment above, the contents relative to the total dry mass of active materials of the adjuvant composition may be expressed relative to the total mass content of aluminum salt and crystallized blast furnace slag, and optionally of alkali or alkaline-earth salt (preferably the content of alkali or alkaline-earth thiocyanate salt), and / or of alkanolamine(s). In the third embodiment above, the contents relative to the total dry mass of active materials of the adjuvant composition may be expressed relative to the total mass content of aluminum salt, calcium salt and crystallized blast furnace slag, and optionally of alkali or alkaline-earth salt (preferably the content of alkali or alkaline-earth thiocyanate salt), and / or of alkanolamine(s). Adjuvanted hydraulic binder composition.

[0076] The present invention also relates to an adjuvanted hydraulic binder composition comprising:

[0077] - a hydraulic binder composition comprising, relative to the total dry mass of the hydraulic binder composition, between 6% and 95% by mass of granulated blast furnace slag, and

[0078] - an adjuvant composition according to the invention.

[0079] Preferably, the content of admixture composition in the admixed hydraulic binder composition, relative to the total dry mass of the hydraulic binder composition, is between 0.05% and 7.0% by mass, preferably between 0.1% and 5.0% by mass, preferably between 0.2% and 4.0% by mass, preferably between 0.3% and 2.5% by mass, preferably between 0.3% and 2.0% by mass.

[0080] The present invention therefore relates to an adjuvanted hydraulic binder composition comprising:

[0081] - a hydraulic binder composition comprising, relative to the total dry mass of the hydraulic binder composition, between 6% and 95% by mass of granulated blast furnace slag,

[0082] - an aluminum salt, and

[0083] - a calcium salt and / or crystallized blast furnace slag.

[0084] For the purposes of the application, the term "adjuvanted hydraulic binder composition" means a composition comprising the hydraulic binder composition and the adjuvant composition (i.e. at least the aluminum salt and the calcium salt and / or the crystallized blast furnace slag) (and possibly the additional adjuvants), and the term "hydraulic binder composition" means the hydraulic binder composition free of adjuvant.

[0085] The contents defined in relation to the total dry mass of the hydraulic binder composition are therefore defined in relation to the sum of the dry mass of each main and secondary constituent of the hydraulic binder composition, the main and secondary components being as defined by standard EN 197-1:2011 or standard EN 197-5:2021.

[0086] Aluminum salt, calcium salt and crystallized blast furnace slag are as defined above for the admixture composition. For the purposes of the invention, a hydraulic binder composition comprising, relative to the total dry mass of the hydraulic binder composition, between 6% and 95% by mass of granulated blast furnace slag, comprises all types of hydraulic binders comprising at least 6% by mass, and up to 95% by mass of granulated blast furnace slag, in particular all cements, for example those referenced in standard EN 197-1:201 1 and standard EN 197-5:2021 which comprise at least 6% by mass, and up to 95% by mass of granulated blast furnace slag. A hydraulic binder composition according to the invention comprises, for example, a mixture of CEM I and between 6% and 95% by mass of granulated blast furnace slag, relative to the total dry mass of the hydraulic binder composition.

[0087] Granulated blast furnace slag is produced by rapid cooling (e.g., water quenching and spraying into water spray) of molten slag, and contains at least two-thirds by weight of vitreous (amorphous) slag. It is therefore distinguished from crystallized blast furnace slag which may be present in the additive composition of the invention.

[0088] Preferably, the granulated blast furnace slag is ground.

[0089] Ground granulated blast furnace slag preferably has a specific surface area of ​​2000 to 10000 cm 2 / g, preferably from 4000 to 9000 cm 2 / g, more preferably from 4300 to 8000 cm 2 / g, measured using the air permeability method (Blaine method) according to EN 196-6.

[0090] Preferably, the granulated blast furnace slag comprises from 67% to 100% by mass, preferably from 95% to 99% by mass, of blast furnace slag in amorphous form, relative to the total mass of granulated blast furnace slag, and the balance being crystallized blast furnace slag.

[0091] The hydraulic binder composition therefore preferably corresponds to a CEM III cement when it comprises from 36% to 95% by mass of granulated blast furnace slag or to a CEM II cement when it comprises from 6% to 35% by mass of granulated blast furnace slag or to a CEM V cement when it comprises from 18% to 49% by mass of granulated blast furnace slag or to a CEM VI cement when it comprises from 31% to 59% by mass of granulated blast furnace slag. These include in particular CEM lll / A, CEM lll / B and CEM lll / C cements, CEM ll / AS and CEM ll / BS cements, CEM ll / AM and CEM ll / BM cements, CEM ll / CM cements, CEM V / A and CEM V / B cements, CEM VI cements as defined in standard NF EN 197-1:2011 and standard EN 197-5:2021.

[0092] Preferably, the hydraulic binder composition further comprises, relative to the total dry mass of the hydraulic binder composition, from 5% to 94% by mass of clinker. The hydraulic binder composition may also comprise mineral additions, up to the amount permitted by standard EN 206:2013+A2:2021 and its National Supplements.

[0093] The term "mineral additions" means granulated blast furnace slags (as defined in standard EN 197-1:2011 paragraph 5.2.2), steelworks slags, pozzolanic materials (as defined in standard EN 197-1:2011 paragraph

[0094] 5.2.3), fly ash (as defined in EN 197-1:2011 paragraph

[0095] 5.2.4), calcined shale (as defined in standard EN 197-1:201 1 paragraph

[0096] 5.2.5), or silica fumes (as defined in standard EN 197-1:201 1 paragraph 5.2.7 or standard EN 197-5:2021 paragraph 5), calcium or magnesium carbonates or their mixtures.

[0097] According to one embodiment, the hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, between 15% and 95% by mass, preferably between 25% and 95% by mass, preferably between 36% and 95% by mass of granulated blast furnace slag. According to this embodiment, the hydraulic binder composition preferably comprises, relative to the total dry mass of the hydraulic binder composition, between 5% and 85% by mass, preferably between 5% and 75% by mass, preferably between 5% and 64% by mass, of clinker. Preferably, the hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, between 36% and 65% by mass of granulated blast furnace slag and between 35% and 64% by mass of clinker.Alternatively, the hydraulic binder composition preferably comprises, relative to the total dry mass of the hydraulic binder composition, between 66% and 80% by mass of granulated blast furnace slag and between 20% and 34% by mass of clinker. Still alternatively, the hydraulic binder composition preferably comprises, relative to the total dry mass of the hydraulic binder composition, between 81% and 95% by mass of granulated blast furnace slag and between 5% and 19% by mass of clinker.

[0098] According to another embodiment, the hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, between 6% and 60% by mass, preferably between 6% and 50% by mass, preferably between 6% and 40% by mass, preferably between 6% and 35% by mass of granulated blast furnace slag. According to this embodiment, the hydraulic binder composition preferably comprises, relative to the total dry mass of the hydraulic binder composition, between 40% and 94% by mass, preferably between 50% and 94% by mass, preferably between 60% and 94% by mass, preferably between 65% and 94% by mass, of clinker. Preferably, the hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, between 12% and 20% by mass of granulated blast furnace slag and between 80% and 88% by mass of clinker.Alternatively, the hydraulic binder composition preferably comprises, relative to the total dry mass of the hydraulic binder composition, between 21% and 35% by mass of granulated blast furnace slag and between 65% and 79% by mass of clinker. Alternatively, the hydraulic binder composition preferably comprises, relative to the total dry mass of the hydraulic binder composition, between 36% and 50% by mass of granulated blast furnace slag and between 50% and 64% by mass of clinker.

[0099] According to yet another embodiment, the hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, between 8% and 70% by mass, preferably between 10% and 60% by mass, preferably between 15% and 55% by mass, preferably between 18% and 49% by mass of granulated blast furnace slag. According to this embodiment, the hydraulic binder composition preferably comprises, relative to the total dry mass of the hydraulic binder composition, between 8% and 85% by mass, preferably between 10% and 80% by mass, preferably between 15% and 75% by mass, preferably between 18% and 70% by mass, preferably between 20% and 64% by mass, of clinker.According to this embodiment, the hydraulic binder composition preferably comprises, relative to the total dry mass of the hydraulic binder composition, preferably between 10% and 60% by mass, preferably between 18% and 49% by mass of mineral additions preferably chosen from pozzolans and siliceous fly ash. Preferably, the hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, between 18% and 30% by mass of granulated blast furnace slag, between 40% and 64% by mass of clinker and between 18% and 30% by mass of mineral additions preferably chosen from pozzolans and siliceous fly ash.Alternatively, the hydraulic binder composition preferably comprises, relative to the total dry mass of the hydraulic binder composition, between 31% and 49% by mass of granulated blast furnace slag, between 20% and 38% by mass of clinker and between 31% and 49% by mass of mineral additions preferably chosen from pozzolans and siliceous fly ash.

[0100] According to yet another embodiment, the hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, between 10% and 80% by mass, preferably between 20% and 70% by mass, preferably between 31% and 59% by mass of granulated blast furnace slag. According to this embodiment, the hydraulic binder composition preferably comprises, relative to the total dry mass of the hydraulic binder composition, between 20% and 90% by mass, preferably between 30% and 80% by mass, preferably between 35% and 49% by mass of clinker. According to this embodiment, the hydraulic binder composition preferably comprises, relative to the total dry mass of the hydraulic binder composition, between 6% and 20% by mass, of mineral additions preferably chosen from natural pozzolans, siliceous fly ash and calcium or magnesium carbonate.

[0101] Preferably, the admixed hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, from 0.05% to 3.0% by mass, preferably from 0.1% to 2.0% by mass, preferably from 0.2% to 1.5% by mass, preferably from 0.3% to 1.0% by mass, preferably from 0.4% to 0.8% by mass, preferably from 0.5% to 0.7% by mass of aluminum salt.

[0102] Preferably, the admixed hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, from 0.01% to 1.0% by mass, preferably from 0.05% to 0.8% by mass, preferably from 0.08% to 0.6% by mass, preferably from 0.1% to 0.5% by mass of calcium salt and / or crystallized blast furnace slag.

[0103] Preferably, the mass ratio between the mass content of aluminum salt and the mass content of calcium salt and / or crystallized blast furnace slag is between 0.1 and 15, preferably between 0.5 and 10, preferably between 1 and 8, preferably between 1.5 and 6, preferably between 2 and 5.

[0104] Preferably, the admixed hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, between 0.01% and 0.9% by mass, preferably between 0.02% and 0.6% by mass, preferably between 0.05% and 0.3% by mass, preferably between 0.08% and 0.15% by mass, preferably between 0.08% and 0.12% by mass of alkali or alkaline earth salt of thiocyanate.

[0105] Preferably, the admixed hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, between 0.01% and 0.9% by mass, preferably between 0.02% and 0.6% by mass, preferably between 0.05% and 0.3% by mass, preferably between 0.08% and 0.15% by mass, preferably between 0.08% and 0.12% by mass of alkanolamine.

[0106] Preferably, the admixed hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, between 0.01% and 1% by mass, preferably between 0.05% and 0.8% by mass, preferably between 0.08% and 0.6% by mass, preferably between 0.1% and 0.5% by mass, preferably between 0.15% and 0.4% by mass of reducing or high water reducing admixture. According to a first embodiment, the admixed hydraulic binder composition comprises:

[0107] - a hydraulic binder composition as defined above comprising, relative to the total dry mass of the hydraulic binder composition, between 6% and 95% by mass of granulated blast furnace slag,

[0108] - an aluminum salt as defined above, and

[0109] - a calcium salt as defined above.

[0110] According to a second embodiment, the adjuvanted hydraulic binder composition comprises:

[0111] - a hydraulic binder composition as defined above comprising, relative to the total dry mass of the hydraulic binder composition, between 6% and 95% by mass of granulated blast furnace slag,

[0112] - an aluminum salt as defined above, and

[0113] - crystallized blast furnace slag as defined above.

[0114] According to a third embodiment, the adjuvanted hydraulic binder composition comprises:

[0115] - a hydraulic binder composition as defined above comprising, relative to the total dry mass of the hydraulic binder composition, between 6% and 95% by mass of granulated blast furnace slag,

[0116] - an aluminum salt as defined above, and

[0117] - a mixture of calcium salt and crystallized blast furnace slag as defined above.

[0118] All characteristics of the admixture composition and the admixed hydraulic binder composition apply independently to any of these three embodiments. In particular, the contents and ratios defined in relation to the calcium salt and the crystallized blast furnace slag apply independently to the calcium salt and the crystallized blast furnace slag. Thus, for example, in the first embodiment, the calcium salt content is between 0.01% and 1.0% by mass, preferably between 0.05% and 0.8% by mass, preferably between 0.08% and 0.6% by mass, preferably between 0.1% and 0.5% by mass relative to the total dry mass of the hydraulic binder composition;in the second embodiment, the content of crystallized blast furnace slag is between 0.01% and 1.0% by mass, preferably between 0.05% and 0.8% by mass, preferably between 0.08% and 0.6% by mass, preferably between 0.1% and 0.5% by mass relative to the total dry mass of the hydraulic binder composition; and for example, in the third embodiment, each of the calcium salt and the crystallized blast furnace slag is independently present in a content between 0.01% and 1.0% by mass, preferably between 0.05% and 0.8% by mass, preferably between 0.08% and 0.6% by mass, preferably between 0.1% and 0.5% by mass relative to the total dry mass of the hydraulic binder composition.;

[0119] The alkali or alkaline earth thiocyanate salt, the alkanolamine and the reducing or high water reducing adjuvant are as defined above for the adjuvant composition.

[0120] The admixed hydraulic binder composition may further comprise at least one additive as described above for the admixture composition.

[0121] Hydraulic composition

[0122] The present invention also relates to a hydraulic composition comprising:

[0123] - a hydraulic binder composition, as defined above, comprising, relative to the total dry mass of the hydraulic binder composition, between 6% and 95% by mass of granulated blast furnace slag,

[0124] - an adjuvant composition according to the invention,

[0125] - water,

[0126] - possibly an aggregate, and

[0127] - possibly a mineral addition.

[0128] The present invention therefore relates to a hydraulic composition comprising:

[0129] - an admixed hydraulic binder composition as defined above (according to any embodiment),

[0130] - water,

[0131] - possibly an aggregate, and

[0132] - possibly a mineral addition.

[0133] The hydraulic composition is preferably a composition of concrete, mortar or screed.

[0134] By "aggregates" we mean a set of mineral grains with an average diameter of between 0 and 125 mm. Depending on their diameter, aggregates are classified into one of the following six families: fillers, sand, gravel, gravel and ballast (standards EN 12620 and EN 13242+A1). The most commonly used aggregates are: - fillers, which have a diameter of less than 2 mm and for which at least 85% of the aggregates have a diameter of less than 1.25 mm and at least 70% of the aggregates have a diameter of less than 0.063 mm,

[0135] - sands with a diameter between 0 and 6.3 mm

[0136] - gravel with a diameter greater than 6.3 mm gravel with a diameter between 2 mm and 63 mm

[0137] Sands are therefore included in the definition of aggregate according to the invention.

[0138] Fillers can be of limestone or dolomitic origin.

[0139] The term "mineral additions" means granulated blast furnace slag (as defined in standard EN 197-1:2011 paragraph 5.2.2), steelworks slag, pozzolanic materials (as defined in standard EN 197-1:2011 paragraph

[0140] 5.2.3), fly ash (as defined in EN 197-1:201 1 paragraph

[0141] 5.2.4), calcined shale (as defined in standard EN 197-1:2011 paragraph

[0142] 5.2.5), or silica fumes (as defined in standard EN 197-1:201 1 paragraph 5.2.7 or standard EN 197-5:2021 paragraph 5), calcium or magnesium carbonates or their mixtures.

[0143] The hydraulic composition may further comprise at least one additive as described above for the adjuvant composition.

[0144] Hydraulic binder and hydraulic compositions are conventionally prepared by mixing the above-mentioned constituents. The admixture composition is added at the time of mixing or at the time of grinding the hydraulic binder composition.

[0145] The present invention also relates to the use of an adjuvant composition according to the invention, for improving the mechanical compressive strengths, preferably in the short term, of a hydraulic binder composition comprising, relative to the total dry mass of the hydraulic binder composition, between 6% and 95% by mass of granulated blast furnace slag.

[0146] The expressions "from ... to ...", "between ... and ...", "ranging from ... to ...", "varies from ... to ...", and "less than ..." must be understood inclusively, unless otherwise specified.

[0147] The invention is illustrated in the following examples.

[0148] Example 1: Description of the adjuvant compositions The adjuvant compositions were prepared by mixing the ingredients described in the following table with the indicated contents, expressed in relation to the total mass of the adjuvant composition. The adjuvant compositions were prepared and mixed, according to the contents indicated in Table 1, using a 3D dynamic mixer (rotational, translational and inversion movements) for a period of 15 minutes.

[0149] [Table 1]

[0150] : comparative Example 2: Testing of adjuvant compositions in mortar-type hydraulic compositions

[0151] The mortars used have the compositions shown in Tables 2 to 4 below. [Table 2] - Mortar 1

[0152]

[0153] [Table 3] - Mortar 2

[0154] [Table 4] - Mortar 3

[0155] Polymer 1 with superplasticizing effect used to admix mortars consists of the following units: 65, b = 35 and z = 53. Compositions C1*, C2* and C3 of example 1 were added to mortar 1 in the contents of the following table (expressed as a percentage by mass of each admixture relative to the total dry mass of binder).

[0156] [Table 5] - Mortar 1 with admixture

[0157] : comparison

[0158] These results clearly demonstrate the synergistic effect between aluminum hydroxide and calcium nitrate. Indeed, when used alone, calcium nitrate has no effect on the 24-hour compressive strength; but when mixed with aluminum hydroxide, it improves its effect on the compressive strength. This is all the more unexpected since CEM lll / C cement is a very difficult cement to accelerate due to its very low clinker content.

[0159] Compositions C4*, C5* and C6 of example 1 were added to mortar 2 in the contents of the following table (expressed as a percentage by mass of each admixture relative to the total dry mass of binder).

[0160] [Table 6] - Mortar 2 with admixture

[0161] : comparative These results clearly demonstrate the synergistic effect between aluminum hydroxide and crystallized blast furnace slag. Indeed, used alone, crystallized blast furnace slag has a deleterious effect on the mechanical compressive strengths at 24 h; but when mixed with aluminum hydroxide, it improves its effect on the mechanical compressive strengths.

[0162] Compositions C1*, C7*, C8, C9, C10, C11* and C12* of example 1 were added to mortar 3 in the contents of the following table (expressed as a percentage by mass of each admixture relative to the total dry mass of binder).

[0163] [Table 7] - Mortar 3 with admixture

[0164] : comparison

[0165] These results clearly demonstrate the synergistic effect between aluminum hydroxide and calcium nitrate. Indeed, when used alone, calcium nitrate has a deleterious effect on the 24-hour compressive strength; but when mixed with aluminum hydroxide, it improves its effect on the compressive strength.

[0166] The results obtained in the additional presence of sodium thiocyanate or DEIPA are also very surprising because, although these compounds are known as clinker activators, they have a very deleterious effect on the compressive strength when used alone on hydraulic binders comprising granulated blast furnace slag (see compositions CH36* and CH37*). On the other hand, used in a mixture with aluminum hydroxide and calcium nitrate, they significantly improve the compressive strength.

Claims

CLAIMS 1. Adjuvant composition comprising, relative to the total dry mass of active materials in the adjuvant composition: - from 40% to 98% by mass of an aluminum salt, and - a calcium salt and / or crystallized blast furnace slag.

2. Adjuvant composition according to claim 1, in which the aluminum salt content is between 45% and 95% by mass, preferably between 50% and 85% by mass, preferably between 50% and 80% by mass, preferably between 50% and 75% by mass, relative to the total dry mass of active materials in the adjuvant composition.

3. Adjuvant composition according to claim 1 or 2, wherein the content of calcium salt and / or crystallized blast furnace slag is between 1% and 60% by mass, preferably between 2% and 60% by mass, preferably between 5% and 50% by mass, preferably between 10% and 50% by mass, preferably between 15% and 45% by mass, preferably between 20% and 40% by mass, relative to the total dry mass of active materials in the adjuvant composition.

4. Adjuvant composition according to any one of the preceding claims, wherein the aluminum salt is selected from aluminum carbonate, aluminum chloride, aluminum nitrate, aluminum trihydroxide, aluminum sulfate, aluminum oxalate, aluminum acetate, aluminum thiocyanate, preferably the aluminum salt is aluminum trihydroxide.

5. Adjuvant composition according to any one of the preceding claims, wherein the calcium salt is selected from calcium chloride, calcium nitrate, calcium dihydroxide, calcium sulfate, calcium oxalate, calcium acetate, calcium thiocyanate, preferably the calcium salt is calcium nitrate.

6. An adjuvant composition according to any one of the preceding claims, further comprising an alkali or alkaline earth salt selected from alkali or alkaline earth salts of formate, carbonate, chloride, hydroxide, oxalate, thiocyanate, silicate, sulfate or nitrate or a mixture thereof, preferably comprising a salt alkali or alkaline earth thiocyanate, preferably comprising sodium or calcium thiocyanate.

7. Adjuvant composition according to claim 6, in which the content of alkali or alkaline earth salt is between 3% and 30% by mass, preferably between 5% and 25% by mass, preferably between 7% and 20% by mass, preferably between 8% and 15% by mass, relative to the total dry mass of active materials in the adjuvant composition.

8. Adjuvant composition according to any one of the preceding claims, further comprising an alkanolamine, preferably selected from diethanolisopropanolamine, triisopropanolamine, N,N-bis(2-hydroxypropyl)-N-(hydroxyethyl)amine, triethanolamine, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, methyldiethanolamine, bis-(2-hydroxypropyl)-amine and diethanolamine, preferably is diethanolisopropanolamine.

9. Adjuvant composition according to claim 8, wherein the alkanolamine content is between 3% and 30% by mass, preferably between 5% and 25% by mass, preferably between 7% and 20% by mass, preferably between 8% and 15% by mass, relative to the total dry mass of active materials in the adjuvant composition.

10. An adjuvant composition according to any one of the preceding claims, further comprising a water reducing or high reducing adjuvant selected from polyalkoxylated polycarboxylate polymers and polyalkoxylated phosphonate polymers, and any mixture thereof.

11. Adjuvant composition according to any one of the preceding claims, in the form of a suspension, preferably aqueous, or a powder, preferably in the form of an aqueous suspension.

12. Composition of adjuvanted hydraulic binder comprising: - a hydraulic binder composition comprising, relative to the total dry mass of the hydraulic binder composition, between 6% and 95% by mass of granulated blast furnace slag, and - an adjuvant composition according to any one of claims 1 to 11.

13. The admixed hydraulic binder composition according to claim 12, wherein the content of admixture composition in the admixed hydraulic binder composition is between 0.05% and 7.0% by mass, preferably between 0.1% and 5.0% by mass, preferably between 0.2% and 4.0% by mass, preferably between 0.3% and 2.5% by mass, preferably between 0.3% and 2.0% by mass, relative to the total dry mass of the hydraulic binder composition.

14. An admixed hydraulic binder composition according to claim 12 or 13, comprising, relative to the total dry mass of the hydraulic binder composition: - between 0.05% and 3.0% by mass of aluminum salt, and - between 0.01% and 1.0% by mass of a calcium salt and / or crystallized blast furnace slag.

15. Hydraulic composition comprising: - a hydraulic binder composition comprising, relative to the total dry mass of the hydraulic binder composition, between 6% and 95% by mass of granulated blast furnace slag, - an adjuvant composition as defined according to any one of claims 1 to 11, - water, - possibly an aggregate, and - possibly a mineral addition.

16. Use of an adjuvant composition as defined according to any one of claims 1 to 11, for improving the mechanical compressive strengths, preferably in the short term, of a hydraulic binder composition comprising, relative to the total dry mass of the hydraulic binder composition, between 6% and 95% by mass of granulated blast furnace slag.

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