Novel accelerators for binders comprising granulated blast furnace slag and calcium sulfate

Abstract

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

Description

[0001] New binder accelerators comprising granulated blast furnace slag and calcium sulfate

[0002] The present invention relates to a specific combination of admixtures for hydraulic binders mainly comprising granulated blast furnace slag and calcium sulfate, and in particular for oversulfated cements.

[0003] The present invention also relates to compositions comprising said combination of adjuvants and hydraulic binders mainly comprising granulated blast furnace slag and calcium sulfate, and in particular oversulfated cements.

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

[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] The aim is to reduce the clinker content of cementitious compositions in order to reduce greenhouse gas emissions linked to their production (carbon footprint), while maintaining their mechanical and rheological properties. The possibility of using cements resistant to agents such as sulfates is also being investigated, particularly for work in aggressive environments, as well as cements with a low heat of hydration intended for massive structures subject to the risk of thermal cracking.

[0007] For these applications, a particular distinction is made between binders and cements mainly comprising granulated blast furnace slag and also comprising a significantly high calcium sulfate content (typically between 5% and 20% by mass), and in particular supersulfated cements (CSS), described in standard EN 15743:2010+A1:2015.

[0008] However, such proportions of granulated blast furnace slag and calcium sulfate induce a reduction in short-term compressive strengths, in particular compressive strengths at 24 hours. 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 mainly based on granulated blast furnace slag and calcium sulfate, and in particular based on oversulfated cement.

[0009] 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 and calcium sulfate, 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.

[0010] The present invention therefore relates to an adjuvant composition comprising, relative to the total mass of the adjuvant composition:

[0011] - from 1% to 60% by mass of a calcium salt, and

[0012] - crystallized blast furnace slag and / or an aluminum salt.

[0013] Indeed, the inventors have surprisingly discovered that the combination of crystallized blast furnace slag and / or an aluminum salt with a calcium salt improves the effect of the calcium salt on the compressive strengths, in particular the short-term compressive strengths. They have 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 a hydraulic binder composition mainly comprising granulated blast furnace slag and calcium sulfate, for example oversulfated cements.

[0014] 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:

[0015] - from 40% to 98% by mass of a calcium salt, and

[0016] - crystallized blast furnace slag and / or an aluminum salt.

[0017] Adjuvant composition

[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 dihydroxide.

[0019] 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.

[0020] 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.

[0021] Depending on the cooling process of the molten slag, we therefore distinguish two families:

[0022] - crystallized slag, obtained by slow cooling which transforms it into a hard artificial and chemically stable rock; and

[0023] - vitrified slag (granulated) obtained by sudden cooling in water, which gives it a vitreous (amorphous) structure allowing it to develop hydraulic binder properties.

[0024] 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.

[0025] The mineralogical phase contents are determined by the X-ray diffraction technique. This technique makes it possible to determine the nature and proportion of the crystalline phases and to deduce the proportion of amorphous phase and the quantification of these phases is carried out by RIETVELD refinement.

[0026] In contrast, granulated blast furnace slag such as that included in CSS is obtained by sudden cooling in order to vitrify it; it is overwhelmingly amorphous.

[0027] The crystallized blast furnace slag is preferably as defined in the French experimental standard P18-302 published by AFNOR in December 1991. Typically, a crystallized blast furnace slag is composed essentially 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 calcium salt content is between 5% and 50% by mass, preferably between 8% and 40% by mass, preferably between 10% and 35% by mass, preferably between 15% and 30% by mass, preferably between 18% and 25% 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 calcium salt content is preferably between 45% and 95% by mass, preferably between 50% and 90% by mass, preferably between 60% and 85% by mass, preferably between 65% and 85% by mass.

[0033] Preferably, the content of crystallized blast furnace slag and / or aluminum salt is between 0.5% and 40% by mass, preferably between 1% and 30% by mass, preferably between 2% and 20% by mass, preferably between 3% and 15% by mass, preferably between 4% and 10% 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 crystallized blast furnace slag and / or aluminum salt is preferably between 1% and 60% by mass, preferably between 2% and 60% by mass, preferably between 2.5% and 55%, 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 40% by mass, preferably between 18% and 35% by mass, or between 1% and 40% by mass, preferably between 2% and 40% by mass, preferably between 5% and 40% by mass, preferably between 10% and 40% by mass.

[0035] Preferably, the mass ratio between the mass content of calcium salt and the mass content of crystallized blast furnace slag and / or aluminum salt is between 0.02 and 40, preferably between 0.5 and 20, preferably between 0.7 and 10, preferably between 1 and 8, preferably between 1.2 and 5, preferably between 1.5 and 3.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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, clays (preferably sepiolite or bentonite), and mixtures thereof.The suspension may also include biocides, colorants, and antifoaming agents. Other additives may be present in the adjuvant composition of the present invention.

[0040] 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.

[0041] 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) and methyldiethanolamine (MDEA), bis-(2-hydroxypropyl)-amine (DIPA) and diethanolamine (DEA), preferably the alkanolamine is diethanolisopropanolamine (DEIPA).

[0042] 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.

[0043] Preferably, the polyalkoxylated polycarboxylate polymers comprise units of the following formulas (I) and (II): in which

[0044] - “R2” and “R3” independently represent hydrogen or methyl,

[0045] - “M” represents independently of each other H + or a cation of valence v selected from an alkali metal cation, an alkaline earth metal cation, a bi- or trivalent metal cation, an ammonium cation or an organic ammonium cation, - when “M” represents H, “v” represents 1, and when “M” represents a cation (as defined above), “v” is the valence of the cation M,

[0046] - “R7” and “R8” independently represent hydrogen, methyl or a group of formula -COO(M)i / v with M and v as defined above,

[0047] - “m” represents 0, 1 or 2,

[0048] - “p” represents 0 or 1,

[0049] - “X” is O or NR9, “R9” representing H, a C1-C20 alkyl group, a cycloalkyl group or an alkylaryl group, and

[0050] - “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 between 2 and 250,

[0051] - “a” is a number between 0.05 and 0.95, “a” being the mole fraction of units of formula (I) in the polymer, and

[0052] - “b” is a number between 0.05 and 0.95, “b” being the mole fraction of units of formula (II) in the polymer.

[0053] Preferably, the polyalkoxylated phosphonate polymers are of the following formula (III): in which

[0054] “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;

[0055] “Q” is a hydrocarbon group containing from 2 to 18 carbon atoms and optionally one or more heteroatoms;

[0056] “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: - the A-PO3H2 group, A having the aforementioned meaning,

[0057] - 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,

[0058] "m" is a number greater than or equal to 0,

[0059] “r” is the number of [R5-O(Ri-O)m] groups carried by all Rj,

[0060] “q” is the number of [R5-O(Ri-O)m] groups carried by Q, the sum “r+q” is between 1 and 10,

[0061] “y” is an integer between 1 and 3,

[0062] “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.

[0063] 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 a calcium salt, and crystallized blast furnace slag. 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 a calcium salt, and an aluminum salt.

[0064] 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 a calcium salt, and a mixture of crystallized blast furnace slag and aluminum salt. According to this embodiment, the mass ratio between the mass content of crystallized blast furnace slag and the mass content of aluminum salt is between 0.1 and 10, preferably between 0.2 and 5, preferably between 0.5 and 2.

[0065] 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 crystallized blast furnace slag and the aluminum salt apply independently to the crystallized blast furnace slag and the aluminum salt.

[0066] Thus, for example, in the first embodiment, the crystallized blast furnace slag content is preferably between 0.5% and 40% by mass, preferably between 1% and 30% by mass, preferably between 2% and 20% by mass, preferably between 3% and 15% by mass, preferably between 4% and 10% 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%, 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 40% by mass, preferably between 18% and 35% by mass, or between 1% and 40% by mass, preferably between 2% and 40% by mass, preferably between 5% and 40% by mass,preferably between 10% and 40% by mass when the content is expressed relative to the total dry mass of active materials in the adjuvant composition); in the second embodiment, the aluminum salt content is preferably between 0.5% and 40% by mass, preferably between 1% and 30% by mass, preferably between 2% and 20% by mass, preferably between 3% and 15% by mass, preferably between 4% and 10% 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%, 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 40% by mass, preferably between 18% and 35% by mass, or between 1% and 40% by mass, preferably between 2% and 40% by mass). mass, preferably between 5% and 40% by mass,preferably between 10% and 40% by mass when the content is expressed relative to the total dry mass of active materials in the adjuvant composition); and for example, in the third embodiment, each of the crystallized blast furnace slag and the aluminum salt is independently present in a content preferably of between 0.5% and 40% by mass, preferably between 1% and 30% by mass, preferably between 2% and 20% by mass, preferably between 3% and 15% by mass, preferably between 4% and 10% by mass, relative to the total mass of the admixture composition (or preferably of between 1% and 60% by mass, preferably between 2% and 60% by mass, preferably between 2.5% and 55%, 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 40% by mass, preferably between 18% and 35% by mass, or between 1% and 40% by mass, preferably between 2% and 40% by mass,preferably between 5% and 40% by mass, preferably between 10% and 40% by mass when the content is expressed relative to the total dry mass of active materials in the adjuvant composition).

[0067] 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.

[0068] In particular, the contents relative to the total dry mass of active materials in the adjuvant composition are expressed relative to the total mass content of calcium salt, crystallized blast furnace slag and / or aluminum salt. In the first embodiment above, the contents relative to the total dry mass of active materials in the adjuvant composition may be expressed relative to the total mass content of calcium salt and crystallized blast furnace slag. In the second embodiment above, the contents relative to the total dry mass of active materials in the adjuvant composition may be expressed relative to the total mass content of calcium salt and aluminum salt.In the third embodiment above, the contents relative to the total dry mass of active materials in the adjuvant composition can be expressed relative to the total mass content of calcium salt, aluminum salt and crystallized blast furnace slag.

[0069] Hydraulic binder composition with admixture

[0070] The present invention also relates to an adjuvanted hydraulic binder composition comprising:

[0071] - a hydraulic binder composition comprising granulated blast furnace slag and calcium sulfate, and

[0072] - an adjuvant composition according to the invention.

[0073] Preferably, the content of adjuvant composition in the adjuvanted hydraulic binder composition, relative to the total dry mass of the hydraulic binder composition, is between 0.05% and 7% by mass, preferably between 0.1% and 5% by mass, preferably between 0.2% and 4% by mass, preferably between 0.3% and 2.5% by mass, preferably between 0.3% and 2% by mass. The present invention therefore relates to an adjuvanted hydraulic binder composition comprising:

[0074] - a hydraulic binder composition comprising granulated blast furnace slag and calcium sulfate,

[0075] - a calcium salt, as defined above, and

[0076] - crystallized blast furnace slag and / or an aluminum salt, as defined above.

[0077] 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 calcium salt, and the crystallized blast furnace slag and / or the aluminum salt) (and possibly the additional adjuvants), and the term "hydraulic binder composition" means the hydraulic binder composition free of adjuvant.

[0078] Calcium salt, crystallized blast furnace slag and aluminum salt are as defined above for the admixture composition.

[0079] Preferably, the hydraulic binder composition comprises (or consists of), relative to the total dry mass of hydraulic binder composition:

[0080] - from 50% to 99% by mass, preferably from 60% to 98% by mass, preferably from 70% to 95% by mass of granulated blast furnace slag,

[0081] - from 1% to 50% by mass, preferably from 2% to 40% by mass, preferably from 3% to 30% by mass of calcium sulfate, and

[0082] - optionally from 0% to 20% by mass, preferably from 0% to 15% by mass, preferably from 1% to 10% by mass of clinker.

[0083] Preferably, the hydraulic binder composition comprises (or consists of) a supersulfated cement.

[0084] Preferably, the hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, from 80% to 100% by mass, preferably from 90% to 100% by mass, preferably from 95% to 99% by mass, of supersulfated cement.

[0085] A supersulfated cement is a hydraulic binder comprising primarily granulated blast furnace slag and calcium sulfate. The granulated blast furnace slag is produced by rapid cooling (e.g., water quenching and spraying) of molten slag, and contains at least two-thirds by mass of vitreous (amorphous) slag. It is therefore distinguished from the crystallized blast furnace slag of the admixture composition of the invention. Preferably, the granulated blast furnace slag is ground.

[0086] 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.

[0087] Calcium sulfate includes gypsum (calcium sulfate dihydrate, CaSO4-2H2O) and / or hemihydrate (CaSC>4-1 / 2 H2O) and / or anhydrite (calcium sulfate anhydrous, CaSCU) or any mixture thereof.

[0088] Preferably, the granulated blast furnace slag of the oversulfated cement comprises from 67% to 100% by mass of blast furnace slag in amorphous form, relative to the total mass of granulated blast furnace slag contained in the oversulfated cement, preferably from 95% to 99% by mass, and the remainder being crystallized blast furnace slag.

[0089] According to the invention, the hydraulic binder composition therefore comprises granulated blast furnace slag, calcium sulfate, and optionally clinker.

[0090] A supersulfated cement according to the invention is as defined in standard EN 15743:2010+A1:2015.

[0091] Preferably, the supersulfated cement comprises (or consists of), relative to the total dry mass of supersulfated cement, 75% or more, preferably from 75% to 95% by mass of granulated blast furnace slag, from 5% to 20% by mass of calcium sulfate, and optionally from 0% to 5% by mass of clinker and optionally from 0% to 5% of secondary constituents (as defined by standard EN 15743:2010+A1:2015).

[0092] The hydraulic binder composition may also include 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 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

[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), limestones or their mixtures.

[0097] Preferably, the admixed hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, from 0.05% to 2% by mass, preferably from 0.1% to 1.5% by mass, preferably from 0.2% to 1% by mass, preferably from 0.2% to 0.8% by mass, preferably from 0.2% to 0.6% by mass of calcium salt.

[0098] Preferably, the admixed hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition, from 0.05% to 1.5% by mass, preferably from 0.06% to 0.8% by mass, preferably from 0.07% to 0.6% by mass, preferably from 0.08% to 0.5% by mass, preferably from 0.09% to 0.3% by mass of crystallized blast furnace slag and / or aluminum salt.

[0099] Preferably, the mass ratio between the mass content of calcium salt and the mass content of crystallized blast furnace slag and / or aluminum salt is between 0.02 and 40, preferably between 0.5 and 20, preferably between 0.7 and 10, preferably between 1 and 8, preferably between 1.2 and 5, preferably between 1.5 and 3.

[0100] The admixed hydraulic binder composition may further comprise at least one additive as described above for the admixture composition.

[0101] According to a first embodiment, the adjuvanted hydraulic binder composition comprises:

[0102] - a hydraulic binder composition as defined above comprising granulated blast furnace slag and calcium sulfate, and in particular comprising supersulfated cement,

[0103] - a calcium salt as defined above, and

[0104] - crystallized blast furnace slag as defined above.

[0105] According to a second embodiment, the adjuvanted hydraulic binder composition comprises:

[0106] - a hydraulic binder composition as defined above comprising granulated blast furnace slag and calcium sulfate, and in particular comprising supersulfated cement,

[0107] - a calcium salt as defined above, and

[0108] - an aluminum salt as defined above.

[0109] According to a third embodiment, the adjuvanted hydraulic binder composition comprises:

[0110] - a hydraulic binder composition as defined above comprising granulated blast furnace slag and calcium sulfate, and in particular comprising supersulfated cement,

[0111] - a calcium salt as defined above, and - a mixture of crystallized blast furnace slag and an aluminum salt, as defined above.

[0112] 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 crystallized blast furnace slag and the aluminum salt in the admixed hydraulic binder composition apply independently to the crystallized blast furnace slag and the aluminum salt. Thus, for example, in the first embodiment, the content of crystallized blast furnace slag is between 0.05% and 1.5% by mass, preferably between 0.06% and 0.8% by mass, preferably between 0.07% and 0.6% by mass, preferably between 0.08% and 0.5% by mass, preferably between 0.09% and 0.3% by mass relative to the total dry mass of the hydraulic binder composition;in the second embodiment, the aluminum salt content is between 0.05% and 1.5% by mass, preferably between 0.06% and 0.8% by mass, preferably between 0.07% and 0.6% by mass, preferably between 0.08% and 0.5% by mass, preferably between 0.09% and 0.3% by mass relative to the total dry mass of the hydraulic binder composition; and for example, in the third embodiment, each of the crystallized blast furnace slag and the aluminum salt is independently present in a content of between 0.05% and 1.5% by mass, preferably between 0.06% and 0.8% by mass, preferably between 0.07% and 0.6% by mass, preferably between 0.08% and 0.5% by mass, preferably between 0.09% and 0.3% by mass relative to the total dry mass of the hydraulic binder composition.;

[0113] Hydraulic composition

[0114] The present invention also relates to a hydraulic composition comprising:

[0115] - a hydraulic binder composition mainly consisting of granulated blast furnace slag and calcium sulfate, and in particular supersulfated cement, as defined above,

[0116] - an adjuvant composition according to the invention,

[0117] - water,

[0118] - possibly an aggregate, and

[0119] - possibly a mineral addition.

[0120] The present invention therefore relates to a hydraulic composition comprising:

[0121] - an admixed hydraulic binder composition as defined above, - water,

[0122] - possibly an aggregate, and

[0123] - possibly a mineral addition.

[0124] The hydraulic composition is preferably a composition of concrete, mortar or screed.

[0125] Aggregates are defined as 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:

[0126] - fillers, which have a diameter less than 2 mm and for which at least 85% of the aggregates have a diameter less than 1.25 mm and at least 70% of the aggregates have a diameter less than 0.063 mm,

[0127] - sands with a diameter between 0 and 6.3 mm,

[0128] - gravel with a diameter greater than 6.3 mm, gravel with a diameter between 2 mm and 63 mm.

[0129] Sands are therefore included in the definition of aggregate according to the invention.

[0130] Fillers can be of limestone or dolomitic origin.

[0131] 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

[0132] 5.2.3), fly ash (as defined in EN 197-1:201 1 paragraph

[0133] 5.2.4), calcined shale (as defined in standard EN 197-1:2011 paragraph

[0134] 5.2.5), or silica fumes (as defined in standard EN 197-1:2011 paragraph 5.2.7 or standard EN 197-5:2021 paragraph 5), limestones or their mixtures.

[0135] The hydraulic composition may further comprise at least one additive as described above for the adjuvant composition.

[0136] 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.

[0137] The present invention also relates to the use of an adjuvant composition according to the invention, for improving the compressive mechanical strengths, preferably in the short term, of a hydraulic binder composition comprising granulated blast furnace slag and calcium sulfate, and in particular comprising a supersulfated cement. The expressions "from ... to ...", "between ... and ...", "ranging from ... to ...", "varies from ... to ...", and "less than ..." must be understood inclusively, unless otherwise specified.

[0138] The invention is illustrated in the following examples.

[0139] Example 1: Description of adjuvant compositions

[0140] The adjuvant compositions were prepared by mixing the ingredients described in the following table with the indicated contents, expressed relative 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.

[0141] [Table 1]

[0142] : comparison

[0143] [Table 2] Granulometry and Blaine Specific Surface Area of ​​Ground Crystallized Blast Furnace Slag and Siliceous Filler

[0144] Example 2: Testing of adjuvant compositions in mortar-type hydraulic compositions The mortar used has the composition shown in Table 3 below.

[0145] [Table 3] The superplasticizing polymers used to admix the mortar are as follows:

[0146] - Polymer 1 consisting of the following units: with a = 82.3, b = 17.7 and z = 53.

[0147] - Polymer 2 consisting of the following units: with a = 55, b = 23.5, c = 21.5 and z = 17. [Table 4] Mineralogical composition of supersulfated cement (SSC) determined by X-ray diffraction and Rietveld refinement

[0148] [Table 5] Elemental composition of the amorphous phase of supersulfated cement (SSC) determined by X-ray fluorescence spectrometry

[0149] [Table 6] Granulometry and Blaine Specific Surface of supersulfated cement (CSS)

[0150] The compositions of Example 1 were added to this mortar in the contents of the following table (expressed as a percentage by mass of each adjuvant relative to the total dry mass of binder).

[0151] [T able 7]

[0152] : comparison

[0153] These results clearly demonstrate the synergistic effect between calcium hydroxide and crystallized blast furnace slag and / or aluminum hydroxide. Indeed, when used alone, crystallized blast furnace slag and aluminum hydroxide have a deleterious effect on the 24-hour compressive strength; but when mixed with calcium hydroxide, they improve its effect on the compressive strength.

[0154] The result obtained with the CH8* composition illustrates that too much aluminum salt is detrimental to mechanical resistance in compression.

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 a calcium salt, and - from 1% to 40% by mass of crystallized blast furnace slag and / or from 1% to 40% by mass of an aluminum salt.

2. Adjuvant composition according to claim 1, in which the content of crystallized blast furnace slag and / or aluminum salt is between 2% and 40% by mass, preferably between 5% and 40% by mass, preferably between 10% and 40% by mass, preferably between 15% and 40% by mass, preferably between 18% and 35% 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 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 dihydroxide.

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, in which the mass ratio between the mass content of calcium salt and the mass content of crystallized blast furnace slag and / or aluminum salt is between 0.02 and 40, preferably between 0.5 and 20, preferably between 0.7 and 10, preferably between 1 and 8, preferably between 1.2 and 5, preferably between 1.5 and 3.

6. An admixture composition according to any one of the preceding claims, wherein the crystallized blast furnace slag comprises from 0% to 40% by mass of amorphous phase and from 60% to 100% by mass of crystalline phase, relative to the total mass of crystallized blast furnace slag, preferably from 0% to 20% by mass of amorphous phase and from 80% to 100% by mass of crystalline phase, preferably from 0% to 15% by mass of amorphous phase and from 85% to 100% by mass of crystalline phase.

7. Adjuvant composition according to any one of the preceding claims, wherein the size of the crystallized blast furnace slag particles is between 10 nm and 500 pm, preferably between 0.2 pm and 400 pm.

8. 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.

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

10. Composition of adjuvanted hydraulic binder comprising: - a hydraulic binder composition comprising granulated blast furnace slag and calcium sulfate, in particular comprising a supersulfated cement, and - an adjuvant composition according to any one of claims 1 to 9.

11. An admixed hydraulic binder composition according to claim 10, wherein the content of admixture composition is between 0.05% and 7% by mass, preferably between 0.1% and 5% by mass, preferably between 0.2% and 4% by mass, preferably between 0.3% and 2.5% by mass, preferably between 0.3% and 2% by mass, relative to the total dry mass of the hydraulic binder composition.

12. An admixed hydraulic binder composition according to claim 10 or 11, wherein the hydraulic binder composition comprises, relative to the total dry mass of the hydraulic binder composition: - from 50% to 99% by mass, preferably from 60% to 98% by mass, preferably from 70% to 95% by mass of granulated blast furnace slag, - from 1% to 50% by mass, preferably from 2% to 40% by mass, preferably from 3% to 30% by mass of calcium sulfate, and - optionally from 0% to 20% by mass, preferably from 0% to 15% by mass, preferably from 1% to 10% by mass of clinker.

13. An admixed hydraulic binder composition according to any one of claims 10 to 12, wherein the hydraulic binder composition comprises a supersulfated cement.

14. An admixed hydraulic binder composition according to any one of claims 10 to 13, comprising, relative to the total dry mass of the hydraulic binder composition: - from 0.05% to 2% by mass of calcium salt, and - from 0.05% to 1.5% by mass of crystallized blast furnace slag and / or aluminum salt.

15. Hydraulic composition comprising: - a hydraulic binder composition comprising granulated blast furnace slag and calcium sulfate, and in particular comprising a supersulfated cement, - an adjuvant composition as defined according to any one of claims 1 to 9, - 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 9, for improving the mechanical compressive strengths, preferably in the short term, of a hydraulic binder composition comprising granulated blast furnace slag and calcium sulfate, and in particular comprising a supersulfated cement.

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