Method for accelerating and fluidizing wet concrete or mortar compositions containing activators, water-reducing polymers, comprising the use of a performance additive containing chaotropic ions, and its use in low-carbon alternative binder compositions

Abstract

The present invention relates to a method for fluidizing a wet concrete or industrial mortar composition comprising (a) at least one hydraulic binder, (b) at least one water-reducing polymer, (c) at least one accelerator in the form of a salt containing at least one kosmotropic ion, (d) water, and (e) optionally one or more auxiliary cementitious materials, and (f) optionally one or more filler materials, the method comprising the step of adding at least one salt (ch) containing at least one chaotropic ion to the concrete or industrial mortar composition.

Description

[Technical Field]

[0001] The technical field of the present invention relates to mineral binder compositions that provide accelerating and fluidizing effects. More specifically, the present invention relates to a method for accelerating and fluidizing a wet concrete or mortar composition comprising at least one activator comprising a kosmotropic ion and at least one water reducing polymer by adding at least one salt comprising a chaotropic ion that co-fluidizes the wet concrete or mortar composition with the water reducing polymer.

[0002] The present invention also relates to the use of at least one salt containing chaotropic ions to provide good fresh state rheology and early hardened mechanical properties across the concrete industry, which is comprised of some combination of hydraulic binder, supplemental cementitious material, and filler material, and which includes at least one activator containing kosmotropic ions and at least one water-reducing polymer. [Background technology]

[0003] Due to the strong negative environmental impact of ordinary Portland cement production due to the large amount of carbon dioxide emissions, supplementary cementitious materials (SCMs), such as mortars and concretes containing large amounts of ground granulated blast furnace slag (GGBS), are increasingly being used. In cement production, CO2 is essentially generated during the calcination of raw materials at very high temperatures (1450°C) in kilns due to the decarbonation of limestone (Equation (1)). CaCO3(s)→CaO(s)+CO2(g) (Equation (1)) Additionally, carbon dioxide is released as a result of the burning of fossil fuels required to heat cement kilns. Add in the additional emissions from grinding, and you get almost one tonne of CO2 per tonne of Portland cement. Overall, the cement industry accounts for around 7-9% of global carbon dioxide emissions.

[0004] Furthermore, to produce mortar or concrete with desired early mechanical properties, it is generally necessary to add accelerators to the binder containing a large amount of SCM. Activators are often used to accelerate the strength development of these alternative binders. Activators are compounds that induce alkaline conditions favorable for strength development in SCM-containing binders. Activators are most commonly compounds with sodium or potassium as the cation and hydroxide, silicate, sulfate, or carbonate as the anion. However, these salts can have a negative effect on Portland cement. WO 2019 / 077389 discloses a method to avoid this negative effect by incorporating a retarder into the cement composition and adding the accelerator at least 30 seconds after mixing the other components.

[0005] To improve the fluidity and workability of mortar and concrete, it is common to add water-reducing polymers, also known as plasticizers or superplasticizers. While these water-reducing polymers are generally effective for mortars and concretes with binders made with ordinary Portland cement, they are often less effective at improving the fluidity and workability of mortars and concretes with binders containing SCM. Furthermore, the accelerators generally reduce the solubility of the water-reducing polymers, reducing their efficiency.

[0006] As a result, a given water-reducing polymer may be more or less effective depending on the binder or concrete composition. As a result, in alternative binder compositions made with SCM and activators, the water-reducing polymer cannot perform its role adequately, and the concrete or mortar does not have the expected fluidity and workability.

[0007] To overcome this problem, efforts have been made to develop water-reducing polymers designed for SCM and alternative binder compositions made with alkaline activators. This solution may not be applicable to all binders activated with an activator.

[0008] Therefore, it would be beneficial to have a different solution to the above, which by adapting a few parameters could be suitable for all kinds of alternative binder compositions made with SCM and activators.

[0009] In this regard, the present invention aims to address at least one of the above problems and / or needs by fulfilling at least one of the following objectives: -O1- To provide a method for fluidizing wet mortar and concrete by fluidizing a binder composition comprising some combination of hydraulic binder and optionally supplementary cementitious material and / or filler material. -O2- To provide mortar and concrete with adequate rheology in the wet state before hardening and good mechanical properties after hardening, especially good early strength. -O3- To provide an efficient process for fluidizing a wet concrete or industrial mortar composition before hardening and accelerating strength development after said hardening, said composition comprising at least one water-reducing polymer and at least one alkaline accelerator in the form of a salt containing at least one kosmotropic ion. -O4- To provide ready-mix concrete and precast concrete comprising an alternative binder composition made with SCM, activated with an activator, and fluidized with at least one common water-reducing polymer. Summary of the Invention

[0010] The present invention provides (a) at least one hydraulic binder; (b) at least one water-reducing polymer; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (d) water and (e) one or more auxiliary cementitious materials, as the case may be; and (f) optionally one or more filler materials; 1. A method for fluidizing a wet concrete or industrial mortar composition comprising: The present invention relates to a method comprising the step of adding at least one salt (ch) containing at least one chaotropic ion to a concrete or industrial mortar composition.

[0011] The present invention also relates to the use of at least one salt (ch) containing at least one chaotropic ion as a co-plasticizer with at least one water-reducing polymer (b) for a wet concrete or industrial mortar composition comprising water, at least a binder fraction and at least one aggregate fraction, wherein the binder fraction is (a) at least one hydraulic binder; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (d) water and (e) one or more auxiliary cementitious materials, as the case may be; and (f) optionally one or more filler materials; Regarding use, including

[0012] The present invention provides (a) at least one hydraulic binder; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (d) water and (e) one or more auxiliary cementitious materials, as the case may be; and (f) optionally, one or more filler materials; 1. A method for fluidizing a wet concrete or industrial mortar composition comprising: The present invention further relates to a method comprising the step of adding to a concrete or industrial mortar composition at least one salt comprising at least one chaotropic ion (ch) and at least one water-reducing polymer (b) in amounts that do not increase compared to a wet concrete or industrial mortar composition (CEC) of the same target consistency class comprising components a, c, d, optionally e, and optionally f, but not component c, in order to obtain said wet concrete or industrial mortar composition in a target consistency class according to European Standard EN 206.

[0013] The present invention relates to a performance additive for accelerating and fluidizing wet concrete or industrial mortar compositions comprising at least one hydraulic binder (a), at least one water-reducing polymer (b), at least one accelerator in the form of a salt containing at least one kosmotropic ion (c), the performance additive having a free water content of less than 0.5% by weight, The present invention further relates to a performance additive comprising at least one salt (ch) comprising at least one chaotropic ion.

[0014] Activators are usually incompatible with water-reducing polymers and significantly reduce their ability to fluidize cement systems, but the inventors have surprisingly discovered that the addition of salts containing chaotropic ions, particularly chaotropic anions, can enhance the action of water-reducing polymers.

[0015] One of the merits of the present inventors is that in a building material system comprising a hydraulic binder, in particular GGBS, a water-reducing polymer and an accelerator in the form of at least one salt containing at least one alkali cation and at least one kosmotropic ion, they have demonstrated the detrimental effects of the kosmotropic ions in the accelerator and the elimination or at least mitigation of said detrimental effects by the introduction of chaotropic ions.

[0016] One advantage of the present invention is that it provides a method for producing a powerful fluidization effect. Another advantage is extended open time: not only is the desired fluidizing effect initially present, but the process allows fluidity to remain longer than is typically possible in the presence of activators and water-reducing polymers.

[0017] General definition In accordance with the terminology of this document, the following non-limiting definitions should be considered: - "Binder" refers to a material composed of one or more hydraulic binders, and optionally one or more auxiliary cementitious materials, and optionally one or more filler materials. - "hydraulic binder" refers to a material that hardens upon reaction with water. Here, this term refers to pure ordinary Portland cement and standardized cement made with calcium aluminate cement, calcium sulfoaluminate cement, belite cement, ground granulated blast furnace slag, basic oxygen furnace slag, ladle slag, supersulfated cement, hydraulic lime, cement kiln dust, or mixtures thereof. - "Supplementary cementitious material" refers to a material that contributes to the strength of the binder by virtue of its latent hydraulic or pozzolanic activity, where the term refers to ground blast furnace slag, fly ash, activated clay, silica fume, basic oxygen furnace slag, natural pozzolanic materials, rice husk ash, activated recycled concrete fine aggregate, or mixtures thereof. - "Filler material" refers to a material whose primary role in the binder is physical rather than chemical. Fillers occupy pore space and are less energy intensive, and are therefore used as an alternative to hydraulic binders and auxiliary cementitious materials. Here, the term refers to crushed limestone, crushed dolomite, marble powder, siliceous sand, recycled concrete fine aggregate, or mixtures thereof. - "Slag" means the stony waste material separated from the metal during the smelting or refining of ores. - "GGBS" or "GGBFS": Ground blast furnace slag, which is equivalent to blast furnace slag, granulated blast furnace slag (GBFS), granulated blast furnace slag powder, and blast furnace slag fine aggregate. - "Cement" is understood to mean a powdered substance prepared for use in making mortar or concrete. It is an inorganic binder, which may in some cases contain no organic compounds. It includes ordinary Portland cement, Portland slag cement, Portland silica fume cement, Portland pozzolana cement, Portland fly ash cement, Portland burnt shale cement, Portland limestone cement, Portland composite cement, blast furnace slag cement, supersulphated cement, calcium aluminate cement, pozzolanic cement, and composite cement. - "Mortar" refers to a material composed of a binder and an aggregate such as sand. - "Concrete" refers to a material composed of a binder and aggregates such as sand and (fine) gravel. - "Dry weight" is the weight of a material in its natural state (without the addition of exogenous water or other solutions). - "Apparent viscosity" is the shear stress applied to a fluid divided by the shear rate. It is used to describe the viscosity of non-Newtonian fluids whose viscosity depends on the shear rate. In the International System of Units (IS), apparent viscosity is expressed in Pascal seconds (Pa.s). [Brief explanation of the drawings]

[0018] [Figure 1] 1 is a graph of the yield stress versus time after mixing of wet binder composition samples, showing the effect of a water-reducing polymer (b), a kosmotropic activator (c), and a salt containing at least one chaotropic ion (ch) on the yield stress of the paste samples. [Figure 2]1 is a graph of the yield stress versus time after mixing of wet binder composition samples, showing the effect of a water-reducing polymer (b), a kosmotropic activator (c), and a salt containing at least one chaotropic ion (ch) on the yield stress of the paste samples. [Figure 3] 1 is a graph of the yield stress versus time after mixing of wet binder composition samples, showing the effect of a water-reducing polymer (b), a kosmotropic activator (c), and a salt containing at least one chaotropic ion (ch) on the yield stress of the paste samples. [Figure 4] 1 is a graph of the yield stress versus time after mixing of wet binder composition samples, showing the effect of a water-reducing polymer (b), a kosmotropic activator (c), and a salt containing at least one chaotropic ion (ch) on the yield stress of the paste samples. [Figure 5] 1 is a graph of the yield stress versus time after mixing of wet binder composition samples, showing the effect of a water-reducing polymer (b), a kosmotropic activator (c), and a salt containing at least one chaotropic ion (ch) on the yield stress of the paste samples. [Figure 6] 1 is a graph of the yield stress versus time after mixing of wet binder composition samples, showing the effect of a water-reducing polymer (b), a kosmotropic activator (c), and a salt containing at least one chaotropic ion (ch) on the yield stress of the paste samples. [Figure 7] 1 is a graph of the yield stress versus time after mixing of wet binder composition samples, showing the effect of a water-reducing polymer (b), a kosmotropic activator (c), and a salt containing at least one chaotropic ion (ch) on the yield stress of the paste samples. [Figure 8]1 is a graph of heat versus time after mixing of wet binder composition samples. The graph shows the effect of the present invention on the heat generated by paste samples over the first 24 hours. Heat can be used as a proxy for assessing the relative early strength of such binders due to the exothermic nature of hydration of cementitious systems. [Figure 9] 1 is a graph of heat versus time after mixing of wet binder composition samples. The graph shows the effect of the present invention on the heat generated by paste samples over the first 24 hours. Heat can be used as a proxy for assessing the relative early strength of such binders due to the exothermic nature of hydration of cementitious systems. [Figure 10] 1 is a graph of heat versus time after mixing of wet binder composition samples. The graph shows the effect of the present invention on the heat generated by paste samples over the first 24 hours. Heat can be used as a proxy for assessing the relative early strength of such binders due to the exothermic nature of hydration of cementitious systems. DETAILED DESCRIPTION OF THE INVENTION

[0019] Method for fluidizing wet concrete or industrial mortar compositions (a) one hydraulic binder; (b) at least one water-reducing polymer; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (d) water and (e) one or more auxiliary cementitious materials, as the case may be; and (f) optionally one or more filler materials; A method for fluidizing a wet concrete or industrial mortar composition, comprising: The method comprises adding at least one salt (ch) comprising at least one chaotropic ion to a concrete or industrial mortar composition.

[0020] As used herein, a "kosmotropic ion" is an ion that enhances the structure of water and decreases the solubility of non-polar solvent molecules or particles. More specifically, in the sense of the present invention, an ion is considered to be cosmotropic if it reduces the water solubility of a given water-reducing polymer. In fact, the effect of the ion depends on the water-reducing polymer used.

[0021] As used herein, a "chaotropic ion" is an ion that disrupts the structure of water and increases the solubility of non-polar solvent molecules or particles. More specifically, within the meaning of the present invention, an ion is considered to be chaotropic if it is capable of solubilizing a given water-reducing polymer. Indeed, the effect of the ion depends on the water-reducing polymer used.

[0022] Use of at least one salt (ch) containing at least one chaotropic ion as a co-fluidizing agent As mentioned above, one object of the present invention is to provide concrete and industrial mortars that have suitable rheology in the wet state before hardening and good mechanical properties after hardening, in particular good early strength. To achieve this object, the present invention relates to the use of at least one salt (ch) containing at least one chaotropic ion as a co-plasticizer with at least one water-reducing polymer (b) for a wet concrete or industrial mortar composition comprising water, at least a binder fraction, and at least one aggregate fraction, wherein the binder fraction is (a) at least one hydraulic binder; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (e) one or more auxiliary cementitious materials, as the case may be; and (f) optionally one or more filler materials; It also relates to the use of

[0023] The amount of salt (ch) containing at least one chaotropic ion as a co-fluidizing agent in the binder fraction depends on the nature and amount of the other components in the binder fraction. Therefore, the content of each component in the binder fraction is determined in relation to the other binder fractions.

[0024] In a preferred embodiment, the binder fraction is, in dry weight % based on the total weight of the hydraulic binder (a), auxiliary cementitious material (e) and filler material (f), the salt (ch) containing at least one chaotropic ion in an amount between 0.001 and 10, preferably between 0.01 and 5, more preferably between 0.1 and 3, said water-reducing polymer (b) between 0.005 and 5.0, preferably between 0.01 and 3.0, more preferably between 0.1 and 2, and said accelerator (c) between 0.1 and 10, preferably between 0.5 and 5, more preferably between 1 and 3; Includes:

[0025] Hydraulic binder (a) Advantageously, the hydraulic binder (a) is selected from the group consisting of ordinary portland cement, calcium aluminate cement, calcium sulfoaluminate cement, belite cement, hydraulic lime, ground blast furnace slag, basic oxygen furnace slag, ladle slag, supersulphated cement, cement kiln dust or mixtures thereof.

[0026] Ordinary Portland cement and standardized cement often contain small amounts of gypsum or calcium sulfate substitutes to act as set regulators, however, gypsum may also be added to hydraulic binders.

[0027] Water-reducing polymer (b) In a preferred embodiment, the water-reducing polymer (b) is selected from the group consisting of lignosulfonate polymers, melamine sulfonate polymers, naphthalene sulfonate polymers, polycarboxylic acid ether polymers, polyoxyethylene phosphonates, vinyl copolymers, and mixtures thereof.

[0028] a promoter in the form of a salt containing at least one kosmotropic anion (c); Kosmotropic ions can be singly or multiply charged.

[0029] In a preferred embodiment, the kosmotropic ion of the promoter (c) is carbonate ion (CO 2- ), sulfate ions (SO4 2- ), hydroxide ion (OH - ), citrate ion (C6H5O7 3- ), phosphate ions (PO4 3- ), hydrogen phosphate ion (HPO4 2- ), dihydrogen phosphate ion (HPO4 - ), tartrate ion (C4H4O6 2- ), acetate ion (CH3COO - ), formate ion (HCOO - ), bicarbonate ion (HCO3 - ), orthosilicate ion (SiO4 4- ), metasilicate ion (SiO3 2- ), pyrosilicate ion (Si2O7 6- ), polyphosphate ions, polysilicate ions and thiosulfate ions (S2O3 2- ) is an anion from the group consisting of

[0030] Advantageously, the cation of the promoter (c) in salt form is selected from the group consisting of sodium, potassium and lithium.

[0031] Salt containing at least one chaotropic ion (ch) The chaotropic ions of the salt (ch) may be monovalent or polyvalent anions or cations.

[0032] In a preferred embodiment, the chaotropic ion of the salt (ch) is chloride ion (Cl - ), bromide ion (Br - ), nitrate ions (NO3 - ), chlorate ion (ClO3 -), perchlorate ion (ClO4 - ), tetrafluoroborate ion (BF4 - ), iodide ion (I - ), thiocyanate ion (SCN - ) Hexafluorophosphate ion (PF6 - ), guanidinium ion (C(NH2)3 + ), trichloroacetate ion (CCl3COO - ), dichloroacetate ion (CHCl2COO - ), chloroacetate ion (CH2ClCOO - ), tribromoacetate ion (CBr3COO - ) or trifluoroacetate ion (CF3COO - Advantageously, it is selected from the group consisting of:

[0033] Advantageously, said salt (ch) comprising at least one chaotropic ion is potassium thiocyanate (KSCN), potassium nitrate (KNO3), potassium chloride (KCl), sodium thiocyanate (NaSCN), sodium nitrate (NaNO3), sodium chloride (NaCl), magnesium chloride (MgCl2), magnesium nitrate (Mg(NO3)2), calcium chloride (CaCl2), calcium nitrate (Ca(NO3)2), calcium thiocyanate (Ca ( SCN ) 2), barium chloride (BaCl2), strontium nitrate (Sr(NO3)2), guanidinium chloride (CH6ClN3) and guanidinium thiocyanate (C2H6N4S).

[0034] Salt (ch) / accelerator (c) ratio The efficiency of chaotropic ions depends on several factors, such as the type of accelerator, the type of water-reducing polymer, and the ratio of water / binder composition / aggregate / gravel in the resulting wet concrete or industrial mortar composition. Those skilled in the art can determine the optimal activator (c) / salt (ch) / water-reducing polymer ratio by routine experimentation.

[0035] However, in a preferred embodiment, in the method according to the invention, the dry weight ratio of salt (ch) including at least one chaotropic ion to said accelerator (c) is comprised between 0.01 and 3.0.

[0036] water (d) In a preferred embodiment, the weight ratio of water to hydraulic binder (d / a) is comprised between 0.08 and 1.0, preferably between 0.25 and 0.9, more preferably including the following ranges, advantageously selected from the group consisting of the following ranges: [0.25;0.35], [0.35;0.45], [0.45;0.6], [0.6;0.9].

[0037] Auxiliary cementitious materials (e) The supplemental cementitious material (e) is preferably selected from the group consisting of fly ash calcined and uncalcined clays, silica fume, basic oxygen furnace slag, natural pozzolanic materials, rice husk ash, activated recycled concrete fine aggregate, or mixtures thereof.

[0038] Filler material (f) The filler material (f) is preferably selected from the group consisting of crushed limestone, crushed dolomite, marble powder, siliceous sand, recycled concrete fine aggregate or mixtures thereof.

[0039] Additional Optional Ingredients The binder composition is advantageously enriched with one or several other ingredients, particularly preferably functional additives selected from the list below. - Moisture retention agent Water retention agents have the ability to retain the mixing water before hardening. The water is trapped in the wet paste formulation, improving adhesion and, to some extent, making the water less likely to be absorbed by the substrate.

[0040] The humectant preferably comprises modified cellulose, modified guar, modified cellulose ether and / or guar ether and mixtures thereof, more preferably selected from the group consisting of methyl cellulose, methyl hydroxypropyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof. - Rheological agents Possible rheological agents (also called "thickeners") are preferably selected from the group comprising, more preferably consisting of, clays, starch ethers, cellulose ethers and / or gums (e.g., welan, guar, xanthan, succinoglycan), modified polysaccharides, preferably modified starch ethers, polyvinyl alcohols, polyacrylamides, clays, sepiolite, bentonite, and mixtures thereof, and more preferably selected from the group of clays, bentonite, montmorillonite. - Defoamer / Anti-foaming agent Possible antifoaming agents are preferably selected in the group comprising, more preferably consisting of, polyether polyols and mixtures thereof. - Biocides Possible biocides are preferably selected in the group comprising, more preferably consisting of, inorganic oxides such as zinc oxide and mixtures thereof. - Pigments Possible pigments are preferably selected in the group comprising, more preferably consisting of, TiO2, iron oxides and mixtures thereof. - Flame retardants Possible flame retardants (or flame retardants) are those that make it possible to increase the fire resistance of the composition and / or reduce the flame propagation speed, preferably minerals, preferably aluminum hydroxide [Al(OH)3, ATH], magnesium hydroxide MDH, hydromagnesium hydrate, red phosphorus and boron compounds, preferably borates; - organic halogen compounds, preferably organic chlorides (organochlorines), more preferably chlorendic acid derivatives and chlorinated paraffins, etc.; organic bromides (organoburomines), such as decabromodiphenyl ether (decaBDE) and decabromodiphenylethane, polymeric brominated compounds, preferably brominated polystyrene, brominated carbonate oligomers (BCO), brominated epoxy oligomers (BEO), tetrabromophthalic anhydride, tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD), antimony, preferably pentoxide and sodium antimonite, organic phosphorus compounds, preferably organic phosphates, TPP, RDP, BPADP, tri-o-cresyl phosphate, phosphonates, preferably DMMP and phosphinates, - chlorophosphates such as TMCP and TDCP, and more preferably selected from the group consisting of: - Air entraining agents The air entraining agent (surfactant) is advantageously selected from the group comprising, more preferably consisting of, natural resins, sulfated or sulfonated compounds, synthetic detergents, organic fatty acids and mixtures thereof, preferably from the group comprising, more preferably consisting of, lignosulfonates, basic soaps of fatty acids and mixtures thereof, more preferably from the group comprising, more preferably consisting of, olefin sulfonates, sodium lauryl sulfate and mixtures thereof. - Retardant The retarding agent is advantageously chosen in the group consisting of tartaric acid and its salts: sodium or potassium salt, citric acid and its salts: sodium (trisodium citrate) and mixtures thereof, more preferably. - Fiber - Dispersion powder - Wetting agent - Polymer resin - Complexing Agents - Polyol-based drying shrinkage reducing agent.

[0041] The total content of these optional other ingredients is preferably comprised between 0.001% and 10% by weight of the total weight of the binder fraction.

[0042] Aggregate fraction Aggregates comprise a broad category of particulate materials used in construction, including sand, gravel, crushed stone, slag (ungranulated), recycled concrete, and geosynthetic aggregates. Aggregates act as reinforcement to add strength to the overall composite material.

[0043] The concrete or industrial mortar composition may also contain fillers based on, for example, quartz, limestone, or clay and mixtures thereof, as well as light fillers such as perlite, diatomaceous earth, expanded mica (vermiculite) and expanded sand, and mixtures thereof.

[0044] Advantageously, said concrete or industrial mortar composition may also comprise, apart from aggregates, one or several components, in particular functional admixtures, additives and fibres, which may be the same as the other optional components mentioned above in the section "Additional optional components".

[0045] The total content of these optional other components in the concrete or industrial mortar composition is preferably comprised between 0.1% and 10% by weight of the total weight of the aggregate fraction. Process for preparing wet concrete or mortar compositions The present invention also provides (a) at least one hydraulic binder; (b) at least one water-reducing polymer; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (d) water and (e) one or more auxiliary cementitious materials, as the case may be; and (f) optionally one or more filler materials; at least one salt (ch) containing at least one chaotropic ion, and At least one aggregate fraction The present invention relates to a process for preparing a wet concrete or mortar composition, comprising the step of mixing together, simultaneously or not simultaneously, separately or not separately,

[0046] According to the present disclosure, the term "mixing" should be understood as any form of mixing. In a preferred embodiment, a portion of the binder and at least a portion of the water are mixed together before mixing with the aggregate.

[0047] In a preferred embodiment, the process is carried out at a weight ratio of water to hydraulic binder (d / a) comprised between 0.08 and 1.0, preferably between 0.25 and 0.9, more preferably including the following ranges, advantageously selected from the group consisting of the following ranges: [0.25; 0.35], [0.35; 0.45], [0.45; 0.6], [0.6; 0.9].

[0048] In a preferred embodiment, for a given amount of said at least one accelerator (c), the amount of said salt (ch) comprising at least one chaotropic ion and said at least one water-reducing polymer (b) is sufficient to both promote and control the fluidity of the wet concrete or mortar composition for the required period after said mixing step, depending on the application, preferably for at least 2 hours after said mixing step.

[0049] Ready-mix or precast concrete compositions The present invention relates to a ready-mix concrete or precast concrete composition, in particular for building construction and civil engineering works, which comprises at least one aggregate fraction, at least one salt (C₁₈) containing at least one chaotropic ion, and (a) at least one hydraulic binder; (b) at least one water-reducing polymer; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (d) water and (e) one or more auxiliary cementitious materials, as the case may be; and (f) optionally one or more filler materials; The present invention also relates to a ready-mix or precast concrete composition comprising:

[0050] The invention is particularly useful for ready-mix or precast concrete, the fluidity of which must in fact be maintained over a period covering production at the factory, delivery and use at the final site of use. [Example]

[0051] The yield stress is the stress threshold for permanent deformation of the composition and characterizes its inherent flowability or workability.

[0052] Time evolution procedure for yield stress The properties and contents of each component are shown in Table 1 below. 1. Weigh out the components of the hydraulic binder and add them to a mixing cup for a total mass of 100 g. If present, add the chaotropic salt and activator to more than 100 g of the dry hydraulic binder. Mix the resulting binder composition using an overhead stirrer (IKA Eurostar 40) equipped with a propeller blade at 150 RPM for 30 seconds. 2. Weigh tap water to the desired mass and add to the mixing cup. 3. Use a syringe to weigh out the water-reducing polymer to the desired mass. 4. Add tap water to the mixing cup containing the binder composition (i.e., hydraulic binder and salt and / or activator). Stir the resulting mixture at 150 RPM for 30 seconds, then at 550 RPM for 90 seconds, and then let it sit for 120 seconds. 5. After said 120 seconds, add the weighed amount of water-reducing polymer and mix the wet composition at 550 RPM for an additional 60 seconds. 6. The wet composition is then poured or scooped into the sample cup of the AR-2000-ex rheometer until the cup is full. The rheometer is equipped with a vane concentric cylinder geometry. The geometry is lowered into the measurement position. 7. Stabilize the binder at approximately 20°C using a rheometer. 8. The wet composition is mixed for 30 seconds at a shear rate of 25 / s to remove air bubbles and ensure uniformity. 9. The rheometer geometry begins to rotate at a shear rate of 0.1 / s. The stress measurement at this shear rate is taken as the yield stress. 10. Measurements are taken at 15 different shear rates, increasing from 0.1 / s to 50 / s, with logarithmic measurement intervals. 11. After the measurement at 50 / s is complete, mix the binder at 25 / s for 30 seconds as in step 8. 12. Measurements are taken as in step 10, but in reverse (starting at 50 / s and slowing down to 0.1 / s). The measurement at 0.1 / s is not taken into account as yield stress due to hysteresis. 13. Repeat steps 8-12 as many times as necessary to cover the desired test period.

[0053] [Table 1]

[0054] FIG. 1 is a graph showing the yield stress versus time after mixing for samples CE1, CE2 and E1. FIG. 2 is a graph showing the yield stress versus time after mixing for samples CE1, CE2 and E2.

[0055] FIG. 3 is a graph of yield stress versus time after mixing for samples CE1, CE2 and E3. FIG. 4 is a graph of yield stress versus time after mixing for samples CE1, CE2 and E4.

[0056] FIG. 5 is a graph of yield stress versus time after mixing for samples CE3, CE4 and E5. FIG. 6 is a graph of yield stress versus time after mixing for samples CE3, CE4 and E6.

[0057] FIG. 7 is a graph of yield stress versus time after mixing for samples CE5, CE6 and E7. As can be seen from these graphs, in the absence of accelerator (c) and salt containing chaotropic ions (ch), the yield stresses of compositions CE1 and CE5 are approximately equal to 0 Pa, and the yield stress of composition CE3 is about 1, and these yield stresses do not change significantly with time. Such low yield stresses are due to the presence of a water-reducing polymer that fluidizes the binder composition.

[0058] Conversely, the addition of accelerator (c) containing kosmotropic ions (CE2, CE4, and CE6) significantly increases the yield stress. Accelerator (c) significantly reduces the fluidity of the sample, and the effect of the water-reducing polymer is significantly reduced.

[0059] Thanks to the addition of the salt (ch) containing the chaotropic ions (E1 to E7) according to the invention, it is possible to reduce the yield stress.

[0060] calorimetry The total heat released from the sample can act as a proxy for initial hydration and / or strength development.

[0061] The nature and content of each component are listed in Table 1 above. 1. Weigh out the binder components and add them to a mixing cup for a total mass of 50 g. If present, add salt and activator to more than 50 g of dry hydraulic binder. Mix the resulting binder composition using an overhead stirrer (IKA Eurostar 40) equipped with a propeller blade at 150 RPM for 30 seconds. 2. Weigh tap water to the desired mass and add to the mixing cup. 3. Use a syringe to weigh out the water-reducing polymer to the desired mass. 4. Add tap water to the mixing cup containing the binder composition (i.e., hydraulic binder and salt and / or activator). Stir the resulting mixture at 150 RPM for 30 seconds, then at 550 RPM for 90 seconds, and then let it sit for 120 seconds. 5. After said 120 seconds, add the weighed amount of water-reducing polymer and mix the wet composition at 550 RPM for an additional 60 seconds. 6. Approximately 5 g of the wet composition is placed into a plastic ampoule. The weight is recorded and the ampoule is sealed. 7. Place the ampoule in the measuring cell of the TAM Air isothermal microcalorimeter. 8. The calorimeter measures the heat flow emanating from the wet composition sample over a predetermined measurement period.

[0062] FIG. 8 is a graph showing the heat generated per unit mass over the first 24 hours after mixing of samples CE1 and E1. FIG. 9 is a graph showing the heat generated per unit mass over the first 24 hours after mixing of samples CE1 and E2.

[0063] FIG. 10 is a graph depicting the heat generated per unit mass over the first 24 hours after mixing of samples CE5 and E7. As can be seen from these graphs, the heat generated by Samples E1 and E2 was greater than that of Sample CE1 over the test period, and the heat generated by Sample E7 was greater than that of Sample CE5 over the test period. Because hydration of cementitious systems is an exothermic process, the amount of heat generated by the paste samples can act as a proxy for strength development. Therefore, mortar and concrete compositions are expected to achieve higher early strengths thanks to the present invention. Specific embodiments of the present invention are as follows. [Aspect 1] (a) at least one hydraulic binder; (b) at least one water-reducing polymer; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (d) water, and (e) one or more auxiliary cementitious materials, as the case may be; and (f) optionally one or more filler materials; 1. A method for fluidizing a wet concrete or industrial mortar composition comprising: A method comprising the step of adding at least one salt (ch) comprising at least one chaotropic ion to said concrete or mortar composition. [Aspect 2] The method according to embodiment 1, wherein the dry weight ratio of the salt (ch) comprising at least one chaotropic ion to the accelerator (c) is between 0.01 and 3.0. [Aspect 3] 3. The method of claim 1 or 2, wherein the water-reducing polymer (b) is selected from the group consisting of lignosulfonate polymers, melamine sulfonate polymers, naphthalene sulfonate polymers, polycarboxylic acid ether polymers, polyoxyethylene phosphonates, vinyl copolymers, and mixtures thereof. [Aspect 4] The kosmotropic ion of the accelerator (c) is a carbonate ion (CO 2- ), sulfate ions (SO 4 2- ), hydroxide ion (OH - ), citrate ion (C 6 H 5 O 7 3- ), phosphate ions (PO 4 3- ), hydrogen phosphate ion (HPO 4 2- ), dihydrogen phosphate ion (HPO 4 - ), tartrate ion (C 4 H 4 O 6 2- ), acetate ion (CH 3 COO - ), formate ion (HCOO - ), bicarbonate ion (HCO 3 - ), orthosilicate ion (SiO 4 4- ), metasilicate ion (SiO 3 2- ), pyrosilicate ion (Si 2 O 7 6- ), polyphosphate ions, polysilicate ions and thiosulfate ions (S 2 O 3 2- 4. The method of any one of embodiments 1 to 3, wherein the anion is from the group consisting of: [Aspect 5] Aspect 5. The method of any one of aspects 1 to 4, wherein the cation of the promoter (c) is selected from the group consisting of sodium, potassium, and lithium. [Aspect 6] The chaotropic ions of the salt (ch) are chloride ions (Cl - ), bromide ion (Br - ), nitrate ion (NO 3 - ), chlorate ion (ClO 3 - ), perchlorate ion (ClO 4- ), tetrafluoroborate ion (BF 4 - ), iodide ion (I - ), thiocyanate ion (SCN - ), hexafluorophosphate ion (PF 6 - ), guanidinium ion (C(NH 2 ) 3 + ), trichloroacetate ion (CCl 3 COO - ), dichloroacetate ion (CHCl 2 COO - ), chloroacetate ion (CH 2 ClCOO - ), tribromoacetate ion (CBr 3 COO - ) or trifluoroacetate ion (CF 3 COO - 6. The method of any one of embodiments 1 to 5, wherein the method is selected from the group consisting of: [Aspect 7] The salt (ch) containing at least one chaotropic ion is potassium thiocyanate (KSCN), potassium nitrate (KNO 3 ), potassium chloride (KCl), sodium thiocyanate (NaSCN), sodium nitrate (NaNO 3 ), sodium chloride (NaCl), magnesium chloride (MgCl 2 ), magnesium nitrate (Mg(NO 3 ) 2 ), calcium chloride (CaCl 2 ), calcium nitrate (Ca(NO 3 ) 2 ), calcium thiocyanate (Ca(SCN) 2 ), barium chloride (BaCl 2 ), strontium nitrate (Sr(NO 3 ) 2 ), guanidinium chloride (CH 6 ClN 3 ) and guanidinium thiocyanate (C 2 H 6 N 4 7. The method of any one of embodiments 1 to 6, wherein the compound is selected from the group consisting of: [Aspect 8] Aspect 8. The method of any one of aspects 1 to 7, wherein the hydraulic binder (a) is selected from the group consisting of ordinary portland cement, calcium aluminate cement, calcium sulfoaluminate cement, belite cement, hydraulic lime, ground blast furnace slag, basic oxygen furnace slag, ladle slag, supersulfated cement, cement kiln dust, or a mixture thereof. [Aspect 9] Aspect 9. The method of any one of aspects 1 to 8, wherein the supplemental cementitious material (e) is selected from the group consisting of fly ash, activated clay, silica fume, basic oxygen furnace slag, natural pozzolanic material, rice husk ash, activated recycled concrete fine aggregate, or mixtures thereof; and / or the filler material (f) is selected from the group consisting of crushed limestone, crushed dolomite, marble powder, siliceous sand, recycled concrete fine aggregate, or mixtures thereof. [Aspect 10] Use of at least one salt (ch) containing at least one chaotropic ion as a co-flow-inducing agent with at least one water-reducing polymer (b) for a wet concrete or industrial mortar composition comprising water, at least a binder fraction and at least one aggregate fraction, wherein the binder fraction is (a) at least one hydraulic binder; (b) at least one promoter in the form of a salt containing at least one kosmotropic ion; (e) one or more auxiliary cementitious materials, as the case may be; and (f) optionally one or more filler materials; Including, use. [Aspect 11] the binder fraction being, in dry weight % based on the total weight of the hydraulic binder (a), the auxiliary cementitious material (e), and the filler material (f), the salt (ch) containing at least one chaotropic ion in an amount between 0.001 and 10, preferably between 0.01 and 5, more preferably between 0.1 and 3, said water-reducing polymer (b) between 0.005 and 5.0, preferably between 0.01 and 3.0, more preferably between 0.1 and 2, and said accelerator (c) between 0.1 and 10, preferably between 0.5 and 5, more preferably between 1 and 3; 11. The use according to embodiment 10, comprising: [Aspect 12] 1. A process for preparing a wet concrete or mortar composition, comprising: (a) at least one hydraulic binder; (b) at least one water-reducing polymer; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (d) water, and (e) one or more auxiliary cementitious materials, as the case may be; and (f) optionally one or more filler materials; at least one salt (ch) containing at least one chaotropic ion, and At least one aggregate fraction 1. A process for preparing a wet concrete or mortar composition comprising the steps of: mixing together, simultaneously or not simultaneously, separately or not separately, [Aspect 13] A ready-mix or precast concrete composition, in particular for building construction and civil engineering works, comprising at least one aggregate fraction, at least one salt (ch) containing at least one chaotropic ion, and (g) at least one hydraulic binder; (h) at least one water-reducing polymer; (i) at least one promoter in the form of a salt containing at least one kosmotropic ion; (j) water, and (k) one or more auxiliary cementitious materials, as the case may be; and (l) optionally one or more filler materials; 1. A ready-mix or precast concrete composition comprising: [Aspect 14] (a) at least one hydraulic binder; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (d) water, and (e) one or more auxiliary cementitious materials, as the case may be; and (f) optionally one or more filler materials; 1. A method for fluidizing a wet concrete or industrial mortar composition comprising: 1. A method comprising the step of adding to said concrete or industrial mortar composition at least one salt (ch) comprising at least one chaotropic ion and at least one water-reducing polymer (b) in amounts that do not increase compared to a wet concrete or industrial mortar composition (CEC) of the same target consistency class comprising components a, c, d, optionally e, and optionally f, but not component c, in order to obtain said wet concrete or industrial mortar composition of a target consistency class in accordance with European Standard EN 206. [Aspect 15] 1. A performance additive for accelerating and fluidizing wet concrete or industrial mortar compositions comprising at least one hydraulic binder (a), at least one water-reducing polymer (b), at least one accelerator in the form of a salt containing at least one kosmotropic ion (c), the performance additive having a free water content of less than 0.5% by weight, A performance additive comprising at least one salt (ch) comprising at least one chaotropic ion.

Claims

1. (a) at least one hydraulic binder; (b) at least one water-reducing polymer; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (d) water, and (e) optionally one or more auxiliary cementitious materials; and (f) optionally one or more filler materials 1. A method for fluidizing a wet concrete or industrial mortar composition comprising: adding at least one salt (ch) containing at least one chaotropic ion to the concrete or mortar composition, the kosmotropic ion is a sulfate ion (SO 4 2− ), The method as described above, wherein the chaotropic ion of the salt (ch) is selected from the group consisting of chloride ion (Cl − ), nitrate ion (NO 3 − ) and thiocyanate ion (SCN − ).

2. 2. The method of claim 1, wherein the dry weight ratio of the salt (ch) containing at least one chaotropic ion to the facilitating agent (c) is comprised between 0.01 and 3.

0.

3. 3. The method of claim 1 or 2, wherein the water-reducing polymer (b) is selected from the group consisting of lignosulfonate polymers, melamine sulfonate polymers, naphthalene sulfonate polymers, polycarboxylic acid ether polymers, polyoxyethylene phosphonates, vinyl copolymers, and mixtures thereof.

4. 4. The method of claim 1, wherein the cation of the promoter (c) is selected from the group consisting of sodium, potassium, and lithium.

5. The salt (ch) containing at least one chaotropic ion is selected from the group consisting of potassium thiocyanate (KSCN), potassium nitrate (KNO ３ ), potassium chloride (KCl), sodium thiocyanate (NaSCN), sodium nitrate (NaNO ３ ), sodium chloride (NaCl), magnesium chloride (MgCl ２ ), magnesium nitrate (Mg(NO ３ ) ２ ), calcium chloride (CaCl ２ ), calcium nitrate (Ca(NO ３ ) ２ ), calcium thiocyanate (Ca(SCN)2), barium chloride (BaCl ２ ), strontium nitrate (Sr(NO ３ ) ２ ), guanidinium chloride (CH ６ ClN ３ ) and guanidinium thiocyanate (C ２ H ６ N ４ 5. The method of claim 1, wherein the compound is selected from the group consisting of:

6. 6. The method of any one of claims 1 to 5, wherein the hydraulic binder (a) is selected from the group consisting of ordinary portland cement, calcium aluminate cement, calcium sulfoaluminate cement, belite cement, hydraulic lime, ground blast furnace slag, basic oxygen furnace slag, ladle slag, supersulfated cement, cement kiln dust, or mixtures thereof.

7. 7. The method of any one of claims 1 to 6, wherein the supplemental cementitious material (e) is selected from the group consisting of fly ash, activated clay, silica fume, basic oxygen furnace slag, natural pozzolanic material, rice husk ash, activated recycled concrete fine aggregate, or mixtures thereof, and / or the filler material (f) is selected from the group consisting of crushed limestone, crushed dolomite, marble powder, siliceous sand, recycled concrete fine aggregate, or mixtures thereof.

8. Use of at least one salt (ch) containing at least one chaotropic ion as a co-fluidizing agent with at least one water-reducing polymer (b) for a wet concrete or industrial mortar composition comprising water, at least a binder fraction and at least one aggregate fraction, wherein the binder fraction is (a) at least one hydraulic binder; (b) at least one promoter in the form of a salt containing at least one kosmotropic ion; (e) optionally one or more auxiliary cementitious materials; and (f) optionally one or more filler materials Including, the kosmotropic ion is a sulfate ion (SO 4 2− ), The above use, wherein the chaotropic ion of the salt (ch) is selected from the group consisting of chloride ion (Cl − ), nitrate ion (NO 3 − ) and thiocyanate ion (SCN − ).

9. the binder fraction being, in dry weight percent based on the total weight of the hydraulic binder (a), the auxiliary cementitious material (e), and the filler material (f), said salt (ch) comprising at least one chaotropic ion in an amount between 0.001 and 10, preferably between 0.01 and 5, more preferably between 0.1 and 3, said water-reducing polymer (b) between 0.005 and 5.0, preferably between 0.01 and 3.0, more preferably between 0.1 and 2, and said accelerator (c) between 0.1 and 10, preferably between 0.5 and 5, more preferably between 1 and 3; The use according to claim 8, comprising:

10. 1. A process for preparing a wet concrete or mortar composition, comprising: (a) at least one hydraulic binder; (b) at least one water-reducing polymer; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (d) water, and (e) optionally one or more auxiliary cementitious materials; and (f) optionally one or more filler materials; At least one salt (ch) containing at least one chaotropic ion, and At least one aggregate fraction together, either simultaneously or not simultaneously, separately or not separately, the kosmotropic ion is a sulfate ion (SO 4 2− ), The process for preparing the wet concrete or mortar composition, wherein the chaotropic ions of the salt (ch) are selected from the group consisting of chloride ions (Cl − ), nitrate ions (NO 3 − ) and thiocyanate ions (SCN − ).

11. A ready-mix or precast concrete composition, in particular for building construction and civil engineering works, comprising at least one aggregate fraction, at least one salt (ch) containing at least one chaotropic ion, and (a) at least one hydraulic binder; (b) at least one water-reducing polymer; (c) at least one promoter in the form of a salt containing at least one kosmotropic ion; (d) water, and (e) optionally one or more auxiliary cementitious materials; and (f) optionally one or more filler materials Including, the kosmotropic ion is a sulfate ion (SO 4 2− ), The ready-mixed concrete or precast concrete composition, wherein the chaotropic ion of the salt (ch) is selected from the group consisting of chloride ion (Cl − ), nitrate ion (NO 3 − ) and thiocyanate ion (SCN − ).

12. 1. A performance additive for accelerating and fluidizing wet concrete or industrial mortar compositions comprising at least one hydraulic binder (a), at least one water-reducing polymer (b), at least one accelerator in the form of a salt containing at least one kosmotropic ion (c), the performance additive having a free water content of less than 0.5% by weight, At least one salt (ch) containing at least one chaotropic ion, the kosmotropic ion is a sulfate ion (SO 4 2− ), The performance additive, wherein the chaotropic ion of the salt (ch) is selected from the group consisting of chloride ion (Cl − ), nitrate ion (NO 3 − ) and thiocyanate ion (SCN − ).

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