Low water demand high fluidity cement compositions

Abstract

The present invention relates to a high flowability cement composition comprising from 85 to 94 dry weight % of a hydraulic binder (HB) having a d 10 50 µm, a d 50 3.5 µm to 4.5 µm, and a d 85 12 µm to 15 µm, and comprising: a. from 1 to 40 dry weight % of at least one lime source; b. from 5 to 69 dry weight % of at least one supplementary cementitious material; c. from 30 to 90 dry weight % of at least one filler; d. from 0.1 to 5 dry weight % of a sulphate relative to the total weight of components a, b and c; said filler being a mixture of particles: - from 1 to 25 dry weight % relative to the total weight of the filler of particles having a d 50 greater than or equal to 0.05 µm and strictly less than 2 µm, - from 75 to 99 dry weight % relative to the total weight of the filler of particles having a d 50 greater than or equal to 2 µm and strictly less than 200 µm.

Description

Technical Field

[0001] This invention relates to the field of hydraulic binder compositions comprising auxiliary cementitious materials (SCM) for preparing high-flowability cementitious compositions. Specifically, the technical field of this invention relates to hydraulic mineral binders having a high filler content and a low lime source content (such as Portland clinker, cement according to EN 197-1, EN 197-5, EN 197-6, natural hydraulic lime, hydraulic lime, slaked lime, and any lime source in general), wherein the SCM comprises finely ground blast furnace slag (GGBS or slag) or any other pozzolanic material, used in compositions capable of setting and hardening, such as high-flowability cementitious compositions, more specifically grouting mortars and high-performance concrete. Background Technology

[0002] High-flowability cement compositions that can be used to prepare formulations such as grouting mortars require a combination of extremely high flowability with the ability to harden and dry rapidly. In particular, grouting mortars need to achieve extremely high mechanical strengths exceeding 100 MPa in less than 28 days.

[0003] To the applicant's knowledge, commercially available high-flowability cement compositions contain Portland cement as a binder and are combined with fast-hardening cements (such as aluminate cement and sulfoaluminate cement) and calcium sulfate sources to meet the requirements of rapid hardening and rapid drying.

[0004] In addition, calcium aluminate cement plays a major role in enabling the hardened product obtained from a highly fluid cement composition to achieve the required mechanical strength.

[0005] While these highly fluid cement compositions are satisfactory, limiting carbon dioxide emissions remains a major concern. For example, Portland cement production has a significant negative environmental impact due to its substantial carbon dioxide emissions. Cement production inherently generates CO2 during the calcination of raw materials in a kiln at extremely high temperatures (1450°C) via limestone decarburization (Equation (1)). CaCO3(s) → CaO(s) + CO2(g) (Equation (1)) In addition, the combustion of fossil fuels needed to heat cement kilns also releases carbon dioxide. Adding the additional emissions from grinding, every ton of Portland cement produces almost one ton of CO2. Overall, the cement industry accounts for approximately 7% to 9% of global CO2 emissions.

[0006] Most current research on novel adhesives aims to replace cement in various applications by using adhesives with less environmental impact. One approach is to utilize resources that do not require expensive processing, such as byproducts of other industries (waste for one industry but a major resource for another). For example, blast furnace slag is a byproduct of the steel industry. By grinding this product into a fine powder (GGBS), a cementitious material can be obtained, which can be used to partially replace cement or used alone by adding some chemical activators.

[0007] Hydraulic binders based on these sources, particularly ground granulated blast furnace slag (GGBS), have become highly efficient. However, despite their significant impact on CO2 emissions, these binders may require substantial amounts of water in high-flowability applications. It is important to note that the required water volume is highly dependent on the type of high-flowability cement composition. In fact, for example, workability, flowability, setting time, or desired elasticity all depend on the intended use of the high-flowability cement composition. However, the water volume does affect mechanical strength. Therefore, it would be beneficial to develop a hydraulic binder capable of producing workable, high-flowability cement compositions with desired properties while limiting the increase in water content.

[0008] Furthermore, the rapid drying and mechanical strength are provided by aluminate cement, which also generates carbon dioxide emissions. Therefore, there is a need to develop grouting mortars in which Portland cement and aluminate cement (at least partially) are replaced by one or more components with lower carbon dioxide impact.

[0009] In this case, the present invention aims to solve at least one of the above-mentioned problems and / or needs by achieving at least one of the following objectives: -O1- Provides a binder based on auxiliary cementitious materials (SCM) (such as GGBS), or a high-flowability cement composition containing said GGBS-based binder, which serves as an attractive alternative to conventional Portland cement (OPC) and allows for reduced aluminate cement content.

[0010] -O2- provides a slag-based binder, or a high-flowability cement composition containing the GGBS-based binder, which is environmentally friendly.

[0011] -O3- provides a slag-based binder, or a high-flowability cement composition comprising the GGBS-based binder, which is capable of producing a wet formulation with suitable rheological properties, i.e., stable rheological properties (good workability) within the conventional setting time (e.g., from minutes to hours) required by the user of the wet formulation. Summary of the Invention

[0012] At least one of the above objectives is achieved by an optimized dry, high-flowability cement composition that allows for the production of high-flowability mortars comprising 85% to 94% dry weight of hydraulic binder (HB) and 6% to 15% dry weight of rapid-hardening cement, such as calcium aluminate cement (CAC) and sulfoaluminate cement (CSA). The HB has a d value less than or equal to 1µm. 10 d, 3.5µm to 4.5µm 50 and d from 12µm to 15µm 85 And includes: a. At least one lime source, ranging from 1% to 40% dry weight; b. At least one auxiliary cementitious material, ranging from 5% to 69% dry weight; c. At least one type of filler, ranging from 30% to 90% dry weight; d. Sulfates of 0.1% to 5% dry weight relative to the total weight of components a, b, and c; The filler is a mixture of the following particles: - For particles with a total filler weight of 1% to 25% of dry weight, their d 50 Greater than or equal to 0.05µm and strictly less than 2µm, - Relative to particles weighing 75% to 99% of the total filler weight, its d 50 Greater than or equal to 2µm and strictly less than 200µm, d 10 d 50 and d 85 Measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a laser diffraction analyzer, such as that commercially available from SYMPATEC.

[0013] The present invention also relates to a wet high-flowability cement preparation comprising the dry high-flowability cement composition as described above and water.

[0014] The present invention further relates to hardened high-flowability cement products obtained from the wet high-flowability cement preparations described above.

[0015] The present invention also relates to a method for preparing the wet high-flowability cement as described above, comprising the step of mixing a dry high-flowability cement composition as defined above with water, wherein the dry high-flowability cement composition is prepared prior to the mixing step, or is prepared in situ during a mixing step in which the different components of the dry high-flowability cement composition are mixed individually and / or in the form of a premix.

[0016] definition Based on the terminology used in this paper, the following non-restrictive definitions should be considered: "Adhesive" refers to "hydraulic adhesive," meaning any material that can harden simply by adding water, such as cement.

[0017] The source of lime should be understood as any source of lime, including but not limited to Portland clinker, cement, natural hydraulic lime, hydraulic lime, slaked lime and any other source of lime in general.

[0018] "Cement" should be understood as a powdery substance used to make mortar or concrete. These are mineral binders and may not contain any organic components. It refers to any ordinary cement, including ordinary Portland cement, ordinary Portland cement blends, pozzolanic materials and / or fillers, and alkali-activated cement.

[0019] "Clinker" should be understood as the main component phase of ordinary Portland cement obtained by co-calcination of limestone and aluminosilicate sources.

[0020] "Mortar" and "concrete" refer to materials composed of binders, aggregates (such as fillers and sand), and other components (such as admixtures).

[0021] "Dry high-flowability binder for high-flowability cementitious preparations" refers to a material composed of binder and possibly other components (such as admixtures).

[0022] "Wet high-flowability cementitious preparations" refers to materials composed of binders, aggregates (such as sand and gravel), other components (such as admixtures), and water.

[0023] "Hardened high-flowability cement products" refers to hardened products obtained by reacting and evaporating water from wet high-flowability cement preparations.

[0024] “d 10 "" represents the median size of the material's particle size distribution (usually measured in micrometers for cementitious materials). It means that 10% of the particles are smaller than d. 10 Numerical values, and 90% of the particles are larger than d. 10 Numerical value. d 10 Measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a laser diffraction analyzer, such as that commercially available from SYMPATEC.

[0025] “d 50 "" represents the median size of the material's particle size distribution (usually measured in micrometers for cementitious materials). It means that 50% of the particles are smaller than d. 50 Numerical values, and 50% of the particles are larger than d. 50 Numerical value. d 50Measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a laser diffraction analyzer, such as that commercially available from SYMPATEC.

[0026] “d 85 "" represents the median size of the material's particle size distribution (usually measured in micrometers for cementitious materials). It means that 85% of the particles are smaller than d. 85 Numerical values, and 15% of the particles are larger than d. 85 Numerical value. d 85 Measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a laser diffraction analyzer, such as that commercially available from SYMPATEC.

[0027] “d 90 "" represents the median size of the material's particle size distribution (usually measured in micrometers for cementitious materials). It means that 90% of the particles are smaller than d. 90 Numerical values, and 10% of the particles are larger than d. 90 Numerical value. d 90 Measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a laser diffraction analyzer, such as that commercially available from SYMPATEC.

[0028] Detailed Implementation Plan Dry high fluidity cement composition According to the present invention, a "dry" high-flowability binder for high-flowability cement compositions refers to a composition in powder form prepared for mixing with water. In other words, the dry high-flowability cement compositions of the present invention may contain some moisture, but primarily comprise solid components intended to be mixed with water prior to their application.

[0029] In some embodiments, the dry, high-flowability cement composition further comprises aggregates.

[0030] Aggregates comprise a large category of granular materials used in construction, including sand, gravel, crushed stone, slag (non-granulated), recycled concrete, and geosynthetic aggregates. They act as reinforcing materials, increasing the strength of overall composite materials.

[0031] Advantageously, in addition to aggregates, the dry high-flowability cement composition may also contain one or more components, particularly functional admixtures, additives and fibers, which may be the same as other optional components mentioned in the detailed description of hydraulic binders (HB) as defined below.

[0032] In one embodiment, the high-flowability cement composition is grouting mortar.

[0033] In one embodiment, the high-flowability cement composition is high-performance concrete.

[0034] Calcium aluminate cement (CAC) CAC refers to cement containing calcium aluminate (CaAl2O4, CaO·Al2O3) as the main component and calcium silicate or calcium aluminate as the minor component. CAC may also contain calcium aluminate. CAC is identified according to NF 14 647 standard. In some embodiments, CAC is rich in calcium aluminate (CA) and / or calcium aluminate (C). 12 A7).

[0035] In a preferred embodiment, the CAC is crystalline or amorphous. In another preferred embodiment, the CAC is a mixture of crystalline and amorphous CAC.

[0036] Calcium sulfoaluminate cement (CSA) CSA cement can be clinker and / or cement containing calcium sulfoaluminate.

[0037] Hydraulic adhesives (HB) The hydraulic adhesive according to the invention has a d value less than or equal to 1 µm. 10 d, 3.5µm to 4.5µm 50 and d from 12µm to 15µm 85 And includes: a. At least one lime source, ranging from 1% to 40% dry weight; b. At least one finely ground blast furnace slag, ranging from 5% to 69% dry weight; c. At least one type of filler, ranging from 30% to 90% dry weight; d. Sulfates of 0.1% to 5% dry weight relative to the total weight of components a, b, and c; The filler is a mixture of the following particles: - For particles with a total filler weight of 1% to 25% of dry weight, their d 50 Greater than or equal to 0.05µm and strictly less than 2µm, - Relative to particles weighing 75% to 99% of the total filler weight, its d 50 Greater than or equal to 2µm and strictly less than 200µm, d 10 d 50 and d 85 Measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a laser diffraction analyzer, such as that commercially available from SYMPATEC.

[0038] Particle size distribution The adhesive according to the invention has the following particle size distribution: d 10 Less than or equal to 1µm, d 50 The thickness ranges from 3.5µm to 4.5µm, and d 85 The value is 12µm to 15µm.

[0039] In some embodiments, the hydraulic adhesive composition has a dm of 17µm to 20µm. 90 d 90 Measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a laser diffraction analyzer, such as that commercially available from SYMPATEC.

[0040] In some embodiments, the hydraulic adhesive composition has a d = 38 µm or less. 99 d 99 Measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a commercially available laser diffraction analyzer such as those from SYMPATEC. Component a The adhesive composition according to the invention comprises 1% to 40% dry weight, preferably 3% to 35%, more preferably 5% to 30% of component a, i.e., a lime source.

[0041] Preferably, the lime source is Portland clinker, Portland cement, or lime, such as hydraulic lime, natural hydraulic lime, calcium hydroxide, hydrated lime, quicklime, and lime slurry, or mixtures thereof.

[0042] Typically, Portland clinker D 50 ≥11µm and Blaine surface area ≤5500 cm² 2 / g,D 50 Measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a laser diffraction analyzer, such as that commercially available from SYMPATEC.

[0043] When the lime source is Portland cement, it is advantageous that it is at least partially ultrafine cement, whose d 50 Less than or equal to 8µm, preferably less than or equal to 3.5µm, d 50The measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a laser diffraction analyzer, such as those commercially available from SYMPATEC. This implementation is advantageous because it yields increased compressive strength compared to other implementations.

[0044] Component b The adhesive composition according to the invention comprises 5% to 69% dry weight, preferably 10% to 60%, more preferably 15% to 50%, and even more preferably 20% to 40% of component b, which is at least one auxiliary gelling material.

[0045] Auxiliary cementitious materials (SCMs) are materials that contribute to the properties of hardened cement through hydraulic or pozzolanic activity. In one embodiment, the auxiliary cementitious material is selected from the group consisting of, preferably, slag cement, such as finely ground blast furnace slag (GGBS), and pozzolanic materials such as silica fume, natural volcanic ash, volcanic ash, pumice, zeolite-modified tuff, argillaceous tuff, fly ash, calcined shale, metakaolin, calcined clay, especially illite, bentonite, montmorillonite, saponite, biomass ash, rice husk ash, diatomaceous earth, waste glass powder, finely ground opal, carbonized alkaline oxygen converter slag, carbonized olivine, silica fume, and mixtures thereof.

[0046] In some embodiments, the auxiliary cementitious material is GGBS, which may be standard GGBS, ultrafine GGBS, or a mixture thereof. Ultrafine GGBS is composed of d... 50 The composition consists of particles greater than or equal to 1µm and strictly less than 5µm.

[0047] Component c The adhesive composition according to the invention comprises 30% to 90% dry weight, preferably 30% to 80%, more preferably 40% to 70%, and even more preferably 50% to 60% of component d, which is a filler.

[0048] The filler is a finely ground, inert inorganic material. In other words, the filler cannot react with lime or cement to form hydrates in the presence of water.

[0049] In one embodiment, the filler is limestone filler, more preferably, the filler is natural material from a quarry, such as calcite and its polymorphs (e.g., aragonite or spherulite), marble powder, siliceous sand, recycled concrete fine aggregate, and dolomite or precipitated calcium carbonate and mixtures thereof.

[0050] In another embodiment, the packing material is biochar. Biochar should be understood as a solid residue obtained through controlled thermal decomposition (pyrolysis) and gasification of biomass under limited oxygen conditions. Significant control parameters include heating rate, temperature, feed rate, and residence time. Changing these parameters, as well as the selection and quality of the feedstock, will affect the structure, chemical composition, and yield of the resulting biochar. Biochar is black, but brown when unconcentrated, and is rich in carbon.

[0051] In yet another embodiment, the packing material is a mixture of limestone packing material and biochar as defined above.

[0052] According to the present invention, the filler is a mixture of the following particles: - For particles with a total filler weight of 1% to 25% of dry weight, their d 50 Greater than or equal to 0.05µm and strictly less than 2µm, - Relative to particles weighing 75% to 99% of the total filler weight, its d 50 Greater than or equal to 2µm and strictly less than 200µm.

[0053] This combination of filler zoning and overall particle size distribution of the adhesive achieves the technical effect of reducing the amount of water required when mixing the hydraulic adhesive composition of the present invention with water to form a slurry.

[0054] In some embodiments, the filler is a mixture of the following particles: - The particles, with a dry weight percentage (d) of 3% to 20% relative to the total weight of the filler, preferably 5% to 15% dry weight, and more preferably 8% to 12% dry weight, have a d 50 Greater than or equal to 0.05µm and strictly less than 2µm; - The d of the particles relative to the total weight of the filler is 80% to 97% dry weight, preferably 85% to 95% dry weight, more preferably 88% to 92% dry weight. 50 Greater than or equal to 2µm and less than 200µm.

[0055] Surprisingly, the adhesive of the present invention, which exhibits a fine particle size distribution and contains fillers, has a portion (1% to 25% dry weight) of d 50 Greater than or equal to 0.05µm and strictly less than 2µm. In fact, it is generally believed that the finer the adhesive particles, the greater the water requirement.

[0056] Component d According to the present invention, the adhesive composition further comprises 0.1% to 5% of sulfate relative to the total weight of components a, b and c.

[0057] The sulfate content is determined based on the distribution of components a, b, and c. In other words, the dry weight percentage of sulfate is determined by considering that the total content of components a, b, and c is 100% dry weight.

[0058] Preferably, the sulfate is derived from sodium sulfate, potassium sulfate, calcium sulfate, anhydrous gypsum, recycled gypsum, or mixtures thereof; more preferably, the sulfate is derived from anhydrous gypsum, which is natural anhydrous calcium sulfate.

[0059] Other optional components The hydraulic adhesive (HB) may also contain at least one water-reducing polymer at a rate of up to 1% of the total dry weight of components a, b and c.

[0060] The water-reducing polymer content is determined based on the distribution of components a, b, and c. In other words, the dry weight percentage of the water-reducing polymer is determined by considering that the total content of components a, b, and c is 100% dry weight.

[0061] Preferably, the water-reducing polymer is selected from the group consisting of: lignin sulfonate polymers, melamine sulfonate polymers, naphthalene sulfonate polymers, polycarboxylic acid ether polymers, copolymers derived from (meth)acrylic acid monomers (such as HPEG, IPEG and MPEG), copolymers derived from maleic acid monomers (such as APEG), polyoxyethylene phosphonates, vinyl copolymers (such as VPEG), zwitterionic polymers and mixtures thereof.

[0062] The hydraulic adhesive composition may further comprise at least one activator different from d, representing up to 5% of the total dry weight of components a, b, and c.

[0063] Unlike d, the activator content is determined based on the distribution of components a, b, and c. In other words, the dry weight percentage of the activator is determined by considering that the sum of the contents of components a, b, and c is 100% dry weight.

[0064] Preferably, the activator, unlike d, is an alkali metal salt, preferably sodium chloride, calcium chloride, potassium chloride, lithium chloride, sodium carbonate, potassium carbonate, magnesium carbonate, calcium formate, lithium carbonate, calcium nitrate, sodium nitrate, potassium nitrate, lithium nitrate, sodium nitrite, potassium nitrite, lithium nitrite, calcium nitrite, alkali metal oxide, aluminum oxide, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, alkanolamines (such as triethanolamine (TEA), triisopropanolamine (TIPA), diethanolamine (DEA)) or mixtures thereof, preferably calcium nitrate.

[0065] The adhesive composition is advantageously enriched with one or more other components, which are ingredients, particularly functional additives, preferably selected from the following list: ●Water-retaining agent Water-retaining agents have the property of holding the mixed water in place before solidification. Water is thus trapped in the wet formulation slurry, thereby improving its bindability. To some extent, less water is absorbed by the support.

[0066] The water-retaining agent is preferably selected from the group consisting of modified cellulose, modified guar gum, modified cellulose ether and / or guar gum ether and mixtures thereof, and more preferably consists of the group consisting of methylcellulose, methyl hydroxypropyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof.

[0067] ● Rheology modifiers Possible rheology modifiers (also known as "thickeners") are preferably selected from the group consisting of: starch ethers, cellulose ethers and / or gums (such as vegan gum, xanthan gum, succinyl polysaccharide), modified polysaccharides (preferably modified starch ethers), polyvinyl alcohol, polyacrylamide, sepiolite and mixtures thereof.

[0068] ● Defoamer / Antifoaming agent Possible defoamers are preferably selected from the group consisting of, more preferably, polyether polyols and mixtures thereof.

[0069] ● bactericide Possible bactericides are preferably selected from the group consisting of, more preferably, mineral oxides (such as zinc oxide) and mixtures thereof.

[0070] ● Pigments Possible pigments are preferably selected from the group consisting of, more preferably, TiO2, iron oxide and mixtures thereof.

[0071] ●Flame retardant Flame retardants (or fire retardants) can improve the fire resistance of the composition and / or reduce the flame spread rate.

[0072] ●Entraining agent The air-entraining agent (surfactant) is advantageously selected from the group consisting of, more preferably, natural resins, sulfated or sulfonated compounds, synthetic detergents, organic fatty acids and mixtures thereof, preferably selected from the group consisting of, more preferably, lignin sulfonates, fatty acid alkaline soaps and mixtures thereof, more preferably selected from the group consisting of, more preferably, sulfonated olefins, sodium dodecyl sulfate and mixtures thereof.

[0073] ●Retarder The retarder is advantageously selected from the group consisting of, more preferably, tartaric acid and its salts: sodium or potassium salts, citric acid and its salts: sodium salts (trisodium citrate) and mixtures thereof.

[0074] In addition, other components may be: ●Plasticizers ● Fiber ●Dispersed powder ●Wetting agent ●Polymer resin ● Complexing agents ● Polyol-based drying shrinkage reducing agents ● Lubricant The total amount of these optional other components in the adhesive composition is preferably from 0.001% to 10% by weight of the total weight of the adhesive composition.

[0075] Wet high-flowability cement preparations The present invention also relates to wet high-flowability cementitious preparations, particularly grouting mortars and high-performance concretes, which comprise the aforementioned dry high-flowability cementitious composition and water.

[0076] Method for preparing wet, high-flowability cementitious agents The present invention also relates to a method for preparing the above-mentioned wet high-flowability cementitious formulation, comprising the step of mixing the above-mentioned hydraulic binder composition with water, wherein the hydraulic binder composition is prepared prior to the mixing step, or is prepared in situ during a mixing step in which different components of the hydraulic binder composition are individually and / or in the form of a premix with at least one aggregate.

[0077] In other words, wet, high-flowability cementitious formulations can be prepared by two different methods.

[0078] In the first method, a dry, highly fluid cement composition is prepared and then mixed with water.

[0079] In the second method, a wet high-flowability cement formulation is prepared by mixing each component of the dry high-flowability cement composition in water.

[0080] According to this disclosure, the term "mixture" should be understood as any form of mixture.

[0081] In a preferred embodiment, a portion of the hydraulic binder (HB) of the dry high-flowability cement composition is mixed with at least a portion of water, and then mixed with aggregate.

[0082] In a preferred embodiment, the weight ratio of water to water-hardening adhesive (HB) and CAC is 0.1 to 0.5, advantageously 0.15 to 0.45, and more advantageously 0.2 to 0.4 when the method is carried out.

[0083] Hardened high-flowability cement products The present invention also relates to hardened high-flowability cement products obtained from the above-mentioned wet high-flowability cement preparation.

[0084] Example Example 1: Synergistic effect of filler particle size distribution and overall hydraulic binder particle size distribution Three hydraulic adhesive compositions were prepared. Their compositions are shown in Table 1 below:

[0085] Table 1 The three hydraulic adhesives were then mixed with water. The amount of water required to wet the powder was then measured according to the Beta P test.

[0086] The Beta P test involves filling a truncated cone mold (in two layers) with slurry and placing it on a glass plate. The mold is then lifted, and its diameter spread is measured to obtain an average value between 140 mm and 280 mm. This procedure is then repeated with other proportions of material and water until sufficient points are obtained to show up. Figure 1 The linear relationship.

[0087] Then, the relative flow area (R) is calculated using eq1 by measuring the average diameter (D) of the expansion.

[0088] R= (eq1) according to Figure 1 A linear relationship was obtained based on the ratio of the relative flow area to the water volume and the powder volume.

[0089] The water-to-powder ratio was calculated using eq2, which showed a clear dependence on the relative flow area (R).

[0090] 𝑉 𝑊 / 𝑉 𝑃 = β 𝑃 + 𝑅 𝐸 p (eq2) β P This represents the water ratio, taking into account water within the pores of the material particles and interstitial water between particles. Therefore, it indicates the minimum amount of water required for the powder to become a slurry. E, defined as the deformation coefficient... P Describe the sensitivity of slurry flowability to changes in water content.

[0091] Then these three hydraulic adhesives are mixed with water. For example... Figure 1 As shown, the water / powder volume ratio required to form a slurry using the adhesive (E1) of the present invention is approximately 1.26, while the water / powder volume ratio required to form a slurry using adhesives other than those of the present invention (CE1 and CE2) is approximately 1.35.

[0092] Adhesive CE1 is free of d particles with a diameter greater than or equal to 0.05 µm and strictly less than 2 µm. 50 The filler particles have a d size of less than or equal to 1µm. 10 d, 3.5µm to 4.5µm 50 and d from 12µm to 15µm 85 .

[0093] Adhesive CE2 contains neither d-type particles with a diameter greater than or equal to 0.05 µm but strictly less than 2 µm. 50 The filler particles do not have a d size less than or equal to 1µm. 10 d, 3.5µm to 4.5µm 50 and d from 12µm to 15µm 85 .

[0094] Therefore, the overall particle size distribution of the adhesive is insufficient to reduce the required water content, according to the content of d according to the present invention. 50 The presence of filler particles greater than or equal to 0.05µm and strictly less than 2µm is also necessary.

[0095] Example 2: Grouting mortar according to the present invention Two types of wet grouting mortars were prepared by mixing the components detailed in Table 2 below.

[0096] Table 2 According to standard 196-1, grouting mortars E2 and E3 exhibit compressive strength (C) and flexural strength (F) on 4×4×16 cm prism specimens at 1 day, 7 days and 28 days.

[0097] The flexural strengths of grouting mortar E2 at 1 day, 7 days and 28 days were 4.5, 13 and 16 MPa, respectively.

[0098] The compressive strengths of grouting mortar E2 at 1 day, 7 days and 28 days are 31.6, 78.2 and 105.5 MPa, respectively.

[0099] The flexural strengths of grouting mortar E3 at 1 day, 7 days, and 28 days were 7, 12.1, and 15.6 MPa, respectively.

[0100] The compressive strengths of grouting mortar E3 at 1 day, 7 days and 28 days are 39.5, 65.2 and 89.4 MPa, respectively.

Claims

1. A dry, high-flowability cement composition comprising 85% to 94% dry weight of hydraulic binder (HB) and 6% to 15% dry weight of rapid-hardening cement, such as calcium aluminate cement (CAC) and sulfoaluminate cement (CSA). The HB has a d value less than or equal to 1µm. 10 d, 3.5µm to 4.5µm 50 and d from 12µm to 15µm 85 And includes: a. At least one lime source, ranging from 1% to 40% dry weight; b. At least one auxiliary cementitious material, ranging from 5% to 69% dry weight; c. At least one type of filler, ranging from 30% to 90% dry weight; d. Sulfates of 0.1% to 5% dry weight relative to the total weight of components a, b, and c; The filler is a mixture of the following particles: - For particles with a total filler weight of 1% to 25% of dry weight, their d 50 Greater than or equal to 0.05µm and strictly less than 2µm, - Relative to particles weighing 75% to 99% of the total filler weight, its d 50 Greater than or equal to 2µm and strictly less than 200µm, d 10 d 50 and d 85 Measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a laser diffraction analyzer, such as that commercially available from SYMPATEC.

2. The dry, high-flowability cement composition according to claim 1, wherein the HB has a dm of 17µm to 20µm. 90 , d 10 d 50 and d 85 Measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a laser diffraction analyzer, such as that commercially available from SYMPATEC.

3. The dry, high-flowability cement composition according to any one of the preceding claims, wherein the HB has a d value equal to or less than 38 µm. 99 , d 10 d 50 and d 85 Measurements were performed using laser diffraction analysis (also known as laser diffraction spectroscopy) with a dry method using a laser diffraction analyzer, such as that commercially available from SYMPATEC.

4. The dry, high-flowability cement composition according to any one of the preceding claims, wherein the lime source is Portland clinker, Portland cement, or lime, such as hydraulic lime, natural hydraulic lime, calcium hydroxide, hydrated lime, quicklime, and lime slurry, and mixtures thereof.

5. The dry, high-flowability cement composition according to any one of the preceding claims, wherein the auxiliary cementitious material is selected from the group consisting of, preferably, the following: Slag cement, such as finely ground blast furnace slag (GGBS), and pozzolanic materials, such as silica fume, natural volcanic ash, volcanic ash, pumice, zeolite-modified tuff, argillaceous tuff, fly ash, calcined shale, metakaolin, calcined clay, especially illite, bentonite, montmorillonite, saponite, biomass ash, rice husk ash, diatomaceous earth, waste glass powder, finely ground opal, carbonized alkaline oxygen converter slag, carbonized olivine, silicon carbide wollastonite and mixtures thereof.

6. The dry, high-flowability cement composition according to any one of the preceding claims, wherein the filler is a natural material from a quarry, such as calcite and its polymorphs such as aragonite or spheroidal aragonite and dolomite, or precipitated calcium carbonate and mixtures thereof.

7. The dry, high-flowability cement composition according to any one of the preceding claims, wherein the calcium aluminate cement is crystalline or amorphous.

8. The dry, high-flowability cement composition according to any of the preceding claims, wherein the sulfate is derived from sodium sulfate, potassium sulfate, calcium sulfate, sulfuric anhydride, recycled gypsum, or a mixture thereof.

9. The dry, high-flowability cement composition according to any one of the preceding claims, wherein the water-reducing polymer is present and selected from the group consisting of: lignin sulfonate polymers, melamine sulfonate polymers, naphthalene sulfonate polymers, polycarboxylic acid ether polymers, copolymers derived from (meth)acrylic acid monomers such as HPEG, IPEG and MPEG, copolymers derived from maleic acid monomers such as APEG, polyoxyethylene phosphonates, vinyl copolymers such as VPEG, zwitterionic polymers and mixtures thereof.

10. The dry, high-flowability cement composition according to any one of the preceding claims, wherein it further comprises an activator different from d., said activator being advantageously an alkali metal salt, preferably sodium chloride, calcium chloride, potassium chloride, lithium chloride, sodium carbonate, potassium carbonate, magnesium carbonate, calcium formate, lithium carbonate, calcium nitrate, sodium nitrate, potassium nitrate, lithium nitrate, sodium nitrite, potassium nitrite, lithium nitrite, calcium nitrite, alkali metal oxides, alumina, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, alkanolamines such as triethanolamine (TEA), triisopropanolamine (TIPA), diethanolamine (DEA) or mixtures thereof, preferably calcium nitrate.

11. The dry, high-flowability cement composition according to any one of the preceding claims, wherein it further comprises aggregate.

12. A wet high-flowability cementitious preparation comprising the dry high-flowability cement composition of any of the preceding claims and water.

13. A hardened high-flowability cement product obtained from the wet high-flowability cement preparation according to claim 12.

14. A method for preparing the wet high-flowability cementitious formulation of claim 12, comprising the step of mixing a dry high-flowability cement composition according to any one of claims 1 to 10 with water, wherein the dry high-flowability cement composition is prepared prior to the mixing step, or prepared in situ during a mixing step in which the different components of the dry high-flowability cement composition are mixed individually and / or in the form of a premix.

15. The method of claim 14, wherein the ratio of water to the water-hardening adhesive and the CAC composition is 0.1 to 0.5, advantageously 0.15 to 0.45, and more advantageously 0.2 to 0.4.

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