Adjuvants for improving the particle size distribution of mineral compositions with reduced clinker content

Abstract

This invention relates to a grinding method comprising grinding a mineral composition to be ground in the presence of an additive composition comprising at least one polymer (P) of formula (1), wherein: -M independently represent H + Alternatively, it may be a cation with a valence of v selected from alkali metal cations, alkaline earth metal cations, divalent or trivalent metal cations, ammonium cations, or organic ammonium cations. - If M = H, then v = 1, and if "M" represents a cation, then v is the valence of cation M. - R2, R3, R4, and R5 independently represent H, CH3, or -COO(M). 1 / v -m = 0, 1, or 2; p = 0 or 1; X is O or N; and -R1 indicates -[alkyl-O]. z -R6, wherein each "alkyl" is independently a straight-chain or branched C2 to C4 alkylene group, R6 represents H, C1 to C20 alkyl, cyclohexyl or alkylaryl, and z ≥ 40, wherein the number of units (I) and (II) in the polymer (P) is defined by a repeating unit (A) comprising one unit (II) and "a" units (I), wherein a > 0, n is 1.5 to 50, and the molecular weight Mw of the repeating unit (A) is... (A) ≤6500g / mol, and the mineral composition to be ground contains 0% to 80% clinker relative to the total weight of the mineral composition to be ground. (1).

Description

Technical Field

[0001] The present invention relates to a method for grinding mineral compositions in the presence of a specific mixture.

[0002] The present invention also relates to mineral compositions and hydraulic compositions comprising such mixtures.

[0003] The present invention also relates to the use of the mixture for improving grindability, particularly for improving the particle size distribution of the mineral composition. Background Technology

[0004] Typical cement compositions, and even those containing mineral admixtures, contain a significant proportion of clinker. For example, most ordinary cements, as defined in standard EN 197-1:2011 "Composition, specifications and consistency of ordinary cement", contain at least 65% by weight of clinker.

[0005] The search seeks to reduce the clinker content in cement compositions and hydraulic cementitious materials to decrease their carbon shock while maintaining their mechanical and rheological properties. New cement compositions and hydraulic cementitious materials have emerged in which a portion of the clinker is replaced by mineral admixtures, particularly natural or artificial volcanic ash, silica fume, calcined clay, fly ash, and limestone, as described in CEM II / CM, which contains 50% to 64% clinker, as described in standard EN 197-5:2021 "Cement - Part 5: Silicate composite cement CEM II / CM and composite cement CEM VI".

[0006] Furthermore, grinding is a central stage in cement composition production because it is energy-intensive, complex, and the fineness and particle size distribution of the resulting cement composition will determine the properties of the hydraulic compositions (e.g., mortars and concretes) containing it, particularly water requirements and compressive mechanical strength. For example, a particle size fraction smaller than 32 μm, and more specifically, a particle size fraction from 2 μm to 32 μm, is an important parameter for obtaining strength. In fact, particles that are too fine (<2 μm) lead to excessively rapid setting, with an associated risk of cracking. Furthermore, they may reduce the workability of hydraulic compositions containing mineral components. Conversely, particles that are too coarse (>32 μm) cannot hydrate quickly enough to significantly contribute to obtaining the strength expected in conventional applications.

[0007] In addition, from an environmental perspective, there is a desire to increase the production of grinding equipment with the lowest possible energy consumption.

[0008] It is well known that glycols or alkanolamines are used to facilitate the crushing of materials and reduce grinding time. However, these grinding aids are not entirely satisfactory, especially when grinding mineral compositions with reduced clinker content. Furthermore, grinding control is more complex when several mineral compounds are co-ground in the same composition and have different hardnesses, as is the case with compositions with reduced clinker content mentioned above. In fact, co-grinding materials of different hardnesses can lead to over-grinding of the less hard materials and insufficient grinding of the harder materials. These conditions can result in a decrease in the compressive mechanical strength of hydraulic compositions containing mineral compositions, particularly when the mineral composition contains clinker or blast furnace slag. When mineral compositions reach a fine particle size, it is also necessary to control their water requirements, which affects the processability of hydraulic compositions containing mineral compositions. This is especially true when using large proportions of calcined clay, limestone, or volcanic ash. Moreover, properly grinding brittle mineral materials is very difficult because the ground particles tend to agglomerate and accumulate on the surface of the grinding mill, such as the balls in a ball mill, rendering the grinding ineffective. Summary of the Invention

[0009] Therefore, there is a need for a new method for improving the grinding and grindability of mineral compositions with reduced clinker content, especially when grinding involves co-grinding several different mineral compounds or grinding fragile mineral materials.

[0010] There is a particular need for a new method that can increase the proportion of 2-32 μm fractions in the particle size distribution of mineral compositions with reduced clinker content.

[0011] There is also a need for new mineral compositions with reduced clinker content, characterized by high fineness and high 2-32 μm fraction.

[0012] Another object of the present invention is to provide a hydraulic composition based on a mineral composition with reduced clinker content, which exhibits good mechanical properties, particularly good compressive mechanical strength, especially short-term mechanical properties, such as mechanical properties at 1 day and 2 days, and improved processability, particularly when the mineral composition contains a large proportion of calcined clay, fly ash, limestone and / or volcanic ash.

[0013] Therefore, the present invention relates to a grinding method comprising grinding a mineral composition to be ground in the presence of an additive composition comprising at least one polymer (P) of the following formula:

[0014]

[0015] in:

[0016] - “M” independently represents H +Alternatively, it may be a cation with a valence of v selected from alkali metal cations, alkaline earth metal cations, divalent or trivalent metal cations, ammonium cations, or organic ammonium cations.

[0017] - When "M" represents H, "v" represents 1, and when "M" represents a cation, "v" is the valence of the cation M.

[0018] - “R2” and “R3” independently represent hydrogen, methyl, or the formula -COO(M) having M and v as defined above. 1 / v The group, preferably hydrogen or methyl,

[0019] - “R4” and “R5” independently represent hydrogen, methyl, or the formula -COO(M) having M and v as defined above. 1 / v group,

[0020] - “m” represents 0, 1, or 2.

[0021] - “p” represents 0 or 1.

[0022] - “X” is O or N, and

[0023] - “R1” indicates -[alkyl-O] z -R6, where "alkyl" in each [alkyl-O] unit independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms, "R6" represents H, C1 to C20 alkyl, cyclohexyl or alkylaryl, and "z" is greater than or equal to 40. The number of units (I) and (II) in the polymer (P) is defined by a repeating unit (A) containing one unit (II) and "a" units (I), and the repeating unit (A) is present "n" times in the polymer (P).

[0024] - "a" is a non-zero positive number.

[0025] - “n” is between 1.5 and 50, and

[0026] - The molecular weight of the repeating unit (A) is less than or equal to 6500 g / mol, and the mineral composition to be ground contains 0 to 80% by weight of clinker relative to the total weight of the mineral composition to be ground.

[0027] In addition, the polymer (P) is formulated to contain n repeating units of the following formula (A) or even to consist of n repeating units of the following formula (A):

[0028] Units (I) and (II) are as defined above.

[0029] It should be understood that the repeating units (A) of the polymer (P) may be different from each other, but are preferably all the same.

[0030] In fact, the inventors have unexpectedly discovered that, during the grinding of mineral compositions with reduced clinker content, the use of a specific polymer (P) as described above allows for improved grindability of the composition, particularly increasing the 2-32 μm fraction of the particle size distribution of the ground mineral composition. It is the combination of the length of the side chains (parameter "z"), the number of repeating units (A) (parameter "n"), and the size of the repeating units (molecular weight of the repeating unit (A)), optionally in conjunction with the number of units (I) (parameter "a"), that enables the resolution of the technical problems mentioned herein.

[0031] The present invention also relates to a mixed-grind mineral composition comprising a mineral composition and a polymer (P) as defined above, wherein the mineral composition comprises clinker in a weight of 0% to 80% by weight relative to the total dry weight of the mineral composition.

[0032] The present invention also relates to the use of a polymer (P) as defined above for improving the grindability of a mineral composition to be ground, wherein the mineral composition to be ground comprises clinker in a weight of 0% to 80% by weight relative to the total weight of the mineral composition; preferably for increasing the proportion of the 2-32 μm fraction in the particle size distribution of the ground mineral composition, advantageously increasing the proportion of the 2-32 μm fraction in the particle size distribution of the ground mineral composition by at least 6% relative to the proportion of the 2-32 μm fraction in the particle size distribution of a mineral composition ground in the absence of the polymer (P), wherein the ground mineral composition comprises clinker in a weight of 0% to 80% by weight relative to the total weight of the mineral composition.

[0033] Grinding method

[0034] The present invention relates to a grinding method comprising grinding a mineral composition to be ground in the presence of an additive composition comprising at least one polymer (P).

[0035] According to one embodiment, the method includes a stage of preparing a mixture to be ground, the stage of which includes mixing a mineral composition to be ground and an additive composition; followed by a grinding stage of the mixture to be ground.

[0036] According to another embodiment, the method includes a stage of introducing the mineral composition to be ground into a grinder, followed by a stage of adding an additive composition into the grinder during the grinding of the mineral composition to be ground.

[0037] In a continuous process, various components are introduced into the mill via a belt conveyor or air chute, which processes the various materials in the desired proportions through specific feeders associated with each component before the main feed of the mill.

[0038] The additive composition is added to the material at the level of the conveyor belt before it enters the mill through a nozzle and then through an injection gun in the first or second chamber.

[0039] Preferably, the grinding process is carried out in a grinding apparatus, the most common of which is:

[0040] - Ball mill, followed by, or not, a first-, second-, or third-generation separator. In the latter case, the level of circulating load is a definite parameter used to improve grinding efficiency and its output. Filters and / or cyclone separators allow fine particles from the airflow to be collected at the separator and mill, which are then reintroduced into the finished product at the separator outlet.

[0041] - Vertical grinding mills are becoming increasingly common due to their lower energy consumption. Because of the lower grinding temperature, this grinding process requires a higher tolerance for the moisture content of the raw materials. Bag filters allow for the separation of the airflow from the bed of ground solid particles.

[0042] - A series of grinding mills can be used to increase productivity, for example, by using a roller press to reduce the particle size of the clinker at the mill inlet.

[0043] - Other grinding mills that are particularly effective at reducing grinding energy, including those with cages containing abrasives such as silica microspheres, can be used in series with other more conventional grinding mills. These subsequent processes enable the achievement of very high levels of fineness.

[0044] According to a first alternative, the grinding method is a co-grinding method of at least one first mineral material to be ground and at least one second mineral material to be ground. According to this alternative, the grinding method includes a stage of preparing a mineral composition to be ground, said stage comprising mixing at least one first mineral material to be ground and at least one second mineral material to be ground to obtain the mineral composition to be ground.

[0045] The first mineral material to be ground and the second mineral material to be ground are defined below in the description of the mineral composition to be ground.

[0046] According to the second alternative, the grinding method is the individual grinding of materials in the mineral composition. Therefore, preferably, the grinding process includes a stage of grinding a first mineral material to be ground in the presence of an additive composition containing at least one polymer (P) to obtain a first ground mineral material, optionally grinding a second mineral material to be ground in the presence of an additive composition containing at least one polymer (P) to obtain a second ground mineral material, and a stage of mixing the first ground mineral material and the second ground mineral material to obtain a ground mineral composition.

[0047] The first mineral material to be ground and the second mineral material to be ground are defined below in the description of the mineral composition to be ground.

[0048] The additive composition can be mixed with the first and second mineral materials to be ground before being introduced into the mill or during the grinding process.

[0049] Polymer (P)

[0050] The additive composition for the grinding method comprises at least one polymer (P), said polymer (P) comprising units of formulas (I) and (II):

[0051]

[0052] in:

[0053] - “M” independently represents H + Alternatively, it may be a cation with a valence of v selected from alkali metal cations, alkaline earth metal cations, divalent or trivalent metal cations, ammonium cations, or organic ammonium cations.

[0054] - When "M" represents H, "v" represents 1, and when "M" represents a cation, "v" is the valence of the cation M.

[0055] - “R2” and “R3” independently represent hydrogen, methyl, or the formula -COO(M) having M and v as defined above. 1 / v The group, preferably hydrogen or methyl,

[0056] - “R4” and “R5” independently represent hydrogen, methyl, or the formula -COO(M) having M and v as defined above. 1 / v group,

[0057] - “m” represents 0, 1, or 2.

[0058] - “p” represents 0 or 1.

[0059] - “X” is O or N, and

[0060] - “R1” indicates -[alkyl-O] z -R6, where "alkyl" in each [alkyl-O] unit independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms, "R6" represents H, C1 to C20 alkyl, cyclohexyl, or alkylaryl, and "z" is greater than or equal to 40. The number of units (I) and (II) in the polymer (P) is modeled by repeating units (A) containing one unit (II) and "a" units (I), with repeating units (A) present "n" times in the polymer (P), where:

[0061] - "a" is a non-zero positive number.

[0062] - “n” is between 1.5 and 50, and

[0063] - The molecular weight of the repeating unit (A) is less than or equal to 6500 g / mol.

[0064] Therefore, the polymer (P) can be represented by the following formula:

[0065] ,

[0066] “R2”, “R3”, “M”, “v”, “R4”, “R5”, “m”, “p”, “X”, “R1”, “a” and “n” are as defined above, or according to any of the implementations defined below.

[0067] It should be understood that the repeating unit (A) is random, and the order of units (I) and (II) in the polymer (P) is not predetermined. Units (I) and (II) are preferably randomly distributed in the polymer (P).

[0068] Preferably, the molecular weight of the repeating unit (A) is 1500 to 6500 g / mol, more preferably 2000 to 6500 g / mol, more preferably 2500 to 6500 g / mol, more preferably 3500 to 6000 g / mol, more preferably 4500 to 6000 g / mol, more preferably 5000 to 6000 g / mol, and even more preferably 5200 to 5600 g / mol.

[0069] “z” indicates the number of [alkyl-O] units in the R1 group.

[0070] Preferably, "z" is greater than or equal to 50, more preferably greater than or equal to 70, more preferably greater than or equal to 80, more preferably greater than or equal to 85, more preferably greater than or equal to 90, more preferably greater than or equal to 100, more preferably z is 40 to 230, more preferably 50 to 200, more preferably 70 to 150, more preferably 80 to 120, more preferably 90 to 120, more preferably 100 to 120.

[0071] “n” represents the number of repeating units (A) in the polymer (P).

[0072] Preferably, "n" is 4-40, more preferably 5-25, more preferably 6-20, and more preferably 7-18.

[0073] Preferably, "a" is 0.2-100, more preferably 0.5-50, more preferably 0.8-25, more preferably 1.0-20, more preferably 2.0-15, more preferably 3.0-10, more preferably 3.9-7, and more preferably 4.0-6.

[0074] Preferably, the grafting ratio of polymer (P) is strictly greater than 5%, preferably greater than or equal to 6%, preferably greater than or equal to 8%, preferably greater than or equal to 10%, preferably greater than or equal to 12%, preferably greater than or equal to 15%, preferably less than or equal to 50%, preferably less than or equal to 30%, preferably less than or equal to 25%, preferably less than or equal to 21%.

[0075] The grafting ratio corresponds to the ratio between the number of units (II) in polymer (P) and the total number of units (I) and (II). The grafting ratio is determined by introducing the molar amount of monomer used to synthesize polymer (P), taking into account the total conversion of the monomers.

[0076] “a” is related to the grafting ratio through the following relationship:

[0077] a = (1 - grafting ratio) / (grafting ratio)

[0078] The molecular weight Mw of the repeating unit (A) (A) It can be represented by the following relation:

[0079] Mw (A) =Mw (单元(II)) +a*Mw (单元(I)) ,

[0080] Mw (单元(I)) Mw represents the molecular weight of the unit (I) of a polymer (P). (单元(II)) This indicates the molecular weight of unit (II) in the polymer (P). Mw (A) The molecular weight is the calculated molecular weight; therefore, the weight-average molecular weight of the repeating unit (A) is equal to the number-average molecular weight of the repeating unit (A).

[0081] n corresponds to the following ratio:

[0082] n=Mw (P) / Mw (A)

[0083] Mw (A) Mw represents the molecular weight of the repeating unit (A) as defined above. (P) Mw represents the number-average molecular weight of polymer (P). (P) Determined by size exclusion chromatography, for example, under the following conditions:

[0084] Columns: Square protective column, PL hydrogel-OH 40, PL hydrogel-OH 30, PL hydrogel-OH 20

[0085] Mobile phase: brine eluent (8.5g NaNO3, 1.4g NaH2PO4, 2H2O, 1.9g Na2HPO4, 2H2O, 0.7g NaN3 in 1 liter of pure water).

[0086] Flow rate: 1 ml / min

[0087] Detector: Refractive index + light scattering + viscometer

[0088] Column compartment temperature: 30℃

[0089] Injection volume: 150 μL

[0090] Concentration: Approximately 10 mg / mL

[0091] Standard product: PEO 45kDa.

[0092] Preferably, in the polymer (P), m=0, p=1 and X=0.

[0093] The following embodiments can be considered independently or in combination with each other, and in combination with any of the preferred embodiments described above:

[0094] - v=1 and M= H + , and / or

[0095] - R2=H, and / or

[0096] - R3=CH3, and / or

[0097] - R4=H, and / or

[0098] - R5=CH3, and / or

[0099] - m=0, and / or

[0100] - p=1, and / or

[0101] - X=O, and / or

[0102] - R1 = [alkyl-O] z -R6, wherein the alkyl group =CH2-CH2 and / or R6 is a C1 to C20 alkyl group, preferably CH3.

[0103] The polymer (P) is preferably used at a ratio of 0.01% to 1% by weight, particularly 0.05% to 0.5% by weight, preferably 0.05% to 0.3% by weight, and most preferably 0.10% to 0.30% by weight, relative to the dry weight of the mineral composition to be ground.

[0104] Therefore, the additive composition is preferably used in an amount that allows the above-mentioned polymer (P) to be obtained.

[0105] Additive composition

[0106] Admixture compositions may contain other ingredients. For this purpose, references may be made to, but are not limited to, alkanolamines, glycols, glycerols, accelerator compounds (including chloride salts, thiocyanates, formates, nitrates and / or nitrites and mixtures thereof), carboxylic acids or their salts (including acetic acid, adipic acid, gluconic acid, formic acid, oxalic acid, citric acid, maleic acid, lactic acid, tartaric acid, malonic acid and mixtures thereof), water-reducing and highly effective water-reducing compounds (including lignin sulfonates, hydroxylated carboxylic acids, comb-type polycarboxylates and mixtures thereof), and packset-reducing compounds (as relative numerical indices, measured in standard ASTM). As described in C1565-19, the following are considered as indicating the tendency of cement to compact during bulk storage or transport: (including polyacrylic acid), surfactants, defoamers (including tributyl phosphate, triisobutyl phosphate, dibutyl phthalate, octanol, alkylamines, water-insoluble carbonates and borates and mixtures thereof), air-entraining agents (including wood resin salts, sulfonated lignin salts and mixtures thereof), retarders (including sugars, corn syrups and molasses and mixtures thereof), and mixtures thereof.

[0107] Preferably, the additive composition further comprises an ingredient selected from alkanolamines, glycols, glycerols, accelerator compounds (including chloride salts, thiocyanates, formates, nitrates and / or nitrites and mixtures thereof), carboxylic acids or their salts (including acetic acid, adipic acid, gluconic acid, formic acid, oxalic acid, citric acid, maleic acid, lactic acid, tartaric acid, malonic acid and mixtures thereof).

[0108] The additive composition is preferably in the form of a solution, suspension or powder, more preferably in the form of a solution.

[0109] Preferably, the polymer (P) content in the additive composition is from 0.10% to 60% by weight, more preferably from 0.10% to 40% by weight, more preferably from 0.10% to 20% by weight, and more preferably from 1% to 10% by weight, relative to the total weight of the composition.

[0110] Depending on the proportions used, the polymer (P), more generally an additive composition, advantageously allows for the attainment of more 2-32 μm fractions in the particle size distribution of the ground mineral composition.

[0111] This distribution is advantageous, especially because it promotes good compressive mechanical strength, particularly in the short term. Short-term compressive mechanical strength refers to the compressive mechanical strength at 16 hours, 1 day, and 2 days, preferably at 2 days. These compressive mechanical strengths are measured according to standard NF EN 196-1 (September 2016) "Methods for testing cement - Part 1: Determination of strength - Methods for testing cement" or standard ASTM C109 / C109M-21.

[0112] Mineral composition to be ground

[0113] The mineral composition to be ground contains 0% to 80% clinker relative to the total dry weight of the mineral composition to be ground.

[0114] Therefore, the mineral composition to be ground preferably contains at least one mineral material to be ground other than clinker and optional clinker.

[0115] Regarding the properties of the mineral composition to be ground, the method according to the invention and the selection of a particular polymer (P) are particularly advantageous when grinding brittle mineral materials or co-grinding hard mineral materials (such as clinker containing brittle mineral materials).

[0116] Within the meaning of this invention, the hardness or brittleness of a mineral material is related to its grindability (its ease of being ground). The grindability of a mineral material can be determined by grinding the material in a closed laboratory ball mill without additives. In practice, if other grinding and milling conditions are otherwise identical, grindability is related to grinding energy, which in turn is directly related to the grinding time necessary to obtain the target Blaine fineness. Blaine fineness is determined according to standard NF EN 196-6. Specifically, the particle size of the mineral material before grinding must correspond to 100% passing through a 2.15 mm sieve.

[0117] Within the meaning of this invention, if used to obtain a Brian fineness of 1500 to 2500 cm... 2 If the grinding time of a mineral material is at least twice as short (preferably twice to twenty times, more preferably twice to ten times) shorter than the grinding time of clinker meeting the requirements of standard NF EN 197-1 for obtaining the same Brian fineness, then the mineral material is brittle. It should be understood that, in order to perform this test, the mineral material and clinker to be tested must be ground under the same conditions (except for the grinding time).

[0118] Examples of fragile materials are: any one of calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash, calcined shale, finely ground shale, diatomaceous earth, and mixtures thereof; more particularly any one of calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash, and mixtures thereof; more particularly any one of calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, and mixtures thereof.

[0119] Conversely, if used to obtain a Brian fineness of 1500 to 2500 cm 2 If the grinding time of a mineral material is 0.8 to 10 times that of clinker that meets the requirements of standard NF EN 197-1 and is used to obtain the same Brønsted fineness, then the mineral material is hard.

[0120] Examples of hard materials are: clinker; silica fume; granular blast furnace slag; crystallized, expanded, vitrified (granular or pellet) blast furnace slag; converter steel slag; electric arc furnace carbon steel slag; ladle slag; quartz; high-alumina cement; sulfoaluminate clinker; ye'elimite; belitic clinkers; recycled glass; zeolite; fine aggregates from demolished recycled concrete; and any mixtures thereof.

[0121] Preferably, relative to the total dry weight of the mineral composition to be ground, the mineral composition to be ground comprises 20% to 100% by weight of mineral materials other than clinker, preferably 20% to 99.99% by weight, preferably 30% to 99% by weight, preferably 40% to 99% by weight, preferably 45% to 95% by weight, preferably 50% to 95% by weight, preferably 60% to 90% by weight of mineral materials other than clinker. If the mineral composition to be ground comprises several mineral materials other than clinker, these contents correspond to the total content of mineral materials other than clinker.

[0122] When the mineral composition to be ground contains clinker, the clinker is present in a content of preferably 0.01% to 80% by weight, preferably 1% to 70% by weight, preferably 1% to 60% by weight, preferably 5% to 55% by weight, preferably 5% to 50% by weight, and preferably 10% to 40% by weight, relative to the total dry weight of the mineral composition to be ground.

[0123] Clinker, especially Portland or sulfo-aluminous clinker, is preferred as defined in "Cement Chemistry" (Harry FWTaylor, version 2, Academic Press, 1990).

[0124] Mineral materials other than clinker can be any mineral material that can be incorporated into the hydraulic cementitious material composition.

[0125] Mineral materials other than clinker suitable for use in this invention include, for example, calcium sulfate; mineral admixtures (e.g., calcined clay, limestone, natural or artificial volcanic ash, silica fume, fly ash, granular blast furnace slag, calcined shale); crystalline, expanded, vitrified (granular or pelletized) blast furnace slag; converter steel slag; electric arc furnace carbon steel slag; ladle slag; finely ground shale; quartz; high-alumina cement; sulfoaluminate clinker; yelimit; belite clinker; recycled glass; zeolite; diatomaceous earth; recycled concrete aggregates from demolition; and any mixtures thereof.

[0126] In particular, mineral materials other than clinker suitable for use in this invention include, for example, calcium sulfate; mineral admixtures (e.g., calcined clay, limestone, natural or artificial volcanic ash, silica fume, fly ash, granular blast furnace slag, calcined shale); crystalline, expanded, vitrified (granular or pelletized) blast furnace slag; converter steel slag; electric arc furnace carbon steel slag; ladle slag; ground shale; quartz; high-alumina cement; sulfoaluminate cement; recycled glass; zeolite; diatomaceous earth; recycled concrete aggregate from demolition; and any mixtures thereof.

[0127] Specifically, the mineral materials other than clinker are selected from any one of calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash, calcined shale, ground shale, diatomaceous earth and mixtures thereof; preferably selected from any one of calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash and mixtures thereof.

[0128] In particular, the mineral materials other than clinker are selected from calcium sulfate and mineral admixtures, more particularly from calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash and blast furnace slag, and even more particularly from any one of calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash and mixtures thereof.

[0129] The term "mineral admixture" refers to granular blast furnace slag as defined in paragraph 5.2.2 of NF EN 197-1 (April 2012), "Composition, specifications and conformity criteria for common cements"; pozzolanic materials, such as calcined clay (as defined in paragraph 5.2.3 of NF EN 197-1 (April 2012), "Composition, specifications and conformity criteria for common cements"); fly ash (as defined in paragraph 5.2.4 of NF EN 197-1 (April 2012), "Composition, specifications and conformity criteria for common cements"); and calcined shale (as defined in NF EN 197-1 (April 2012), "Composition, specifications and conformity criteria for common cements"). (as defined in paragraph 5.2.5 of standard NF EN 197-1 (April 2012) "Composition, specifications and conformity criteria for common cements"); limestone (as defined in paragraph 5.2.6 of standard NF EN 197-1 (April 2012) "Composition, specifications and conformity criteria for common cements"); or silica fume (as defined in paragraph 5.2.7 of standard NF EN 197-1 (April 2012) "Composition, specifications and conformity criteria for common cements"); or mixtures thereof.

[0130] In particular, the mineral materials other than clinker are selected from brittle mineral materials.

[0131] Preferably, the mineral composition to be ground comprises a mixture of at least one first mineral material to be ground and at least one second mineral material to be ground.

[0132] The first and second mineral materials to be ground are preferably selected independently from one of the above list of "mineral materials other than clinker suitable for the present invention", preferably from clinker; calcium sulfate; mineral admixtures (e.g., calcined clay, limestone, natural or artificial volcanic ash, silica fume, fly ash, granular blast furnace slag, calcined shale); crystalline, expanded, vitrified (granular or pelletized) blast furnace slag; converter steel slag; electric arc furnace carbon steel slag; ladle slag; ground shale; quartz; high-alumina cement; sulfoaluminate clinker; yelmet; belite clinker; recycled glass; zeolite; diatomaceous earth and demolition recycled concrete fines, more preferably from any one of clinker, calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash and mixtures thereof.

[0133] According to a specific embodiment, the first mineral material to be ground is a hard mineral material, and the second mineral material to be ground is a brittle mineral material. Therefore, the mineral composition to be ground may comprise at least one hard mineral material and at least one brittle mineral material. Hard mineral materials and brittle mineral materials are as defined above.

[0134] Preferably, relative to the total dry weight of the mineral composition to be ground, the mineral composition to be ground contains 1% to 99% by weight, preferably 10% to 90% by weight, preferably 20% to 80% by weight, preferably 30% to 70% by weight, preferably 40% to 60% by weight of brittle mineral material. If the mineral composition to be ground contains several brittle mineral materials, these contents correspond to the total content of brittle mineral materials.

[0135] Preferably, relative to the total dry weight of the mineral composition to be ground, the mineral composition to be ground contains 1% to 99% by weight, preferably 10% to 90% by weight, preferably 20% to 80% by weight, preferably 30% to 70% by weight, preferably 40% to 60% by weight of hard mineral material. If the mineral composition to be ground contains several hard mineral materials, these contents correspond to the total content of hard mineral materials.

[0136] According to a more specific embodiment, the first mineral material to be ground is clinker, and the second mineral material to be ground is a mineral material other than clinker, preferably selected from one of the above-mentioned lists of "mineral materials other than clinker suitable for the present invention," preferably selected from calcium sulfate; mineral admixtures (e.g., calcined clay, limestone, natural or artificial volcanic ash, silica fume, fly ash, granular blast furnace slag, calcined shale); crystalline, expanded, vitrified (granular or pelletized) blast furnace slag; converter steel slag; electric furnace carbon steel slag; ladle slag; ground shale; quartz; high-alumina cement; sulfoaluminate clinker; yelimit; belite clinker; recycled glass; zeolite; diatomaceous earth; fine aggregates from demolition recycled concrete and mixtures thereof, more preferably selected from calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash, calcined shale, ground shale, diatomaceous earth and mixtures thereof; ... The material is selected from any one of clay, limestone, natural or artificial volcanic ash, fly ash and mixtures thereof, and even more preferably from any one of calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash and mixtures thereof. The clinker content is 0.01% to 80% by weight, preferably 1% to 70% by weight, preferably 1% to 60% by weight, preferably 5% to 55% by weight, preferably 5% to 50% by weight, preferably 10% to 40% by weight, and preferably, the content of the second mineral material to be ground is 20% to 99.99% by weight, preferably 30% to 99% by weight, preferably 40% to 99% by weight, preferably 55% to 95% by weight, preferably 50% to 95% by weight, preferably 60% to 90% by weight, relative to the total dry weight of the mineral composition to be ground.

[0137] Preferably, according to this embodiment, the second mineral material to be ground is a brittle mineral material.

[0138] According to another, more specific embodiment, the first and second mineral materials to be ground are each mineral materials other than clinker, preferably independently selected from one of the above lists of "mineral materials other than clinker suitable for the present invention," preferably selected from calcium sulfate; mineral admixtures (e.g., calcined clay, limestone, natural or artificial volcanic ash, silica fume, fly ash, granular blast furnace slag, calcined shale); crystalline, expanded, vitrified (granular or pelletized) blast furnace slag; converter steel slag; electric arc furnace carbon steel slag; ladle slag; ground shale; quartz. High-alumina cement; sulfoaluminate clinker; yelmitt; belite clinker; recycled glass; zeolite; diatomaceous earth; and any one of the following: fine aggregates of demolition recycled concrete and mixtures thereof, more preferably selected from calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash, calcined shale, ground shale, diatomaceous earth and mixtures thereof; even more preferably selected from calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash and mixtures thereof, and even more preferably selected from calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash and mixtures thereof.

[0139] Preferably, the mineral composition to be ground comprises: a mixture of clinker and calcium sulfate; or a mixture of clinker and calcined clay; or a mixture of clinker and limestone; or a mixture of clinker and volcanic ash (natural or artificial source); or a mixture of calcium sulfate and calcined clay; or a mixture of calcium sulfate and limestone; or a mixture of calcium sulfate and volcanic ash (natural or artificial source); or a mixture of limestone and calcined clay; or a mixture of limestone and volcanic ash (natural or artificial source); or a mixture of calcined clay and volcanic ash (natural or artificial source);

[0140] The mixture may be a mixture of clinker, calcium sulfate, and calcined clay; or a mixture of clinker, calcium sulfate, and limestone; or a mixture of clinker, calcium sulfate, and volcanic ash (natural or artificial); or a mixture of clinker, calcium sulfate, calcined clay, and limestone; or a mixture of clinker, calcium sulfate, volcanic ash (natural or artificial), and limestone; or a mixture of calcined clay, limestone, and volcanic ash (natural or artificial). It should be understood that, when clinker is present, its content relative to the total dry weight of the mineral composition to be ground is from 0.01% to 80% by weight, preferably from 1% to 70% by weight, preferably from 1% to 60% by weight, preferably from 5% to 55% by weight, preferably from 5% to 50% by weight, preferably from 10% to 40% by weight.

[0141] According to one embodiment, the mineral composition to be ground contains calcium sulfate as an additional element, preferably at a content of 0.1% to 10% by weight, more preferably 1% to 5% by weight, relative to the dry weight of the mineral composition to be ground without calcium sulfate. In fact, according to this embodiment, the calcium sulfate content is expressed relative to the total dry weight of all components of the mineral composition to be ground, excluding calcium sulfate. Therefore, according to this embodiment, the content of clinker and all materials other than clinker is also expressed relative to the dry weight of the mineral composition to be ground without calcium sulfate.

[0142] According to this embodiment, calcium sulfate is present in the mineral composition to be ground, in addition to the mineral material to be ground other than clinker and optionally clinker, or in addition to the first mineral material to be ground and the second mineral material to be ground. In this embodiment, the mineral material to be ground other than clinker, or the first mineral material to be ground and the second mineral material to be ground, are as defined above, but are different from calcium sulfate (therefore all embodiments defined above apply, but calcium sulfate is not listed in the compound list).

[0143] According to this embodiment, the mineral composition to be ground preferably comprises, expressed as a percentage of the total dry weight of the mineral composition to be ground (rather than the dry weight of the mineral composition to be ground excluding calcium sulfate):

[0144] - 0 to 80% by weight of clinker, preferably 0.01% to 80% by weight, preferably 1% to 70% by weight, preferably 1% to 60% by weight, preferably 5% to 55% by weight, preferably 5% to 50% by weight, preferably 10% to 40% by weight of clinker.

[0145] - 19% to 95% by weight of mineral materials other than clinker, preferably 19% to 94.99% by weight, preferably 19.9% ​​to 90% by weight, preferably 19.9% ​​to 89.99% by weight, preferably 29% to 94% by weight, preferably 29.9% to 89% by weight, preferably 39% to 94% by weight, preferably 39.9% to 89% by weight, preferably 44.9% to 85% by weight, preferably 44% to 90% by weight, preferably 49% to 90% by weight, preferably 49.9% to 85% by weight, preferably 59% to 85% by weight, preferably 59.9% to 80% by weight of mineral materials other than clinker, and

[0146] - 0.1% to 10% by weight of calcium sulfate, preferably 1% to 5% by weight of calcium sulfate.

[0147] Mixed mineral composition

[0148] The present invention also relates to a mixed mineral composition.

[0149] Within the meaning of this application, the term "mixed mineral composition" refers to a mineral composition further comprising an additive composition as defined above, and "mineral composition" refers to a mineral composition without additives.

[0150] The mixed mineral composition is preferably ground.

[0151] Preferably, the fineness exhibited by the mixed mineral composition is categorized as median diameter (d). 50 The fineness is less than or equal to 20 μm, preferably less than or equal to 15 μm, more preferably less than or equal to 10 μm, and most preferably 1 to 20 μm. This fineness parameter corresponds to the diameter of one half of the particle group being coarser and the other half being finer.

[0152] Preferably, for 9 μm to 11 μm, a median diameter d of about 10 μm is preferred. 50 The mixed mineral composition exhibits at least 70% by volume of 2-32 μm particles, preferably at least 72% by volume, more preferably at least 74% by volume, and more preferably 70% to 95% by volume of 2-32 μm particles relative to the total volume of the mixed mineral composition.

[0153] Median diameter (d) 50 The content of 2-32 μm particles was extracted from the particle size distribution measured by laser particle size analysis, for example, using a MALVERN Mastersizer 3000 device, with a Mie model of 1.68+0.1i (i is the imaginary exponent) measured by dry method.

[0154] Preferably, in the mixed mineral composition, the content of polymer (P) is 0.01% to 1% by weight, more preferably 0.05% to 0.5% by weight, more preferably 0.05% to 0.3% by weight, and more preferably 0.10% to 0.30% by weight, relative to the total dry weight of the mineral composition.

[0155] Preferably, the mixed mineral composition contains 0% to 80% by weight of clinker relative to the total dry weight of the mineral composition.

[0156] Therefore, the mineral composition preferably comprises at least one mineral material to be ground, other than clinker, and optionally clinker.

[0157] Preferably, relative to the total dry weight of the mineral composition, the mixed mineral composition comprises 20% to 100% by weight of mineral materials other than clinker, preferably 20% to 99.99% by weight, preferably 30% to 99% by weight, preferably 40% to 99% by weight, preferably 45% to 95% by weight, preferably 50% to 95% by weight, preferably 60% to 90% by weight of mineral materials other than clinker.

[0158] When the mixed mineral composition contains clinker, the clinker is present in a content of preferably 0.01% to 80% by weight, preferably 1% to 70% by weight, preferably 1% to 60% by weight, preferably 5% to 55% by weight, preferably 5% to 50% by weight, and preferably 10% to 40% by weight, relative to the total dry weight of the mineral composition.

[0159] The mineral materials other than clinker are as defined above for the mineral composition to be ground. According to one embodiment, the mineral materials other than clinker are brittle mineral materials.

[0160] Preferably, the mixed mineral composition comprises a mixture of at least one first mineral material and at least one second mineral material.

[0161] The first and second mineral materials are preferably independently selected from clinker; calcium sulfate; mineral admixtures (e.g., calcined clay, limestone, natural or artificial volcanic ash, silica fume, fly ash, granular blast furnace slag, calcined shale); crystalline, expanded, vitrified (granular or pelletized) blast furnace slag; converter steel slag; electric arc furnace carbon steel slag; ladle slag; ground shale; quartz; high-alumina cement; sulfoaluminate clinker; yelimit; belite clinker; recycled glass; zeolite; diatomaceous earth; and fine aggregates of demolished recycled concrete and mixtures thereof, more preferably selected from clinker, calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash and mixtures thereof. According to a specific embodiment, the first mineral material is a hard mineral material, and the second mineral material is a brittle mineral material, preferably in the content defined above for the mineral composition to be ground.

[0162] According to a more specific embodiment, the first mineral material is clinker, and the second mineral material is selected from calcium sulfate, mineral admixtures (e.g., calcined clay, limestone, natural or artificial volcanic ash, silica fume, fly ash, granular blast furnace slag, calcined shale), crystallized, expanded, vitrified (granular or pelletized) blast furnace slag; converter steel slag; electric arc furnace carbon steel slag; ladle slag; ground shale; quartz; high-alumina cement; sulfoaluminate clinker; yelmitt; belite clinker; recycled glass; zeolite; diatomaceous earth; and any of the following: recycled concrete aggregates and mixtures thereof, more preferably selected from calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash, granulated blast furnace slag, calcined shale, crystallized, expanded, vitrified (granular or pelletized) blast furnace slag; converter steel slag; electric arc furnace carbon steel slag; ladle slag; ground shale; quartz; high-alumina cement; sulfoaluminate clinker; yelmitt; belite clinker; recycled glass; zeolite; diatomaceous earth; and fines from demolition recycled concrete and mixtures thereof, more preferably selected from calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash, granulated shale, calcined ... The mineral composition comprises any one of ash, calcined shale, ground shale, diatomaceous earth, and mixtures thereof; more preferably, it is selected from any one of calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash, and mixtures thereof; even more preferably, it is selected from any one of calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, and mixtures thereof, and the clinker content relative to the total dry weight of the mineral composition is from 0.01% to 80% by weight, preferably from 1% to 70% by weight, preferably from 1% to 60% by weight, preferably from 5% to 55% by weight, preferably from 5% to 50% by weight, preferably from 10% to 40% by weight. Preferably, according to this embodiment, the second mineral material is a brittle mineral material.

[0163] According to another more specific embodiment, the first and second mineral materials are different from clinker and are preferably selected independently from calcium sulfate; mineral admixtures (e.g., calcined clay, limestone, natural or artificial volcanic ash, silica fume, fly ash, granular blast furnace slag, calcined shale); crystalline, expanded, vitrified (granular or pelletized) blast furnace slag; converter steel slag; electric arc furnace carbon steel slag; ladle slag; ground shale; quartz; high-alumina cement; sulfoaluminate clinker; yelmitt; belite clinker; recycled glass; zeolite; diatomaceous earth; and any one of the following: demolition recycled concrete fines and mixtures thereof, more preferably selected from any one of calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash, calcined shale, ground shale, diatomaceous earth and mixtures thereof; even more preferably selected from any one of calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash, fly ash and mixtures thereof, and even more preferably selected from any one of calcium sulfate, calcined clay, limestone, natural or artificial volcanic ash and mixtures thereof.

[0164] Specifically, the mixed mineral composition comprises a mixture of clinker and calcium sulfate; or a mixture of clinker and calcined clay; or a mixture of clinker and limestone; or a mixture of clinker and volcanic ash (natural or artificial source); or a mixture of calcium sulfate and calcined clay; or a mixture of calcium sulfate and limestone; or a mixture of calcium sulfate and volcanic ash (natural or artificial source); or a mixture of limestone and calcined clay; or a mixture of limestone and volcanic ash (natural or artificial source); or a mixture of calcined clay and volcanic ash (natural or artificial source).

[0165] The mixture may be a mixture of clinker, calcium sulfate, and calcined clay; or a mixture of clinker, calcium sulfate, and limestone; or a mixture of clinker, calcium sulfate, and volcanic ash (natural or artificial); or a mixture of clinker, calcium sulfate, calcined clay, and limestone; or a mixture of clinker, calcium sulfate, volcanic ash (natural or artificial) and limestone; or a mixture of calcined clay, limestone, and volcanic ash (natural or artificial). It should be understood that, when clinker is present, its content relative to the total dry weight of the mineral composition is from 0.01% to 80% by weight, preferably from 1% to 60% by weight, preferably from 5% to 55% by weight, preferably from 5% to 50% by weight, and preferably from 10% to 40% by weight.

[0166] According to one embodiment, the mixed mineral composition includes calcium sulfate as an additional element, preferably in a content of 0.1% to 10% by weight, more preferably 1% to 5% by weight, relative to the dry weight of the mineral composition without calcium sulfate. In fact, according to this embodiment, the content of calcium sulfate is expressed relative to the total dry weight of all components of the mineral composition other than calcium sulfate. Therefore, according to this embodiment, the contents of the clinker and all materials other than clinker described above are applicable, but are expressed relative to the dry weight of the mineral composition without calcium sulfate.

[0167] According to this embodiment, calcium sulfate is present in the mixed mineral composition, in addition to mineral materials other than clinker and optional clinker, or in addition to the first mineral material and the second mineral material. In this embodiment, the mineral materials other than clinker, or the first mineral material and the second mineral material, are as defined above, but are different from calcium sulfate (therefore all embodiments defined above apply, but calcium sulfate is not included in the list of mineral compounds).

[0168] According to this embodiment, the mixed mineral composition preferably comprises, expressed as a percentage of the total dry weight of the mineral composition (rather than a percentage of the dry weight of the mineral composition excluding calcium sulfate):

[0169] - 0% to 80% by weight of clinker, preferably 0.01% to 80% by weight, preferably 1% to 70% by weight, preferably 1% to 60% by weight, preferably 5% to 55% by weight, preferably 5% to 50% by weight, preferably 10% to 40% by weight of clinker.

[0170] - 19% to 95% by weight of mineral materials other than clinker, preferably 19% to 94.99% by weight, preferably 19.9% ​​to 90% by weight, preferably 19.9% ​​to 89.99% by weight, preferably 29% to 94% by weight, preferably 29.9% to 89% by weight, preferably 39% to 94% by weight, preferably 39.9% to 89% by weight, preferably 44.9% to 85% by weight, preferably 44% to 90% by weight, preferably 49% to 90% by weight, preferably 49.9% to 85% by weight, preferably 59% to 85% by weight, preferably 59.9% to 80% by weight, and

[0171] - 0.1% to 10% by weight of calcium sulfate, preferably 1% to 5% by weight of calcium sulfate.

[0172] Preferably, the mixed mineral composition is obtained by the grinding method according to the invention.

[0173] The mixed mineral composition may contain other ingredients, which may be added, optionally by adding the mixed composition of this application, before grinding, or after grinding. For this purpose, references may be made to, but are not limited to, alkanolamines, glycols, glycerols, accelerator compounds (including chloride salts, thiocyanates, formates, nitrates and / or nitrites and mixtures thereof), carboxylic acids or their salts (including acetic acid, adipic acid, gluconic acid, formic acid, oxalic acid, citric acid, maleic acid, lactic acid, tartaric acid, malonic acid and mixtures thereof), water-reducing and high-efficiency water-reducing compounds (including lignin sulfonates, hydroxylated carboxylic acids, comb-type polycarboxylate and mixtures thereof), anti-caking compounds (which are relative numerical indices, measured as described in standard ASTM C1565-19, indicating the tendency of cement to compact during bulk storage or transport) (including polyacrylic acid), surfactants, defoamers (including tributyl phosphate, triisobutyl phosphate, dibutyl phthalate, octanol, alkylamines, water-insoluble carbonates and borates and mixtures thereof), air-entraining agents (including wood resin salts, sulfonated lignin salts and mixtures thereof), retarders (including sugars, corn syrup and molasses and mixtures thereof) and mixtures thereof.

[0174] hydraulic compositions

[0175] The present invention also relates to a hydraulic composition comprising:

[0176] - A mixed mineral composition as defined above,

[0177] - water,

[0178] - Optional aggregates, and

[0179] - Optional mineral admixtures.

[0180] The hydraulic composition according to the present invention is preferably a concrete, mortar, or mortar underlay composition.

[0181] The hydraulic composition is prepared by mixing the above components in a conventional manner.

[0182] An "aggregate" refers to a group of mineral particles with an average diameter of 0 to 125 mm. Based on their diameter, aggregates are classified into one of six families: fillers, sablons, sands, gravels, chippings, and ballast (in standard NFP18-545 (September 2011) "Aggregates – Elements of definition, conformity, and codification"). The most commonly used aggregates are as follows:

[0183] - A packing material having a diameter of less than 2 mm, wherein at least 85% of the aggregates have a diameter of less than 1.25 mm, and at least 70% of the aggregates have a diameter of less than 0.063 mm;

[0184] - Medium sand with a diameter of 0 to 4 mm (the diameter can reach 6 mm in standard NF EN 13242+A1 (March 2008) "Aggregates for hydraulicallybound materials and unbound materials for use in civil engineering work and road construction");

[0185] - Gravel with a diameter greater than 6.3 mm;

[0186] - Crushed stone with a diameter of 2mm to 63mm.

[0187] Therefore, medium sand is included in the definition of aggregates according to the present invention.

[0188] The filler may be specifically sourced from limestone or dolomite.

[0189] The hydraulic composition may also contain other additives known to those skilled in the art, such as mineral admixtures and / or additives, such as anti-air entrainment additives, defoamers, accelerators or retarders, rheology modifiers, another fluidizing agent (plasticizer or superplasticizer), especially superplasticizers, such as CHRYSO® Fluid Premix 180 or CHRYSO® Fluid Premix 196 superplasticizer.

[0190] Within the scope of this invention, among retarders, those based on sugar, molasses, or distiller's grains may be particularly mentioned.

[0191] Preferably, the water-reducing and high-efficiency water-reducing admixtures are selected from:

[0192] - Sulfonated salts of naphthalene-formaldehyde condensates, commonly known as polynaphthalene sulfonates or naphthalene-based superplasticizers;

[0193] - Sulfonated salts of melamine-formaldehyde condensate, commonly known as melamine-based superplasticizers;

[0194] - Lignin derivatives, such as lignin sulfonates;

[0195] - Sodium gluconate and sodium gluconate;

[0196] - Polyacrylate;

[0197] - Polyarylene ether (PAE);

[0198] - Products based on polycarboxylic acids, particularly polycarboxylic acid ester comb copolymers, which are branched polymers with a main chain carrying carboxyl groups and side chains consisting of polyether-type sequences, especially polyethylene oxides, such as poly[(meth)acrylic acid-grafted-polyethylene oxide]. Superplasticizers from the CHRYSO® Fluid Optima, CHRYSO® Fluid Premia, and CHRYSO® Plast Omega series sold by CHRYSO, and ADVA®, MIRA®, ZYLA®, and CONCERA® sold by GCP can be used in particular.

[0199] Products based on polyalkoxylated polyphosphonates are specifically described in patent EP0663892 (e.g., CHRYSO® Fluid Optima 100). Detailed Implementation

[0200] The invention will become clearer when reading the following description, which is given by way of non-limiting example only.

[0201] In all embodiments, unless otherwise stated, the content of the mixture is expressed as a weight relative to the total dry weight of the unmixed mineral composition.

[0202] Example

[0203] The various polymers used are detailed in the table below:

[0204] [Table 1]

[0205]

[0206] *:Compare

[0207] Example 1: The effect of the properties of polymers present during the grinding of mineral compositions on the particle size of the ground mineral compositions. Influence of particle distribution

[0208] A mineral composition comprising 55% by weight of clinker, 5% by weight of gypsum, and 40% by weight of natural volcanic ash relative to the dry weight of the mineral composition was ground alone or in a closed system with a capacity of 5 kg in a laboratory ball mill.

[0209] When present, the polymer is introduced into the mill along with various materials before grinding begins.

[0210] For each test, the mineral composition was ground until the lowest possible median diameter (d) was obtained. 50 The fineness parameter (corresponding to the diameter of half the particle group being coarser and the other half finer) was extracted from the particle size distribution measured by dry method using laser particle size distribution with a MALVERN Mastersizer 3000 instrument and Mie model 1.68+0.1i. The proportion of particles with diameters from 2 μm to 32 μm was also extracted from the particle size distribution. This proportion is expressed as a percentage.

[0211] The results are collected in Table 2 below:

[0212] [Table 2]

[0213]

[0214] *:Compare

[0215] These results indicate that the presence of the polymer during milling makes the milling process more efficient than that of a reference system milled without additives, for d 50 For a diameter of 10 μm, the proportion of 2-32 μm particles can be increased, achieving a median diameter lower than the reference. However, polymers B, C, D, and E according to the invention make it possible to achieve a diameter of d... 50For a size of 10 μm, a greater increase in the proportion of 2-32 μm particles can be obtained, i.e., greater than +6%. The maximization of the proportion of 2-32 μm particles obtained with these specific polymers is related to the combination of the length of the grafted chain (the exponent z of unit II) on the one hand and the molecular weight of the repeating unit (A) on the other hand.

[0216] Example 2: The properties of polymers present during the grinding of mineral compositions for use in grinding minerals containing the minerals of Example 1. Effect of the composition on the short-term strength of the hydraulic composition

[0217] According to the scheme of standard NF EN 196-1 (September 2016) "Methods of testing cement - Part 1: Determination of strength - Methods of testing cement", various hydraulic compositions comprising the ground mineral composition of Example 1 were prepared by using water to cement in a composition ratio of 0.5.

[0218] The compressive mechanical strength of the final composition at 24 and 48 hours was evaluated according to standard NF EN 196-1 (September 2016) “Methods of testing cement - Part 1: Determination of strength - Methods of testing cement”.

[0219] The results are shown in Table 3 below:

[0220] [Table 3]

[0221]

[0222] *:Compare

[0223] These results indicate that polymers B, C, D, and E, which enable the production of high-level 2-32 μm particles, also enable further improvement of the 24-hour and 48-hour strength of hydraulic compositions based on mineral compositions milled in the presence of said polymers.

[0224] Example 3: Effect of mineral composition (calcined clay) on the properties

[0225] In this embodiment, a mineral composition comprising 55% by weight clinker, 5% by weight gypsum, and 40% by weight calcined clay relative to the dry weight of the mineral composition was milled alone or in the presence of polymers A, B, or G as defined in Table 1, given at 0.1% by weight relative to the dry weight of the mineral composition as active materials, in a closed system with a grinding capacity of 5 kg. For each test, the mineral composition was milled until the lowest possible median diameter (d) was obtained. 50 ).

[0226] The results are collected in Table 4 below.

[0227] [Table 4]

[0228]

[0229] *:Compare

[0230] The compressive mechanical strength of the hydraulic compositions 3-1*, 3-2* and 3-3, which are similar to those in Example 2 but contain elements of Example 3, at 24 hours and 48 hours was also determined according to the same scheme as in Example 2.

[0231] The results are collected in Table 5 below:

[0232] [Table 5]

[0233]

[0234] These results are similar to those obtained in Example 1, i.e., the polymers that meet the definition according to the invention allow for a higher proportion of 2-32 μm particles than the comparative polymers.

[0235] This indicates that the specific selection of these polymers allows for the maximization of this particle population for different mineral compositions and therefore for short-term compressive mechanical strength, whether these mineral compositions are ground individually or mixed with clinker.

[0236] Example 4: Effect of the proportion of 2-32μm particles

[0237] Short-term compressive mechanical strength (24 hours) was compared between hydraulic compositions containing mineral compositions 3-5 of Example 3 and hydraulic compositions containing similar mineral compositions but not yet milled in the presence of polymer G, the latter being added at the same proportion during mixing, i.e., 0.1% relative to the dry weight of the mineral composition as an active material.

[0238] The results are presented in Table 6 below:

[0239] [Table 6]

[0240]

[0241] *:Compare

[0242] These results illustrate the importance of the 2-32 μm particle ratio for obtaining high short-term compressive strength. In this embodiment, the early hydration delay in the hydraulic composition caused by the acidity of the polymer is compensated by increasing the fineness of the mineral composition.

[0243] Example 5: Comparison with existing grinding aids

[0244] The grinding efficiency of the mineral composition in Comparative Example 3 was determined, depending on whether it was carried out in the presence of 0.1% polymer B or 0.01% triethanolamine, with the dosage expressed as a percentage of active material relative to the weight of the mineral composition. For each test, the mineral composition was ground until a median diameter (d) of 7.5 μm was obtained. 50 ).

[0245] The results are presented in Table 7 below:

[0246] [Table 7]

[0247]

[0248] Based on the results of Examples 1 and 3, polymer B makes it possible for a given d 50 (10μm) But in the final state, it can achieve a higher proportion of particles with a diameter of 2-32μm than the reference system, which is different from triethanolamine, which cannot improve this property.

[0249] Example 6: Effect of mineral composition on properties

[0250] In this embodiment, different mineral compositions were milled in a laboratory ball mill within a closed system with a grinding capacity of 5 kg, with or without polymer G as defined in Table 1, given as an active material at 0.1% relative to the dry weight of the mineral composition. For each test, the mineral composition was milled until a given median diameter (d) was obtained. 50 (represented as "d under consideration") 50 ”).

[0251] The results are collected in Table 8 below:

[0252] [Table 8]

[0253]

[0254] *: Comparison (= No additives)

[0255] Example 7: Mineral admixtures: calcined clay and limestone ground in the presence of polymer G (tests 7-2 and 7-). 4), or using a grinding aid based on triethanolamine acetate (in the case of calcined clay, test 7-1*) or... Grinding without any additives (in the case of limestone, test 7-3**).

[0256] The results are collected in Table 9 below:

[0257] [Table 9]

[0258]

[0259] *: Comparison of grinding in the presence of triethanolamine acetate-based grinding aids

[0260] **: Comparison, grinding without any additives.

[0261] The results of calcined clay studies show that the use of polymers (P) enables the acquisition of even higher 2-32 μm particle content than existing grinding aids, demonstrating the benefits of these polymers as grinding aids for brittle mineral materials such as calcined clay.

[0262] The results for limestone also showed the benefits of polymer (P) as a grinding aid for brittle mineral materials, as a very significant increase in the content of 2-32 μm particles was achieved in the presence of polymer G compared to limestone ground without grinding aid.

Claims

1. A grinding method comprising grinding a mineral composition to be ground in the presence of an additive composition comprising at least one polymer (P), said polymer (P) comprising n repeating units (A) of the following formula: in: - "M" independently represents H + Alternatively, it may be a cation with a valence of v selected from alkali metal cations, alkaline earth metal cations, divalent or trivalent metal cations, ammonium cations, or organic ammonium cations. - When "M" represents H, "v" represents 1, and when "M" represents a cation selected from alkali metal cations, alkaline earth metal cations, divalent or trivalent metal cations, ammonium cations, or organic ammonium cations, "v" is the valence of cation M. - "R2" and "R3" independently represent hydrogen, methyl, or the formula -COO(M) having M and v as defined above. 1 / v The group, preferably hydrogen or methyl, - "R4" and "R5" independently represent hydrogen, methyl, or the formula -COO(M) having M and v as defined above. 1 / v group, - "m" represents 0, 1, or 2. - "p" represents 0 or 1, - "X" is O or N, and - "R1" indicates -[alkyl-O] z -R6, where "alkyl" in each [alkyl-O] unit independently represents a straight-chain or branched alkylene group containing 2 to 4 carbon atoms, "R6" represents H, C1 to C20 alkyl, cyclohexyl or alkylaryl, and "z" is greater than or equal to 40. The number of units (I) and units (II) in the polymer (P) is defined by repeating units (A) containing one unit (II) and "a" units (I). - "a" represents a non-zero positive number. - "n" ranges from 1.5 to 50, and - The molecular weight of the repeating unit (A) is less than or equal to 6500 g / mol, and the mineral composition to be ground contains 0% to 80% by weight of clinker and 20% to 100% by weight of mineral materials other than clinker, relative to the total weight of the mineral composition to be ground.

2. The grinding method according to claim 1, wherein, The repeating unit (A) of the polymer (P) has a molecular weight of 1500 g / mol to 6500 g / mol, preferably 2000 g / mol to 6500 g / mol, more preferably 2500 g / mol to 6500 g / mol, more preferably 4500 g / mol to 6000 g / mol, and even more preferably 5200 g / mol to 5600 g / mol.

3. The grinding method according to claim 1 or 2, wherein, The polymer (P) is such that "z" is greater than or equal to 50, preferably greater than or equal to 70, preferably greater than or equal to 80, preferably greater than or equal to 85, preferably greater than or equal to 90, and preferably greater than or equal to 100.

4. The grinding method according to any one of the preceding claims, wherein, The polymer (P) has "a" of 0.2 to 100, preferably 0.5 to 50, preferably 1.0 to 20, preferably 3.0 to 10, preferably 3.9 to 7, and preferably 4.0 to 6.

5. The grinding method according to any one of the preceding claims, wherein, The grafting ratio of the polymer (P) is strictly greater than 5%, preferably greater than or equal to 6%, more preferably greater than or equal to 10%, and more preferably greater than or equal to 12%.

6. The grinding method according to any one of the preceding claims, wherein, Relative to the total dry weight of the mineral composition to be ground, the mineral composition to be ground comprises at least one mineral material other than clinker and optionally 0.01% to 80% by weight of clinker, wherein the material other than clinker is selected from calcium sulfate; mineral admixtures; Crystallized, expanded, and vitrified blast furnace slag; converter steel slag; electric arc furnace carbon steel slag; ladle slag; finely ground shale; Quartz; high-alumina cement; sulfoaluminate clinker; yelmitt; belite clinker; recycled glass; zeolite; diatomaceous earth; recycled concrete aggregate from demolition; and mixtures thereof, preferably selected from calcium sulfate; calcined clay; limestone; natural or artificial volcanic ash; fly ash; calcined shale; finely ground shale; diatomaceous earth and mixtures thereof.

7. The grinding method according to any one of the preceding claims, wherein, Relative to the total dry weight of the mineral composition to be ground, the mineral composition to be ground comprises at least one mineral material other than clinker, and optionally 0.01% to 80% by weight of clinker, wherein the material other than clinker is selected from brittle mineral materials that achieve a Blaine fineness of 1500 cm⁻¹. 2 / g to 2500cm 2 The grinding time required per g is at least twice as short as that required to obtain the same Brønsted fineness of clinker that meets the requirements of standard NF EN 197-1.

8. The grinding method according to any one of the preceding claims, wherein, The content of the introduced polymer (P) is 0.01% to 1% by weight, preferably 0.05% to 0.5% by weight, relative to the total dry weight of the mineral composition to be ground.

9. The grinding method according to any one of the preceding claims, the grinding method being a co-grinding method of at least one first mineral material to be ground and at least one second mineral material to be ground, and further comprising a stage of preparing a mineral composition to be ground, the stage comprising mixing the at least one first mineral material to be ground and the at least one second mineral material to be ground to obtain the mineral composition to be ground.

10. A mixed-milled mineral composition comprising a mineral composition and a polymer (P) as defined in any one of claims 1 to 5, wherein the mineral composition comprises 0% to 80% by weight of clinker and 20% to 100% by weight of mineral material other than clinker, relative to the total dry weight of the mineral composition.

11. The mixed-milling mineral composition according to claim 10, having a median diameter (d) of less than or equal to 20 μm, preferably less than or equal to 15 μm, and more preferably less than or equal to 10 μm. 50 The level of detail in the representation.

12. The mixed-grind mineral composition according to claim 10 or 11, wherein, The content of the polymer (P) is 0.01% to 1% by weight, preferably 0.05% to 0.5% by weight, relative to the total dry weight of the mineral composition.

13. The mixed-grind mineral composition according to any one of claims 10 to 12, wherein, The clinker content is from 0.01% to 80% by weight, preferably from 1% to 60% by weight, preferably from 5% to 55% by weight, preferably from 5% to 50% by weight, and preferably from 10% to 40% by weight, relative to the total dry weight of the mineral composition.

14. The mineral composition of any one of claims 10 to 13, obtained by the grinding method according to claims 1 to 9.

15. A hydraulic composition comprising: - The mixed-milled mineral composition according to any one of claims 10 to 14, - water, - Optional aggregates, and - Optional mineral admixtures.

16. Use of the polymer (P) as defined in any one of claims 1 to 5 for improving the grindability of a mineral composition to be ground, wherein the mineral composition to be ground comprises 0% to 80% by weight of clinker and 20% to 100% by weight of mineral material other than clinker, relative to the total weight of the mineral composition; preferably for increasing the proportion of the 2-32 μm fraction in the particle size distribution of the ground mineral composition, wherein the ground mineral composition comprises 0% to 80% by weight of clinker and 20% to 100% by weight of mineral material other than clinker, relative to the total weight of the mineral composition.

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