Calcium silicate based hydraulic cementitious binder for forming composites with enhanced properties

Abstract

The present invention relates to the field of hydraulic cements and hardened materials obtained after hydration of said hydraulic cements, in particular cements useful in the medical field, such as dental cements. In particular, the present invention provides a hydraulic cement comprising calcium silicate particles and calcium carbonate particles having a specific particle size. Hydration of the hydraulic cement of the present invention can provide a hardened composite material having enhanced properties, comprising calcium silicate particles dispersed in a solid dispersion phase comprising calcium silicate hydrate (CSH) and a porous interparticulate region of insoluble calcium carbonate particles having a particle size of 1 nm to 1500 nm. 50 a porous interparticulate region of insoluble calcium carbonate particles having a particle size of 1 nm to 1500 nm.

Description

Invention Field

[0001] This invention relates to the field of hydraulic adhesives and the hardened materials obtained by hydrating hydraulic adhesives. In particular, this invention relates to hydraulic adhesives comprising calcium silicate particles and calcium carbonate particles of a specific particle size. Hydration of the hydraulic adhesives of this invention can provide hardened composite materials with enhanced mechanical properties. This invention also relates to methods for manufacturing composite materials and their application in the medical or non-therapeutic adhesive fields. Background of the Invention

[0003] High-performance adhesives made from hydraulic calcium silicate binders, such as silicate binders, are increasingly being used worldwide in medical and non-therapeutic applications (such as construction).

[0004] In any field, there is always a need for hardened cementitious materials with enhanced mechanical properties, such as higher compressive strength. Furthermore, there is always a need for processes for manufacturing these materials that are less time-consuming and therefore more economical.

[0005] The applicant demonstrates that introducing calcium carbonate particles with a specific particle size group into a calcium silicate-based hydraulic binder can provide a hardened cementitious material with enhanced mechanical properties after hydration. Without wishing to be bound by any theory, the applicant believes that the specific particle size distribution of calcium carbonate used in the hydraulic binder of this invention results in the formation of porous intergranular regions with submicron calcium carbonate particles after hydration, which provides improved mechanical properties to the hardened cementitious material.

[0006] The applicant also demonstrates that when the manufacture of the hardened cementitious material includes at least one mixing step involving a powder phase containing calcium silicate particles and calcium carbonate particles with an aqueous phase via vibration, it is possible to provide a hardened material with the same type of reinforcing mechanical properties. Without wishing to be bound by any theory, the applicant proposes that the vibrational mixing step provides self-grinding of at least a portion of the calcium carbonate particles contained in the hydraulic binder, resulting in a group of calcium carbonate particles having a specific particle size according to the invention, such that the ultimately hardened cementitious material contains intergranular regions reinforced with submicron calcium carbonate particles.

[0007] Overview

[0008] The present invention therefore provides a hydraulic adhesive comprising:

[0009] - Calcium silicate particles comprising 15% to 98% by weight of the total binder, wherein 50% by volume of the total volume of the calcium silicate particles has a size of 1 μm to 10 μm; preferably a size of 1 μm to 8 μm; and

[0010] - Calcium carbonate particles comprising 0.5% to 85% by weight of the total binder, wherein:

[0011] Ten percent by volume of the total calcium carbonate particles have a size of less than 0.59 μm;

[0012] 50% by volume of the total calcium carbonate particles have a size of less than 2.5 μm; and

[0013] 40% by volume of the total calcium carbonate particles had a size ranging from 2.5 μm to 20 μm.

[0014] In one implementation scheme, the calcium carbonate particles cause:

[0015] Ten percent by volume of the total calcium carbonate particles have a size of less than 0.55 μm;

[0016] 50% by volume of the total calcium carbonate particles have a size of less than 1.5 μm; and

[0017] 40% by volume of the total calcium carbonate particles had a size ranging from 1.5 μm to 5.5 μm.

[0018] In one embodiment, the calcium silicate particles are selected from tricalcium silicate (C3S), dicalcium silicate (C2S), and any combination thereof; preferably, the calcium silicate particles are tricalcium silicate particles.

[0019] In one embodiment, calcium silicate particles are present in silicate binders and / or mineral trioxide aggregates (MTA).

[0020] In one embodiment, the hydraulic binder further comprises at least one additive, preferably selected from coagulants, radiation-impermeable agents, pigments, pH stabilizers, fillers, texturers / thickeners, water-reducing agents, and mixtures thereof.

[0021] In one embodiment, the radiation-impermeable agent is selected from zirconium oxide, bismuth oxide, cerium oxide, barium sulfate, calcium tungstate, titanium dioxide, ytterbium oxide, and mixtures thereof; preferably, the radiation-impermeable agent is zirconium oxide.

[0022] The present invention also provides a method for manufacturing a hydraulic adhesive according to the invention, comprising mixing...

[0023] - Calcium silicate particles comprising 15% to 98% by weight of the total binder, wherein 50% by volume of the total volume of the calcium silicate particles has a size of 1 μm to 10 μm; preferably a size of 1 μm to 8 μm; and

[0024] - Calcium carbonate particles comprising 0.5% to 85% by weight of the total binder, wherein:

[0025] Ten percent by volume of the total calcium carbonate particles have a size of less than 0.59 μm;

[0026] 50% by volume of the total calcium carbonate particles have a size of less than 2.5 μm; and 40% by volume of the total calcium carbonate particles have a size of 2.5 μm to 20 μm.

[0027] The present invention also provides another method for manufacturing the hydraulic binder according to the invention, comprising a mixing step of at least one powder phase, and simultaneous and / or sequential vibration steps, thereby obtaining the hydraulic binder according to the invention, wherein the powder phase comprises:

[0028] - Calcium silicate particles comprising 15% to 98% by weight of the total binder, wherein 50% by volume of the total volume of the calcium silicate particles has a size of 1 μm to 10 μm; preferably a size of 1 μm to 8 μm; and

[0029] -0.5% by weight to 85% by weight of calcium carbonate particles, of which

[0030] 10% by volume of the total calcium carbonate particles have a size of less than 1 μm;

[0031] 50% by volume of the total calcium carbonate particles have a size of less than 5 μm; and

[0032] 40% by volume of the total calcium carbonate particles have a size of 5 μm to 30 μm.

[0033] In one embodiment, the vibration step is performed at a vibration frequency of 1 rpm to 15,000 rpm, preferably 1,000 rpm to 6,000 rpm, more preferably 3,000 rpm to 5,000 rpm and a vibration time of 1 s to 3,600 s, preferably 1 s to 60 s, more preferably 30 s.

[0034] In one embodiment, the mixing of the powder phase includes mixing via three-dimensional motion.

[0035] The present invention also provides a method for manufacturing composite materials, comprising at least one step of mixing a hydraulic binder according to the invention with an aqueous phase; the mass ratio of the hydraulic binder to the aqueous phase is 2 to 4.5.

[0036] The present invention also relates to a composite material obtained by the method according to the invention, comprising:

[0037] - A solid dispersion phase comprising or consisting of hydrated calcium silicate (CSH);

[0038] - Calcium silicate particles dispersed in a solid dispersion phase;

[0039] - A porous intergranular region located between calcium silicate particles; the porous intergranular region contains insoluble calcium carbonate particles having a d0 of 1 nm to 1500 nm, preferably 1 nm to 1000 nm. 50 granularity.

[0040] This invention also provides a kit for preparing composite materials, the kit comprising:

[0041] - A powder phase comprising the hydraulic binder according to the invention; and

[0042] -Aqueous liquid phase;

[0043] The weight ratio of the powder phase to the aqueous liquid phase in the complete set of supplies is 2 to 5, preferably 2.5 to 4.

[0044] The present invention also relates to the use of the hydraulic adhesive according to the invention in the manufacture of composite materials as reinforcing materials in the field of non-therapeutic adhesives.

[0045] The present invention also relates to a hydraulic adhesive according to the invention, which is used in the medical field, preferably in the dental or orthopedic field, to form a restorative material and / or a filling material.

[0046] definition

[0047] In this invention, the following terms have the following meanings:

[0048] "Additive" means any substance added to a composition, preferably in small amounts, to improve its physicochemical properties according to its intended use. Additives may be selected, for example, from radiation-impermeable agents (e.g., zirconium oxide), coagulants (e.g., calcium oxide, calcium carbonate, calcium chloride), pigments (e.g., iron oxides), water-reducing agents (e.g., modified polycarboxylates), texture agents, pH stabilizers, surfactants, fillers, and mixtures thereof.

[0049] "Aqueous" means any compound or composition that contains water and / or moisture.

[0050] "Calcium silicate" refers to a compound that can be produced by reacting calcium oxide with silicon dioxide in different proportions.

[0051] According to one embodiment, "calcium silicate" refers to a compound made of calcium and silicates, preferably selected from tricalcium silicate, dicalcium silicate or any mixture thereof; more preferably tricalcium silicate C3S (chemical formula Ca3SiO5), dicalcium silicate C2S (chemical formula Ca2SiO4) or any mixture thereof.

[0052] - "Calcium silicate granules": refers to an aggregate containing one or more calcium silicate compounds. The term "calcium silicate granules" also includes aggregates composed of one or more calcium silicate compounds.

[0053] - "Hydrated calcium silicate" refers to the product of calcium silicate hydration. According to one embodiment, the term "hydrated calcium silicate" refers to a compound of formula (I):

[0054] mCaO.nSiO2.pH2O

[0055] Wherein n and m are independently 1 to 3 and p is 3 to 6. According to one embodiment, the term "hydrated calcium silicate" refers to the product of hydrated dicalcium silicate and / or tricalcium silicate. According to one embodiment, the term "hydrated calcium silicate" refers to a compound of formula (I) as defined above, where m equals 3, n equals 2, and p equals 3. According to one embodiment, the term "hydrated calcium silicate" further comprises calcium hydroxide (Ca(OH)₂). In this invention, the term "porous hydrated calcium silicate (p-CSH)" refers to hydrated calcium silicate forming a porous matrix, preferably having pores with a pore size greater than 0 nm to less than 1 μm. According to one embodiment, porous hydrated calcium silicate is a CSH matrix having pores with a pore size greater than 50 nm, preferably 51 nm to 1 μm, and more preferably 51 nm to 100 nm. According to one embodiment, porous hydrated calcium silicate is a CSH matrix having pores with a pore size greater than 2 nm to 50 nm. According to one embodiment, porous hydrated calcium silicate is a CSH matrix having pores with a pore size greater than 0 nm to 2 nm. In this invention, the term "dense hydrated calcium silicate (d-CSH)" refers to a matrix in which the hydrated calcium silicate forms a matrix with poorer porosity than the aforementioned porous hydrated calcium silicate. According to one embodiment, the term "dense hydrated calcium silicate (d-CSH)" refers to a matrix in which the hydrated calcium silicate forms a matrix without any pores.

[0056] - "Composite material" means any material that contains or is composed of a combination of at least two immiscible components whose physical and / or chemical properties differ from those of the components used alone.

[0057] "Dental cement" refers to any composition suitable for dental restorations that acts as an adhesive to bond castings and tooth structures together.

[0058] - "d10 particle size" refers to the average particle size of 10% of the particles being smaller than this value. According to one embodiment, d... 10 The dimensions were measured using laser diffraction.

[0059] - "d50 particle size" refers to the fact that 50% of the particles have an average particle size smaller than this value. According to one embodiment, d... 50 The dimensions were measured using laser diffraction.

[0060] - "d90 particle size" refers to the fact that 90% of the particles have an average particle size smaller than this value. According to one embodiment, d... 90 The dimensions were measured using laser diffraction.

[0061] - "Dispersed phase": refers to the chemical medium in which particles are dispersed.

[0062] - "Hardened dental materials": refers to solid materials suitable for dental applications. "Hardened dental filling materials" specifically refers to hardened dental materials suitable for filling dental restorations.

[0063] - "Hydraulic cementitious adhesive": refers to an adhesive that hardens upon contact with water. According to one embodiment, the adhesive is a dental hydraulic cementitious adhesive. According to one embodiment, the adhesive is a non-therapeutic hydraulic cementitious adhesive.

[0064] - "Laser diffraction analysis": refers to the technique of determining the size of a particle by using a laser beam to pass through the diffraction pattern of the particle.

[0065] - "Pigment": refers to any coloring chemical compound that can be natural or synthetic, inorganic or organic.

[0066] - "Porous": refers to mineral compounds containing mesopores, micropores and / or macropores. Porous materials typically have pore sizes greater than 0 nm to 1 μm, for example, 2 nm to 1 μm.

[0067] - "Silicate binder": refers to a hydraulic material containing at least two-thirds by mass of calcium silicate, with (3CaO·SiO2 and 2CaO·SiO2) as the main component, including compounds containing additional aluminum- and / or iron-containing clinker phases (e.g., tricalcium aluminate and tetracalcium aluminoferrite). The term "silicate binder" includes all silicate binder compositions well known to those skilled in the art, such as those defined by European standard EN 197 and international standard ASTM C150.

[0068] According to ASTM C125, "pozzolanic material" refers to natural or artificial siliceous or siliceous and aluminous materials that have little or no cementing value on their own, but react chemically with calcium hydroxide in a fine form at room temperature in the presence of water to form compounds with cementing properties. Artificial pozzolanic materials may contain or consist of, for example, industrial byproducts such as fly ash, silica powder from silicon smelting, highly reactive metakaolin, slag, silica-rich combustion organic residues such as rice husk ash, calcined clay, or any mixture thereof. Natural pozzolanic materials may contain or consist of, for example, volcanic ash, pumice, zeolite, diatomaceous earth, or any mixture thereof. According to one embodiment, at least one pozzolanic material is selected from fly ash, silica powder, metakaolin, slag, and rice husk ash.

[0069] - "Radiation-blocking agent" or "X-ray-blocking agent": refers to a substance added to a material to make it opaque, especially to make it visible under X-ray imaging.

[0070] - "Enhancing properties": refers to any compound that can improve the physical properties of a material, preferably its mechanical properties, such as compressive strength.

[0071] - "Silicon powder": refers to the amorphous (non-crystalline) polycrystalline form of silicon dioxide. Silicon powder is an ultrafine powder collected as a byproduct of silicon and ferrosilicon alloy production, composed of spherical particles with an average particle size of 150 nm. Silicon powder is also known as microsilicon, with CAS number 69012-64-2 and EINECS number 273-761-1.

[0072] - "Water-reducing agent": refers to a substance that can improve the rheological properties of a composition. In particular, "water-reducing agent" can be a plasticizer or a fluidizing agent.

[0073] Furthermore, in this invention, when referring to a range, the following expressions have the following meanings: "X to Y" means that X and Y are included in the range; "greater than X to Y" means that X is not included in the range but Y is included in the range; "less than X" means that the range includes X or a value less than X.

[0074] Detailed description

[0075] hydraulic adhesives

[0076] This invention relates to hydraulic binders, particularly calcium silicate-based hydraulic powder binders. The hydraulic binders of this invention are capable of forming hardened composite materials upon hydration. Due to the composition of the hydraulic binders of this invention, the resulting hardened composite materials exhibit improved properties compared to control compositions, particularly improved mechanical properties, especially in terms of compressive strength and lower porosity.

[0077] The hydraulic adhesive of the present invention comprises:

[0078] - Calcium silicate particles, preferably selected from tricalcium silicate, dicalcium silicate, silicate binders, mineral trioxide aggregates (MTA), and any combination thereof, more preferably tricalcium silicate; and

[0079] - Calcium carbonate granules.

[0080] The hydraulic adhesive of the present invention is anhydrous.

[0081] Calcium silicate granules

[0082] Therefore, the hydraulic binder of the present invention comprises calcium silicate particles.

[0083] In one embodiment, the calcium silicate particles are selected from tricalcium silicate (C3S), dicalcium silicate (C2S), and any combination thereof; preferably, the calcium silicate particles are tricalcium silicate particles. In another embodiment, the calcium silicate particles are in a silicate binder and / or mineral trioxide aggregate (MTA).

[0084] According to one embodiment, the hydraulic binder comprises calcium silicate particles in an amount of 10% to 98% by weight, preferably 15% to 85% by weight, preferably 20% to 85% by weight, and more preferably 50% to 81% by weight of the total weight of the binder.

[0085] According to one embodiment, 50% by volume of the total volume of calcium silicate particles present in the binder of the present invention has a size of 1 μm to 10 μm; preferably a size of 1 μm to 8 μm.

[0086] According to one embodiment, the calcium silicate particles in the hydraulic binder of the present invention have a d 10 The particle size is greater than 0 μm to 2 μm, preferably 0.1 μm to 2 μm. According to one embodiment, the calcium silicate particles in the binder have a d... 10 The particle size is 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, or 1 μm. According to one embodiment, d as defined above... 10 The particle size range was determined by laser diffraction.

[0087] According to one embodiment, the calcium silicate particles in the hydraulic binder of the present invention have a d 50 The particle size is greater than 0 μm to 10 μm, preferably 1 μm to 8 μm; more preferably 3 μm to 8 μm or 0.5 μm to 3 μm. According to one embodiment, the calcium silicate particles in the binder have a d... 50 The particle size is 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, or 10μm. According to one embodiment, d as defined above... 50 The particle size range was determined by laser diffraction.

[0088] According to one embodiment, the calcium silicate particles in the hydraulic binder of the present invention have a d 90 The particle size is greater than 0 μm to 20 μm, preferably 1 μm to 8 μm; more preferably 1 μm to 7 μm. According to one embodiment, the calcium silicate particles in the binder have a d... 90The particle size is 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm. According to one embodiment, the d in the mixture as defined above... 50 The particle size range was determined by laser diffraction.

[0089] Calcium carbonate granules

[0090] The hydraulic binder of the present invention further comprises calcium carbonate particles.

[0091] According to one embodiment, the hydraulic binder comprises calcium carbonate particles in an amount of 0.5% to 85% by weight, preferably 5% to 50% by weight, and preferably 5% to 20% by weight of the total weight of the binder.

[0092] According to one embodiment, the hydraulic binder comprises calcium carbonate particles in an amount of 0.5% to 85% by weight, preferably 5% to 50% by weight, and preferably 5% to 20% by weight of the total weight of the binder, wherein the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0093] The total volume of calcium carbonate particles is 10% by volume, with a size of less than 0.59 μm, preferably less than 0.55 μm;

[0094] According to one embodiment, the hydraulic binder comprises calcium carbonate particles in an amount of 0.5% to 85% by weight, preferably 5% to 50% by weight, and preferably 5% to 20% by weight of the total weight of the binder, wherein the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0095] Ten percent of the total volume of calcium carbonate particles have a size of less than 0.55 μm.

[0096] According to one embodiment, the hydraulic binder comprises calcium carbonate particles in an amount of 0.5% to 85% by weight, preferably 5% to 50% by weight, and preferably 5% to 20% by weight of the total weight of the binder, wherein the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0097] 50% by volume of the total calcium carbonate particles have a size of less than 2.5 μm, preferably less than 2.35 μm, and more preferably less than 1.5 μm.

[0098] According to one embodiment, the hydraulic binder comprises calcium carbonate particles in an amount of 0.5% to 85% by weight, preferably 5% to 50% by weight, and preferably 5% to 20% by weight of the total weight of the binder, wherein the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0099] 50% by volume of the total calcium carbonate particles have a size of less than 1.5 μm;

[0100] According to one embodiment, the hydraulic binder comprises calcium carbonate particles in an amount of 0.5% to 85% by weight, preferably 5% to 50% by weight, and preferably 5% to 20% by weight of the total weight of the binder, wherein the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0101] 10% by volume of the total calcium carbonate particles have a size of less than 0.59 μm, preferably less than 0.55 μm; and / or

[0102] 50% by volume of the total calcium carbonate particles have a size of less than 2.5 μm, preferably less than 2.35 μm, and more preferably less than 1.5 μm.

[0103] According to one embodiment, the hydraulic binder comprises calcium carbonate particles in an amount of 0.5% to 85% by weight, preferably 5% to 50% by weight, and preferably 5% to 20% by weight of the total weight of the binder, wherein the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0104] 10% by volume of the total calcium carbonate particles have a size of less than 0.55 μm; and / or

[0105] 50% by volume of the total calcium carbonate particles have a size of less than 1.5 μm;

[0106] According to one embodiment, the hydraulic binder comprises calcium carbonate particles in an amount of 0.5% to 85% by weight, preferably 5% to 50% by weight, and preferably 5% to 20% by weight of the total weight of the binder, wherein the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0107] The calcium carbonate particles have a size of 2.5 μm to 20 μm, preferably 2.35 μm to 20 μm, preferably 1.5 μm to 20 μm, and preferably 1.5 μm to 5.5 μm, accounting for 40% of the total volume.

[0108] According to one embodiment, the hydraulic binder comprises calcium carbonate particles in an amount of 0.5% to 85% by weight, preferably 5% to 50% by weight, and preferably 5% to 20% by weight of the total weight of the binder, wherein the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0109] 40% by volume of the total calcium carbonate particles had a size ranging from 1.5 μm to 5.5 μm.

[0110] According to one embodiment, the hydraulic binder comprises calcium carbonate particles in an amount of 0.5% to 85% by weight, preferably 5% to 50% by weight, and preferably 5% to 20% by weight of the total weight of the binder, wherein the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0111] 10% by volume of the total calcium carbonate particles have a size of less than 0.59 μm, preferably less than 0.55 μm; and / or

[0112] The calcium carbonate particles have a size of 2.5 μm to 20 μm, preferably 2.35 μm to 20 μm, preferably 1.5 μm to 20 μm, and preferably 1.5 μm to 5.5 μm, accounting for 40% of the total volume.

[0113] According to one embodiment, the hydraulic binder comprises calcium carbonate particles in an amount of 0.5% to 85% by weight, preferably 5% to 50% by weight, and preferably 5% to 20% by weight of the total weight of the binder, wherein the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0114] 10% by volume of the total calcium carbonate particles have a size of less than 0.55 μm; and / or

[0115] 40% by volume of the total calcium carbonate particles had a size ranging from 1.5 μm to 5.5 μm.

[0116] According to one embodiment, the hydraulic binder comprises calcium carbonate particles in an amount of 0.5% to 85% by weight, preferably 5% to 50% by weight, and preferably 5% to 20% by weight of the total weight of the binder, wherein the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0117] 20% or 30% by volume of the total volume of calcium carbonate particles have a size of less than 1.50 μm, preferably less than 1.0 μm;

[0118] According to one embodiment, the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0119] 50% by volume of the total calcium carbonate particles have a size of less than 2.5 μm, preferably less than 2.35 μm, and most preferably less than 1.5 μm; and / or

[0120] The calcium carbonate particles have a size of 2.5 μm to 20 μm, preferably 2.35 μm to 20 μm, preferably 1.5 μm to 20 μm, and preferably 1.5 μm to 5.5 μm, accounting for 40% of the total volume.

[0121] According to one embodiment, the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0122] 50% by volume of the total calcium carbonate particles have a size of less than 1.5 μm; and / or

[0123] 40% by volume of the total calcium carbonate particles had a size ranging from 1.5 μm to 5.5 μm.

[0124] According to one embodiment, the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0125] The total volume of calcium carbonate particles is 10% by volume, with a size of less than 0.59 μm, preferably less than 0.55 μm;

[0126] 50% by volume of the total calcium carbonate particles have a size of less than 2.5 μm, preferably less than 2.35 μm, and most preferably less than 1.5 μm; and / or

[0127] The calcium carbonate particles have a size of 2.5 μm to 20 μm, preferably 2.35 μm to 20 μm, preferably 1.5 μm to 20 μm, and preferably 1.5 μm to 5.5 μm, accounting for 40% of the total volume.

[0128] According to one embodiment, the calcium carbonate particle group in the hydraulic binder of the present invention is as follows:

[0129] Ten percent by volume of the total calcium carbonate particles have a size of less than 0.55 μm;

[0130] 50% by volume of the total calcium carbonate particles have a size of less than 1.5 μm; and / or

[0131] 40% by volume of the total calcium carbonate particles had a size ranging from 1.5 μm to 5.5 μm.

[0132] According to one embodiment, the calcium carbonate particles in the hydraulic binder of the present invention have a d 10 The particle size is from 1 nm to 1000 nm; preferably 1 nm to 900 nm, 1 nm to 800 nm, 1 nm to 700 nm, 1 nm to 600 nm, 1 nm to 500 nm, 1 nm to 400 nm, 1 nm to 300 nm, 1 nm to 200 nm, or 1 nm to 100 nm. According to one embodiment, the d0 of the calcium carbonate particles in the mixture... 10 The particle size is 590nm or 550nm.

[0133] According to one embodiment, the calcium carbonate particles in the hydraulic binder of the present invention have a d 50The particle size is from 1 nm to 5000 nm; preferably 1 nm to 4000 nm, 1 nm to 3000 nm, 1 nm to 2000 nm, 1 nm to 1000 nm, 1 nm to 900 nm, 1 nm to 800 nm, 1 nm to 700 nm, 1 nm to 600 nm, 1 nm to 500 nm, 1 nm to 400 nm, 1 nm to 300 nm, 1 nm to 200 nm, or 1 nm to 100 nm. According to one embodiment, the calcium carbonate particles in the hydraulic binder of the present invention have a d... 50 The particle size is 2500 nm to 3000 nm. According to one embodiment, the d0.05 of the calcium carbonate particles in the mixture... 50 The particle size is 2500nm, 2350nm or 1500nm.

[0134] According to one embodiment, the calcium carbonate particles in the hydraulic binder of the present invention have a d 90 The particle size ranges from 1 nm to 30,000 nm, preferably from 1 nm to 29,000 nm, 1 nm to 27,000 nm, 1 nm to 26,000 nm, 1 nm to 25,000 nm, 1 nm to 24,000 nm, 1 nm to 23,000 nm, 1 nm to 22,000 nm, 1 nm to 21,000 nm, 1 nm to 20,000 nm, 1 nm to 19,000 nm, 1 nm to 18,000 nm, 1 nm to 17,000 nm, 1 nm to 16,000 nm, 1 nm to 15,000 nm, 1 nm to 14,000 nm, 1 nm to 13,000 nm, and 1 nm to 12,000 nm. 0nm, 1nm to 11000nm, 1nm to 10000nm, 1nm to 9000nm, 1nm to 8000nm, 1nm to 7000nm, 1nm to 6000nm, 1nm to 5000nm, 1nm to 4000nm, 1nm to 3000nm, 1nm to 2000nm, 1nm to 1000nm, 1nm to 900nm, 1nm to 800nm, 1nm to 700nm, 1nm to 600nm, 1nm to 500nm, 1nm to 400nm, 1nm to 300nm, 1nm to 200nm, or 1nm to 100nm. According to one embodiment, the d of the calcium carbonate particles in the binder... 50 The particle size is from 25,000 nm to 30,000 nm. According to one embodiment, the d0.05 of the calcium carbonate particles in the mixture... 90 The particle size is 20000nm or 5500nm.

[0135] Other components

[0136] According to one embodiment, the hydraulic binder of the present invention further comprises at least one additive, preferably selected from coagulants, radiation-impermeable agents, pigments, pH stabilizers, fillers, texturers / thickeners, water-reducing agents, surfactants, and mixtures thereof.

[0137] According to one embodiment, the filler is a pozzolanic material; preferably selected from fly ash, silica fume, metakaolin, slag and rice husk ash; more preferably silica fume.

[0138] According to one embodiment, the radiation-impermeable agent is selected from zirconium oxide, bismuth oxide, cerium oxide, barium sulfate, calcium tungstate, titanium dioxide, ytterbium oxide, and mixtures thereof. In a particular embodiment, the radiation-impermeable agent is zirconium oxide.

[0139] According to one embodiment, the coagulant is calcium carbonate, calcium oxide, calcium phosphate, sodium bicarbonate, calcium lactate, calcium chloride, or a mixture thereof. According to one embodiment, the coagulant is calcium carbonate, calcium oxide, or a mixture thereof. According to one embodiment, the coagulant is calcium chloride.

[0140] According to one implementation scheme, the pigment can be an iron oxide.

[0141] According to one implementation plan, the water-reducing agent is selected from glenium, polynaphthalene sulfonate, and modified polycarboxylate.

[0142] According to one embodiment, the texturing agent may be selected, for example, from silica, polyvinylpyrrolidone (also known as polyvinylpyrrolidone), cellulose or its derivatives such as methylcellulose, hydroxypropylcellulose and hydroxyethylcellulose, polymers such as acrylamide / sodium acryloyldimethyltaurate copolymer isohexadecane and hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer, mineral fillers, fumed silica (hydrophilic and / or hydrophobic), xanthan gum or mixtures thereof.

[0143] According to one implementation plan, the pH stabilizer is an inorganic acid or an organic acid.

[0144] According to one implementation scheme, the surfactant is polysorbate.

[0145] According to one embodiment, the hydraulic adhesive of the present invention comprises at least one additive in an amount of 0% to 60% by weight, preferably 2% to 50% by weight, and more preferably 2% to 35% by weight, of the total weight of the adhesive. According to one embodiment, the hydraulic adhesive of the present invention comprises at least one additive in an amount of 0% to 30% by weight, preferably 1% to 25% by weight, and more preferably 1% to 18% by weight, of the total weight of the adhesive.

[0146] According to one embodiment, the hydraulic adhesive of the present invention comprises 0% to 40% by weight, preferably 2% to 35% by weight, 5% to 35% by weight, preferably 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, or 35% by weight of a radiation-impermeable agent. According to one embodiment, the hydraulic adhesive of the present invention comprises 0% to 20% by weight, preferably 1% to 18% by weight, or 2% to 18% by weight of a radiation-impermeable agent in the total weight of the adhesive.

[0147] According to one embodiment, the radiation-impermeable agent exhibits a Mohs hardness greater than 3.5, preferably greater than 5, and even more preferably greater than 8. According to a specific embodiment, the radiation-impermeable agent is zirconium oxide, and the hydraulic binder of the present invention comprises 0% to 40% by weight, preferably 2% to 35% by weight, or 5% to 35% by weight of the radiation-impermeable agent as a percentage of the total weight of the binder.

[0148] Composite materials

[0149] The present invention also relates to composite materials, preferably hardened composite materials. According to one embodiment, the composite material is a hardened cementitious material. According to one embodiment, the composite material is a solid material. According to one embodiment, the composite material of the present invention is produced by hydration of a hydraulic binder. According to one embodiment, the composite material of the present invention is obtained by hydration of a hydraulic binder comprising a calcium silicate compound; said calcium silicate compound is preferably selected from tricalcium silicate, dicalcium silicate, silicate binders, mineral trioxide aggregates (MTA), and any combination thereof; more preferably, the composite material of the present invention is produced by hydration of a hydraulic binder comprising tricalcium silicate. According to one embodiment, the composite material of the present invention is produced by hydration of a hydraulic binder comprising a calcium silicate compound in particulate form as defined above.

[0150] According to one embodiment, the composite material of the present invention is produced by hydration of the hydraulic binder according to the present invention.

[0151] According to one embodiment, the composite material of the present invention is produced by hydration of a hydraulic binder comprising or comprising a calcium silicate compound, calcium carbonate, and a pozzolanic material, wherein the pozzolanic material is preferably selected from fly ash, silica fume, metakaolin, slag, and rice husk ash, and more preferably silica fume.

[0152] According to one embodiment, the hydration of a hydraulic binder yields a hardened material. According to one embodiment, the composite material of the present invention is a hardened composite material, preferably obtained by the hydration of a hydraulic binder; more preferably obtained by the hydration of a hydraulic binder comprising a calcium silicate compound as defined above.

[0153] According to one embodiment, the (hardened) composite material comprises or is composed of a dispersed phase, preferably a solid dispersed phase, and calcium silicate particles dispersed in the dispersed phase. According to one embodiment, the (hardened) composite material comprises or is composed of a solid dispersed phase and insoluble calcium silicate particles dispersed in the solid dispersed phase. According to one embodiment, the (hardened) composite material comprises or is composed of a solid dispersed phase and non-hydrated calcium silicate particles dispersed in the solid dispersed phase. In this invention, the term "non-hydrated calcium silicate particles" means that the calcium silicate particles do not react with water or moisture.

[0154] According to one embodiment, the (hardened) composite material further comprises at least one additive, preferably selected from accelerators, radiation-impermeable agents, pigments, pH stabilizers, fillers, texture agents / thickeners, water-reducing agents, surfactants, and mixtures thereof.

[0155] According to one embodiment, the filler is a pozzolanic material; preferably selected from fly ash, silica fume, metakaolin, slag, and rice husk ash; more preferably silica fume. According to one embodiment, the radiation-impermeable agent is selected from zirconium oxide, bismuth oxide, cerium oxide, barium sulfate, calcium tungstate, titanium dioxide, ytterbium oxide, and mixtures thereof. In a specific embodiment, the radiation-impermeable agent is zirconium oxide. According to one embodiment, the coagulant is calcium carbonate, calcium oxide, calcium phosphate, sodium bicarbonate, calcium lactate, calcium chloride, or mixtures thereof. According to one embodiment, the coagulant is calcium carbonate, calcium oxide, or mixtures thereof. According to one embodiment, the coagulant is calcium chloride. According to one embodiment, the pigment can be an iron oxide. According to one embodiment, the water-reducing agent is selected from glenium, polynaphthalene sulfonate, and modified polycarboxylate. According to one embodiment, the texturer may be selected, for example, from silica, povidone (also known as polyvinylpyrrolidone), cellulose or its derivatives such as methylcellulose, hydroxypropylcellulose and hydroxyethylcellulose, polymers such as acrylamide / sodium acryloyldimethyl taurate copolymer isohexadecane and hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer, mineral fillers, fumed silica (hydrophilic and / or hydrophobic), xanthan gum or mixtures thereof. According to one embodiment, the pH stabilizer is an inorganic or organic acid. According to one embodiment, the surfactant is polysorbate.

[0156] According to one embodiment, the (cured) composite material comprises at least one additive in an amount of 0% to 60% by weight, preferably 2% to 50% by weight, and more preferably 2% to 35% by weight of the total weight of the composite material. According to one embodiment, the (cured) composite material comprises at least one additive in an amount of 0% to 30% by weight, preferably 1% to 25% by weight, and more preferably 1% to 18% by weight of the total weight of the composite material.

[0157] According to one embodiment, the (hardened) composite material comprises 0% to 40% by weight, preferably 2% to 35% by weight, 5% to 35% by weight, preferably 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, or 35% by weight of a radiation-impermeable agent. According to one embodiment, the (hardened) composite material contains a radiation-impermeable agent comprising 0% to 20% by weight, preferably 1% to 18% by weight, or 2% to 18% by weight of the total weight of the (hardened) composite material.

[0158] Dispersed phase

[0159] According to one embodiment, the dispersed phase is a solid dispersed phase. According to one embodiment, the dispersed phase, preferably a solid dispersed phase, comprises or constitutes a hydrated product of at least one calcium silicate compound; the calcium silicate compound is preferably selected from tricalcium silicate, dicalcium silicate, silicate binders, mineral trioxide aggregates (MTA), and any combination thereof; more preferably, the solid dispersed phase comprises or constitutes a hydrated product of at least one hydraulic binder comprising tricalcium silicate.

[0160] According to one embodiment, the product of hydration of a calcium silicate compound can be hydrated calcium silicate (CSH), calcium oxide (CaO), and / or calcium hydroxide (Ca(OH)2). According to one embodiment, the solid dispersed phase comprises or constitutes the product of hydration of at least one calcium silicate compound selected from calcium silicate hydrate (CSH), calcium oxide (CaO), calcium hydroxide (Ca(OH)2), and mixtures thereof.

[0161] According to one implementation scheme, hydrated calcium silicate (CSH) is produced by the hydration of tricalcium silicate (C3S) and / or dicalcium silicate (C2S).

[0162] According to one embodiment, the solid dispersion phase comprises or consists of at least one hydrated calcium silicate (CSH); preferably, the hydrated calcium silicate of formula (I):

[0163] mCaO.nSiO2.pH2O

[0164] Where n and m are independently 1 to 3 and p is 3 to 6; preferably m equals 3, n equals 2 and p equals 3.

[0165] According to one embodiment, the solid dispersion phase comprises or is composed of dense hydrated calcium silicate (d-CSH) as defined above.

[0166] According to one embodiment, the solid dispersion phase comprises or is composed of porous hydrated calcium silicate (p-CSH) as defined above.

[0167] According to one embodiment, the solid dispersion phase comprises pores with a pore size of 0 nm to 1 μm, preferably 2 nm to 1 μm, more preferably 2 nm to 100 nm, more preferably 2 nm to 50 nm, more preferably 2 nm to 20 nm, and particularly 8 nm to 15 nm.

[0168] According to one embodiment, the dispersed phase further comprises pozzolanic material; the pozzolanic material is preferably selected from fly ash, silica fume, metakaolin, slag and rice husk ash; silica fume is more preferred.

[0169] Dispersed calcium silicate particles

[0170] According to one embodiment, the d of calcium silicate particles in the composite material 10 The particle size is greater than 0 μm to 2 μm, preferably 0.1 μm to 2 μm. According to one embodiment, the calcium silicate particles in the composite material have a d... 10 The particle size is 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, or 1 μm. According to one embodiment, the dm of the non-hydrated calcium silicate particles in the composite material... 10 The particle size is greater than 0 μm to 2 μm, preferably 0.1 μm to 2 μm. According to one embodiment, the dm of the non-hydrated calcium silicate particles in the composite material... 10 The particle size is 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, or 1 μm. According to one embodiment, the d10 particle size range defined above is determined by laser diffraction.

[0171] According to one embodiment, the d of calcium silicate particles in the composite material 50The particle size is greater than 0 μm to 10 μm, preferably 1 μm to 8 μm; more preferably 3 μm to 8 μm or 0.5 μm to 3 μm. According to one embodiment, the calcium silicate particles in the composite material have a d... 50 The particle size is 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm. According to one embodiment, the di of the non-hydrated calcium silicate particles in the composite material... 50 The particle size is greater than 0 μm to 10 μm, preferably 1 μm to 8 μm; more preferably 3 μm to 8 μm or 0.5 μm to 3 μm. According to one embodiment, the dm of the non-hydrated calcium silicate particles in the composite material... 50 The particle size is 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, or 10μm. According to one embodiment, d as defined above... 50 The particle size range was determined by laser diffraction.

[0172] According to one embodiment, the d of calcium silicate particles in the composite material 90 The particle size is greater than 0 μm to 20 μm, preferably 1 μm to 10 μm; more preferably 1 μm to 7 μm. According to one embodiment, the calcium silicate particles in the composite material have a d... 90 The particle size is 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm. According to one embodiment, the di of the non-hydrated calcium silicate particles in the composite material... 90 The particle size is greater than 0 μm to 20 μm, preferably 1 μm to 10 μm; more preferably 1 μm to 7 μm. According to one embodiment, the di of the non-hydrated calcium silicate particles in the composite material... 90 The particle size is 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, 10μm, 11μm, 12μm, 13μm, 14μm, 15μm, 16μm, 17μm, 18μm, 19μm, or 20μm. According to one embodiment, d as defined above... 50 The particle size range was determined by laser diffraction.

[0173] According to one embodiment, the amount of calcium silicate particles in the composite material is 5% to 65% by weight of the total weight of the (hardened) composite material, preferably 8% to 60% by weight, more preferably 10% to 35% by weight. According to one embodiment, the amount of non-hydrated calcium silicate particles is 5% to 65% by weight of the total weight of the (hardened) composite material, preferably 8% to 60% by weight, more preferably 10% to 35% by weight.

[0174] According to one embodiment, the amount of calcium silicate particles in the composite material is 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, or 35 wt% of the total weight of the (hardened) composite material. According to one embodiment, the amount of non-hydrated calcium silicate in the composite material is 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, or 35 wt% of the total weight of the (hardened) composite material.

[0175] Intergranular region

[0176] According to one embodiment, the (hardened) composite material includes one or more intergranular regions, preferably located between and / or around the particles of the calcium silicate compound as defined above. According to one embodiment, the (hardened) composite material includes one or more intergranular regions located between and / or around non-hydrated calcium silicate particles dispersed in the dispersed phase as defined above.

[0177] According to one embodiment, one or more calcium silicate particles as defined above are partially or wholly embedded in the intergranular region. According to one embodiment, one or more non-hydrated calcium silicate particles as defined above are partially or wholly embedded in the intergranular region.

[0178] According to one embodiment, the intergranular region comprises or is composed of calcium carbonate (CaCO3), preferably in particulate and / or aggregate form. According to one embodiment, the intergranular region comprises or is composed of insoluble calcium carbonate (CaCO3), preferably in particulate and / or aggregate form.

[0179] According to one embodiment, the intergranular region further comprises at least one product of the hydration of the calcium silicate compound as defined above; preferably at least one hydration product of a calcium silicate compound selected from tricalcium silicate, dicalcium silicate, and mixtures thereof; more preferably at least one hydration product of tricalcium silicate. According to one embodiment, the intergranular region further comprises one or more hydrated calcium silicate (CSH).

[0180] According to one embodiment, the intergranular region comprises or is composed of at least one hydrated calcium carbonate (CSH) and calcium carbonate (CaCO3), preferably in particulate and / or aggregate form. According to another embodiment, the intergranular region comprises or is composed of at least one hydrated calcium carbonate (CSH) and insoluble calcium carbonate (CaCO3), preferably in particulate and / or aggregate form.

[0181] According to one embodiment, the hydrated calcium silicate (CSH) in the intergranular region is the porous hydrated calcium silicate (p-CSH) as defined above. According to one embodiment, the hydrated calcium silicate (CSH) in the intergranular region is the dense hydrated calcium silicate (d-CSH) as defined above. According to one embodiment, the intergranular region comprises or is composed of porous hydrated calcium silicate (p-CSH) and calcium carbonate (CaCO3). According to one embodiment, the intergranular region comprises or is composed of dense hydrated calcium silicate (d-CSH) and calcium carbonate (CaCO3).

[0182] According to one embodiment, the intergranular region is porous. According to one embodiment, the intergranular region comprises mesopores, micropores, and / or macropores. According to one embodiment, the pore size is determined by mercury porosimetry (MIP). Alternatively, the pore size can be determined by transmission electron microscopy (TEM).

[0183] The porosity of the intergranular region can vary over a wide range. In some embodiments, the porosity of the intergranular region is quite low. This very low porosity in the intergranular region contributes to enhanced mechanical properties of the composite material.

[0184] According to one embodiment, the d of the (insoluble) calcium carbonate particles in the composite material of the present invention 10 The particle size is from 1 nm to 500 nm; preferably 1 nm to 400 nm, 1 nm to 300 nm, 1 nm to 200 nm, 1 nm to 100 nm, 1 nm to 90 nm, 1 nm to 80 nm, 1 nm to 70 nm, 1 nm to 60 nm, or 1 nm to 50 nm. According to one embodiment, the d of (insoluble) calcium carbonate particles... 10 The particle size is 400 nm to 500 nm. According to one embodiment, the d0.05 of the (insoluble) calcium carbonate particles... 10 The particle size is 440nm.

[0185] According to one embodiment, the d of the (insoluble) calcium carbonate particles in the composite material of the present invention 50 The particle size is from 1 nm to 1500 nm; preferably 1 nm to 1400 nm, 1 nm to 1300 nm, 1 nm to 1200 nm, 1 nm to 1100 nm, 1 nm to 1000 nm, 1 nm to 900 nm, 1 nm to 800 nm, 1 nm to 700 nm, 1 nm to 600 nm, 1 nm to 500 nm, 1 nm to 400 nm, 1 nm to 300 nm, 1 nm to 200 nm, 1 nm to 100 nm, 1 nm to 50 nm, or 1 nm to 10 nm. According to one embodiment, the d of (insoluble) calcium carbonate particles... 50 The particle size is 1000 nm to 1200 nm. According to one embodiment, the d0.05 of the (insoluble) calcium carbonate particles... 50 The particle size is 1100nm.

[0186] According to one embodiment, the d of the (insoluble) calcium carbonate particles in the composite material of the present invention 90 The particle size is from 1 nm to 5000 nm; preferably 1 nm to 4000 nm, 1 nm to 3000 nm, 1 nm to 2000 nm, 1 nm to 1000 nm, 1 nm to 900 nm, 1 nm to 800 nm, 1 nm to 700 nm, 1 nm to 600 nm, 1 nm to 500 nm, 1 nm to 400 nm, 1 nm to 300 nm, 1 nm to 200 nm, 1 nm to 100 nm, 1 nm to 50 nm, or 1 nm to 10 nm. According to one embodiment, the d of (insoluble) calcium carbonate particles... 90 The particle size is 3000 nm to 3600 nm. According to one embodiment, the d0.05 of the (insoluble) calcium carbonate particles... 90 The particle size is 3550nm.

[0187] According to one embodiment, the size distribution of the (insoluble) calcium carbonate particles in the composite material of the present invention is as follows:

[0188] At least 10% by volume of the total calcium carbonate particles have a size of less than 0.59 μm, preferably less than 0.55 μm; and / or

[0189] At least 50% by volume of the total volume of calcium carbonate particles have a size of less than 2.5 μm, preferably less than 2.35 μm, and more preferably less than 1.5 μm.

[0190] According to one embodiment, the size distribution of the (insoluble) calcium carbonate particles in the composite material of the present invention is as follows:

[0191] The total volume of calcium carbonate particles is 10% by volume, with a size of less than 0.59 μm, preferably less than 0.55 μm;

[0192] 50% by volume of the total calcium carbonate particles have a size of less than 2.5 μm, preferably less than 2.35 μm, and more preferably less than 1.5 μm; and

[0193] The calcium carbonate particles have a size of 2.5 μm to 20 μm, preferably 2.35 μm to 20 μm, preferably 1.5 μm to 20 μm, and preferably 1.5 μm to 5.5 μm, accounting for 40% of the total volume.

[0194] According to one embodiment, the amount of (insoluble) calcium silicate particles in the composite material of the present invention is greater than 0% to 20% by weight of the total weight of the composite material, preferably 1% to 15% by weight, and more preferably 1% to 7% by weight. According to one embodiment, the amount of (insoluble) calcium silicate particles in the composite material of the present invention is 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, or 20% by weight of the total weight of the composite material.

[0195] According to one implementation scheme, the intergranular region further comprises pozzolanic material; the pozzolanic material is preferably selected from fly ash, silica fume, metakaolin, slag and rice husk ash; silica fume is more preferred.

[0196] According to one embodiment, the amount of pozzolanic material in the composite material of the present invention is greater than 0% to 20% by weight of the total weight of the composite material, preferably 1% to 15% by weight, and more preferably 1% to 7% by weight. According to one embodiment, the amount of pozzolanic material in the composite material of the present invention is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20% by weight of the total weight of the composite material.

[0197] Specific composite materials

[0198] According to one embodiment, the (hardened) composite material comprises or consists of:

[0199] - A dispersed phase comprising or constituting hydrated calcium silicate (CSH), preferably a solid dispersed phase;

[0200] - Calcium silicate particles, preferably tricalcium silicate particles, dispersed in the dispersed phase; and

[0201] - Contains or constitutes one or more intergranular regions that are insoluble calcium carbonate particles;

[0202] d of insoluble calcium carbonate particles 50 The particle size is from 1 nm to 1500 nm, preferably from 1 nm to 1000 nm.

[0203] According to one embodiment, the (hardened) composite material comprises or consists of:

[0204] - A dispersed phase comprising or constituting hydrated calcium silicate (CSH), preferably a solid dispersed phase;

[0205] - Calcium silicate particles, preferably tricalcium silicate particles, dispersed in a solid dispersion phase; and

[0206] - One or more porous intergranular regions located between calcium silicate particles; the porous intergranular regions contain insoluble calcium carbonate particles having a d0 of 1 nm to 1500 nm, preferably 1 nm to 1000 nm. 50 granularity.

[0207] According to one embodiment, the (hardened) composite material comprises or consists of:

[0208] - A dispersed phase comprising or constituting hydrated calcium silicate (CSH), preferably a solid dispersed phase;

[0209] - Calcium silicate particles, preferably tricalcium silicate particles, dispersed in the dispersed phase; and

[0210] - Contains or consists of one or more intergranular regions comprising at least one pozzolanic material and insoluble calcium carbonate particles;

[0211] d of insoluble calcium carbonate particles 50 The particle size is from 1 nm to 1500 nm, preferably from 1 nm to 1000 nm.

[0212] According to one embodiment, the (hardened) composite material comprises or consists of:

[0213] - A dispersed phase comprising or constituting hydrated calcium silicate (CSH), preferably a solid dispersed phase;

[0214] -Calcium silicate particles, preferably tricalcium silicate particles, are dispersed in the dispersed phase relative to 5% to 65% by weight of the total weight of the composite material; and

[0215] - Contains or constitutes one or more intergranular regions that are insoluble calcium carbonate particles;

[0216] d of insoluble calcium carbonate particles 50 The particle size is from 1 nm to 1500 nm, preferably from 1 nm to 1000 nm;

[0217] According to one embodiment, the amount of insoluble calcium carbonate particles is 1% to 20% by weight relative to the total weight of the composite material.

[0218] According to one embodiment, the (hardened) composite material comprises or consists of:

[0219] - A dispersed phase comprising or constituting hydrated calcium silicate (CSH), preferably a solid dispersed phase;

[0220] -Calcium silicate particles, preferably tricalcium silicate particles, are dispersed in the dispersed phase relative to 5% to 65% by weight of the total weight of the composite material; and

[0221] - Contains or consists of one or more intergranular regions comprising at least one pozzolanic material and insoluble calcium carbonate particles;

[0222] d of insoluble calcium carbonate particles 50 The particle size is from 1 nm to 1500 nm, preferably from 1 nm to 1000 nm;

[0223] Choose any location

[0224] The amount of at least one pozzolanic material is 1% to 15% by weight relative to the total weight of the composite material; and the amount of insoluble calcium carbonate particles is 1% to 5% by weight relative to the total weight of the composite material.

[0225] According to one embodiment, the (hardened) composite material comprises or consists of:

[0226] - A solid dispersion phase comprising or consisting of hydrated calcium silicate (CSH);

[0227] - 5% to 65% by weight of non-hydrated calcium silicate particles dispersed in the dispersed phase relative to the total weight of the composite material; and

[0228] - Contains or constitutes one or more intergranular regions that are insoluble calcium carbonate particles;

[0229] d of insoluble calcium carbonate particles 50 The particle size is from 1 nm to 1500 nm, preferably from 1 nm to 1000 nm;

[0230] Optionally, the amount of insoluble calcium carbonate particles is from 1% to 20% by weight relative to the total weight of the composite material. According to one embodiment, the (hardened) composite material comprises or consists of:

[0231] - 5% to 65% by weight, preferably 8% to 60% by weight, more preferably 10% to 35% by weight of calcium silicate particles relative to the total weight of the (hardened) composite material, wherein the calcium silicate particles are preferably selected from tricalcium silicate, dicalcium silicate, silicate binders, mineral trioxide aggregates (MTA) and / or mixtures thereof.

[0232] - 1% to 20% by weight, preferably 2% to 15% by weight, of calcium silicate relative to the total weight of the (hardened) composite material, preferably insoluble calcium silicate particles; and

[0233] - greater than 0% to 50% by weight, preferably 1% to 40% by weight, of mCaO.nSiO2.pH2O(CSH) relative to the total weight of the (hardened) composite material, wherein m and n are independently 1 to 3 and p is 3 to 6.

[0234] According to one embodiment, the (hardened) composite material comprises or consists of:

[0235] - A dispersed phase comprising or consisting of mCaO.nSiO2.pH2O(CSH) of greater than 0% to 50% by weight, preferably 1% to 40% by weight, relative to the total weight of the (hardened) composite material, wherein m and n are independently 1 to 3 and p is 3 to 6.

[0236] - 5% to 65% by weight, preferably 8% to 60% by weight, and more preferably 10% to 35% by weight of calcium silicate particles relative to the total weight of the (hardened) composite material; the calcium silicate particles are preferably selected from tricalcium silicate, dicalcium silicate, silicate binders, mineral trioxide aggregates (MTA), and / or mixtures thereof; the calcium silicate particles are dispersed in a dispersed phase; and

[0237] - 1% to 20% by weight, preferably 2% to 15% by weight, of calcium carbonate particles relative to the total weight of the (hardened) composite material, preferably insoluble calcium carbonate particles; the insoluble calcium carbonate particles are located in one or more intergranular regions between or around the calcium silicate particles.

[0238] According to one embodiment, the compressive strength of the (hardened) composite material, measured 24 hours after mixing the powder phase (or hydraulic binder) and the aqueous phase, is greater than 0 MPa to 400 MPa, preferably 10 MPa to 300 MPa, and more preferably 50 MPa to 250 MPa.

[0239] Method for manufacturing hydraulic adhesives

[0240] The present invention also relates to a method for manufacturing a hydraulic adhesive according to the invention.

[0241] The first method

[0242] In particular, the present invention provides a first method for manufacturing a hydraulic binder according to the invention, comprising mixing powders of calcium silicate and calcium carbonate, both having a target particle size distribution.

[0243] In one embodiment, a first method for manufacturing the hydraulic adhesive according to the invention comprises mixing:

[0244] - Calcium silicate particles comprising 15% to 98% by weight of the total binder, wherein 50% by volume of the total volume of the calcium silicate particles has a size of 1 μm to 10 μm, preferably 1 μm to 8 μm; and

[0245] - Calcium carbonate particles comprising 0.5% to 85% by weight of the total binder, wherein:

[0246] Ten percent by volume of the total calcium carbonate particles have a size of less than 0.59 μm;

[0247] 50% by volume of the total calcium carbonate particles have a size of less than 2.5 μm; and

[0248] 40% by volume of the total calcium carbonate particles had a size ranging from 2.5 μm to 20 μm.

[0249] Mixing can be performed by any method known to those skilled in the art. In particular, gentle mixing can be used in devices that provide three-dimensional motion, such as three-dimensional mixers.

[0250] The second method

[0251] This invention provides a second method for manufacturing the hydraulic binder according to the invention, comprising vibratory mixing of powders of calcium silicate and calcium carbonate having a particle size distribution different from the final target particle size distribution. Specifically, in this method, larger-sized calcium carbonate particles are used, and the target particle size distribution can be achieved through vibratory mixing.

[0252] In one embodiment, a second method for manufacturing the hydraulic adhesive according to the invention comprises a mixing step of at least one powder phase, and a vibration step performed simultaneously and / or sequentially with the mixing step, thereby obtaining the hydraulic adhesive composition according to the invention, wherein the powder phase comprises:

[0253] - Calcium silicate particles comprising 15% to 98% by weight of the total binder, wherein 50% by volume of the total volume of the calcium silicate particles has a size of 1 μm to 10 μm, preferably 1 μm to 8 μm; and

[0254] -0.5% by weight to 85% by weight of calcium carbonate particles, of which

[0255] 10% by volume of the total calcium carbonate particles have a size of less than 1 μm;

[0256] 50% by volume of the total calcium carbonate particles have a size of less than 5 μm; and

[0257] 40% by volume of the total calcium carbonate particles have a size of 5 μm to 30 μm.

[0258] In this second method, the particle size of the calcium silicate and calcium carbonate powders after the mixing step can also be limited as follows.

[0259] According to one embodiment, the powder in the mixing step further includes a radiation-impermeable agent with a Mohs hardness greater than 3.5, preferably greater than 5, and even more preferably greater than 8. According to a specific embodiment, the radiation-impermeable agent is zirconium oxide, and the powder phase in the mixing step comprises 0% to 40% by weight, preferably 2% to 35% by weight, or 5% to 35% by weight relative to the total weight of the binder and the powder phase composition.

[0260] Calcium Silicate Particle Size Determination Method

[0261] According to one embodiment, the d of the calcium silicate particles in the mixture 10 The particle size is greater than 0 μm to 2 μm, preferably 0.1 μm to 2 μm. According to one embodiment, the calcium silicate particles in the mixture have a d... 10 The particle size is 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, or 1 μm. According to one embodiment, the d of the non-hydrated calcium silicate particles in the mixture... 10 The particle size is greater than 0 μm to 2 μm, preferably 0.1 μm to 2 μm. According to one embodiment, the dm of the non-hydrated calcium silicate particles in the mixture... 10 The particle size is 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, or 1 μm. According to one embodiment, d as defined above... 10 The particle size range was determined by laser diffraction.

[0262] According to one embodiment, the d of the calcium silicate particles in the mixture 50 The particle size is greater than 0 μm to 10 μm, preferably 1 μm to 8 μm; more preferably 3 μm to 8 μm or 0.5 μm to 3 μm. According to one embodiment, the calcium silicate particles in the mixture have a d... 50 The particle size is 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm. According to one embodiment, the d of the non-hydrated calcium silicate particles in the mixture...50 The particle size is greater than 0 μm to 10 μm, preferably 1 μm to 8 μm; more preferably 3 μm to 8 μm or 0.5 μm to 3 μm. According to one embodiment, the d of the non-hydrated calcium silicate particles in the mixture... 50 The particle size is 1μm, 2μm, 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, 9μm, or 10μm. According to one embodiment, d as defined above... 50 The particle size range was determined by laser diffraction.

[0263] According to one embodiment, the d of the calcium silicate particles in the mixture 90 The particle size is greater than 0 μm to 20 μm, preferably 1 μm to 10 μm; more preferably 1 μm to 7 μm. According to one embodiment, the calcium silicate particles in the mixture have a d... 90 The particle size is 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm. According to one embodiment, the d of the non-hydrated calcium silicate particles in the mixture... 90 The particle size is greater than 0 μm to 20 μm, preferably 1 μm to 10 μm; more preferably 1 μm to 7 μm. According to one embodiment, the d of the non-hydrated calcium silicate particles in the mixture... 90 The particle size is 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm. According to one embodiment, the d in the mixture as defined above... 50 The particle size range was determined by laser diffraction.

[0264] Calcium carbonate particle size determination method

[0265] According to one embodiment, the d of calcium carbonate particles in the mixture 10 The particle size is from 1 nm to 1000 nm; preferably 1 nm to 900 nm, 1 nm to 800 nm, 1 nm to 700 nm, 1 nm to 600 nm, 1 nm to 500 nm, 1 nm to 400 nm, 1 nm to 300 nm, 1 nm to 200 nm, or 1 nm to 100 nm. According to one embodiment, the d0 of the calcium carbonate particles in the mixture... 10 The particle size is 500 nm to 800 nm. According to one embodiment, the d0.05 of the calcium carbonate particles in the mixture... 10 The particle size is 600nm.

[0266] According to one embodiment, the d of calcium carbonate particles in the mixture50 The particle size is from 1 nm to 5000 nm; preferably 1 nm to 4000 nm, 1 nm to 3000 nm, 1 nm to 2000 nm, 1 nm to 1000 nm, 1 nm to 900 nm, 1 nm to 800 nm, 1 nm to 700 nm, 1 nm to 600 nm, 1 nm to 500 nm, 1 nm to 400 nm, 1 nm to 300 nm, 1 nm to 200 nm, or 1 nm to 100 nm. According to one embodiment, the d of the calcium carbonate particles in the mixture... 50 The particle size is 2500 nm to 3000 nm. According to one embodiment, the d0.05 of the calcium carbonate particles in the mixture... 50 The particle size is 2760nm.

[0267] According to one embodiment, the d of calcium carbonate particles in the mixture 90 The particle size ranges from 1 nm to 30,000 nm, preferably from 1 nm to 29,000 nm, 1 nm to 27,000 nm, 1 nm to 26,000 nm, 1 nm to 25,000 nm, 1 nm to 24,000 nm, 1 nm to 23,000 nm, 1 nm to 22,000 nm, 1 nm to 21,000 nm, 1 nm to 20,000 nm, 1 nm to 19,000 nm, 1 nm to 18,000 nm, 1 nm to 17,000 nm, 1 nm to 16,000 nm, 1 nm to 15,000 nm, 1 nm to 14,000 nm, 1 nm to 13,000 nm, and 1 nm to 12,000 nm. 0 nm, 1 nm to 11000 nm, 1 nm to 10000 nm, 1 nm to 9000 nm, 1 nm to 8000 nm, 1 nm to 7000 nm, 1 nm to 6000 nm, 1 nm to 5000 nm, 1 nm to 4000 nm, 1 nm to 3000 nm, 1 nm to 2000 nm, 1 nm to 1000 nm, 1 nm to 900 nm, 1 nm to 800 nm, 1 nm to 700 nm, 1 nm to 600 nm, 1 nm to 500 nm, 1 nm to 400 nm, 1 nm to 300 nm, 1 nm to 200 nm, or 1 nm to 100 nm. According to one embodiment, the d of the calcium carbonate particles in the mixture... 90 The particle size is from 25,000 nm to 30,000 nm. According to one embodiment, the d0.05 of the calcium carbonate particles in the mixture... 90 The particle size is 27400nm.

[0268] Mixing Step - Vibration

[0269] In a second method of manufacturing the hydraulic binder of the present invention, the mixing step is performed by a vibratory mixer. Without wishing to be bound by any theory, the applicant proposes that the vibratory mixing step provides self-grinding of at least a portion of the calcium carbonate particles contained in the powder mixture, resulting in a calcium carbonate particle group having the specific particle size distribution of the hydraulic binder of the present invention.

[0270] According to one embodiment, the mixing step is performed at a vibration frequency of 1 rpm to 10,000 rpm, preferably 1,000 rpm to 6,000 rpm, and more preferably 3,000 rpm to 5,000 rpm. According to another embodiment, the mixing step is performed at a vibration frequency of approximately 1 rpm, 100 rpm, 200 rpm, 300 rpm, 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm, 900 rpm, 1000 rpm, 2000 rpm, 3000 rpm, 4000 rpm, 5000 rpm, 6000 rpm, 7000 rpm, 8000 rpm, 9000 rpm, or 10,000 rpm.

[0271] According to one embodiment, the vibration mixing step is implemented over a vibration time of 1s to 3600s, preferably 1s to 60s, and more preferably 30s. According to another embodiment, the vibration mixing step is implemented over a vibration time of 1s, 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s, 10s, 11s, 12s, 13s, 14s, 15s, 16s, 17s, 18s, 19s, 20s, 21s, 22s, 23s, 24s, 25s, 26s, 27s, 28s, 29s, or 30s.

[0272] In one embodiment, the composite material of the present invention is obtained in a "one-pot" process via a vibrational mixing step in the presence of an aqueous phase, thereby achieving a "two-step" procedure. During the vibrational mixing process, the calcium carbonate and calcium silicate particles undergo self-grinding (a more significant step in the case of calcium carbonate particles), resulting in the desired particle size distribution. Simultaneously, the presence of water enables the formation of the composite material of the present invention. In this embodiment, the aqueous phase can be defined as follows regarding the manufacture of the composite material.

[0273] In one embodiment, the mixing step may include mixing the powder components by gently mixing them in a device that provides three-dimensional motion (e.g., a three-dimensional mixer).

[0274] Methods for manufacturing composite materials

[0275] The present invention also relates to a method for manufacturing (cured) composite materials, comprising a mixing step of at least one powder phase and an aqueous phase. According to one embodiment, the method for manufacturing (cured) composite materials includes a mixing step of at least one powder phase and an aqueous phase, the powder phase comprising or constituting a hydraulic binder, preferably a hydraulic calcium silicate binder. According to one embodiment, the aqueous phase is an aqueous liquid or an aqueous solution.

[0276] According to one embodiment, a method for manufacturing a (hardened) composite material includes at least one step of mixing a powder phase comprising calcium silicate particles and calcium carbonate particles with an aqueous phase. According to one embodiment, a method for manufacturing a (hardened) composite material includes at least one step of mixing a powder phase comprising calcium silicate particles, at least one pozzolanic material, and calcium carbonate particles with an aqueous phase. According to one embodiment, a method for manufacturing a (hardened) composite material includes at least one step of mixing a powder phase comprising calcium silicate particles, at least one pozzolanic material, and calcium carbonate particles with an aqueous phase, wherein the pozzolanic material is selected from fly ash, silica fume, metakaolin, slag, and rice husk ash.

[0277] According to one embodiment, the powder phase is anhydrous. According to one embodiment, the powder phase is a hydraulic binder. According to one embodiment, the powder phase comprises or consists of a calcium silicate compound, preferably a calcium silicate compound in particulate form. According to one embodiment, the calcium silicate compound is selected from tricalcium silicate, dicalcium silicate, silicate binders, and / or mineral trioxide aggregates (MTA). According to one embodiment, the powder phase is an anhydrous calcium silicate binder powder phase.

[0278] The first method

[0279] This invention provides a first method for manufacturing (hardened) composite materials, comprising at least one step of mixing a powder phase containing a hydraulic binder according to the invention with an aqueous phase. In this method, the mixing step can be performed by any means known to those skilled in the art.

[0280] According to one implementation scheme, the aqueous liquid phase includes water, preferably purified water.

[0281] According to one implementation scheme, the aqueous liquid phase is composed of water.

[0282] In another embodiment, the aqueous liquid phase is an aqueous solution.

[0283] According to one embodiment, the aqueous liquid phase comprises 10% to 100% by weight, preferably 20% to 90% by weight, preferably 30% to 90% by weight, and preferably 35% to 85% by weight of water relative to the total weight of the aqueous liquid phase. According to another embodiment, the liquid phase comprises 50% to 90% by weight, preferably 60% to 90% by weight, preferably 60% to 85% by weight, and preferably 65% ​​to 85% by weight of water relative to the total weight of the liquid phase.

[0284] According to one embodiment, the aqueous phase is an aqueous liquid phase and contains at least one additive, wherein the additive is preferably selected from coagulants and water-reducing agents. According to one embodiment, the aqueous liquid phase contains one or more additives selected from coagulants (e.g., calcium chloride), water-reducing agents (e.g., modified polycarboxylates, glenium, polynaphthalene sulfonates, or mixtures thereof), or mixtures thereof.

[0285] According to one embodiment, the aqueous liquid phase contains at least one additive in an amount of 0% to 40% by weight, preferably 10% to 35%, more preferably 15% to 35% relative to the total weight of the liquid phase.

[0286] The second method

[0287] The present invention also provides a second method for manufacturing (hardened) composite materials, comprising the step of mixing a powder mixture of calcium silicate and calcium carbonate particles having a particle size larger than the final target particle size distribution with an aqueous phase by vibration. This corresponds to the “one-pot” method (or “two-step” method) described above for manufacturing the hydraulic binder of the present invention.

[0288] The mixing step via vibration can be carried out under the same conditions as the vibration frequency and vibration time detailed above.

[0289] Without being bound by any theoretical constraints, the specific features of the second method, similar to the case of directly using calcium silicate and calcium carbonate particles of the particle size distribution of interest, also appear to provide the acquisition of porous intergranular regions with relatively low porosity, thereby enhancing the mechanical properties of the composite material.

[0290] In the second method for manufacturing the (hardened) composite material, the aqueous phase can be as described above. The powder phase can comprise calcium silicate, calcium carbonate, and additives as described above in the second method for manufacturing the hydraulic binder of the present invention.

[0291] According to one embodiment, the powder phase comprises calcium silicate particles in an amount of 10% to 100% by weight, preferably 10% to 98% by weight, preferably 15% to 60% by weight, and preferably 20% to 55% by weight of the total weight of the powder phase.

[0292] Other components

[0293] According to one embodiment, the powder phase, aqueous phase, and / or mixture further comprise at least one additive, preferably selected from coagulants, radiation-impermeable agents, pigments, pH stabilizers, fillers, texture agents / thickeners, water-reducing agents, and mixtures thereof. According to one embodiment, the filler is a pozzolanic material; preferably selected from fly ash, silica fume, metakaolin, slag, and rice husk ash; more preferably silica fume.

[0294] According to one embodiment, the radiation-impermeable agent is selected from zirconium oxide, bismuth oxide, cerium oxide, barium sulfate, calcium tungstate, titanium dioxide, ytterbium oxide, and mixtures thereof. In a particular embodiment, the radiation-impermeable agent is zirconium oxide. According to one embodiment, the coagulant is calcium carbonate, calcium oxide, calcium phosphate, sodium bicarbonate, calcium lactate, calcium chloride, or mixtures thereof. According to one embodiment, the coagulant is calcium carbonate, calcium oxide, or mixtures thereof. According to one embodiment, the coagulant is calcium chloride. According to one embodiment, the pigment may be an iron oxide. According to one embodiment, the water-reducing agent is selected from glenium, polynaphthalene sulfonate, and modified polycarboxylate. According to one embodiment, the texturer may be selected, for example, from silica, povidone (also known as polyvinylpyrrolidone), cellulose or its derivatives such as methylcellulose, hydroxypropylcellulose and hydroxyethylcellulose, polymers such as acrylamide / sodium acryloyldimethyl taurate copolymer isohexadecane and hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer, mineral fillers, fumed silica (hydrophilic and / or hydrophobic), xanthan gum, or mixtures thereof. According to one embodiment, the pH stabilizer is an inorganic or organic acid. According to one embodiment, the surfactant is a polysorbate.

[0295] powder phase

[0296] According to one embodiment, based on the total weight of the powder phase, the powder phase comprises or consists of:

[0297] -85% by weight of at least one calcium silicate compound, preferably selected from tricalcium silicate, dicalcium silicate, and mixtures thereof; and

[0298] -15% by weight of calcium carbonate.

[0299] According to one embodiment, based on the total weight of the powder phase, the powder phase comprises or consists of:

[0300] -50% of at least one calcium silicate compound, preferably selected from tricalcium silicate, dicalcium silicate, and mixtures thereof; and

[0301] -50% by weight of calcium carbonate.

[0302] According to one embodiment, the powder phase, aqueous phase, and / or mixture comprises at least one additive in an amount of 0% to 60% by weight, preferably 2% to 50% by weight, and more preferably 2% to 35% by weight of the total weight of the mixture. According to one embodiment, the powder phase, aqueous phase, and / or mixture comprises at least one additive in an amount of 0% to 30% by weight, preferably 1% to 25% by weight, and more preferably 1% to 18% by weight of the total weight of the mixture.

[0303] According to one embodiment, the powder phase, aqueous phase, and / or mixture comprises 0% to 40% by weight, preferably 2% to 35% by weight, 5% to 35% by weight, preferably 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, or 35% by weight of a radiation-impermeable agent. According to one embodiment, the powder phase, aqueous phase and / or mixture contains 0% to 20% by weight, preferably 1% to 18% by weight, or 2% to 18% by weight of a radiation-impermeable agent as a percentage of the total weight of the mixture.

[0304] According to one embodiment, the mass ratio of the powder phase to the aqueous phase is 2 to 4.5. According to another embodiment, the mass ratio of the powder phase to the aqueous phase is 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, or 4.5.

[0305] According to one implementation, based on the total amount of the powder phase, the powder phase comprises:

[0306] - Calcium silicate granules;

[0307] - At least one pozzolanic material, greater than 0% to 15% by weight; preferably selected from fly ash, silica fume, metakaolin, slag, and rice husk ash; more preferably, pozzolanic material containing silica fume; and

[0308] - Calcium carbonate greater than 0% to 15% by weight.

[0309] According to one embodiment, based on the total weight of the mixture, the powder phase comprises:

[0310] - Calcium silicate granules;

[0311] - At least one pozzolanic material, greater than 0% to 15% by weight; preferably selected from fly ash, silica fume, metakaolin, slag, and rice husk ash; more preferably, pozzolanic material containing silica fume; and

[0312] - Calcium carbonate greater than 0% to 15% by weight.

[0313] Uses and methods of treatment

[0314] Another object of the present invention is the use of the composite material as defined above. According to one embodiment, the (hardened) composite material of the present invention is used as a reinforcing material in the field of non-therapeutic adhesives. According to one embodiment, the field of non-therapeutic adhesives is the construction field. According to one embodiment, the composite material of the present invention is used in the medical field, preferably in the dental or orthopedic field, as a restorative and / or filling material.

[0315] According to one embodiment, the composite material of the present invention can also be used in orthopedic surgery, bone repair, craniofacial and / or maxillofacial surgery.

[0316] In one embodiment, the present invention relates to dental crowns for treating objects in need, such as enamel restorations, permanent dentin restorations, restorations of deep or large caries damage, restorations of deep neck or root damage, pulp capping or pulpotomy; and / or methods for treating tooth roots, such as root and furcation perforations, internal / external resorption, apexification, or retrograde surgical filling, including using the compositions and kits of the present invention as described above.

[0317] According to one embodiment, the composite material of the present invention can be used to treat bone and / or dental conditions or diseases in a subject in need. According to one embodiment, the present invention relates to the use of the composite material of the present invention for treating bone and / or dental conditions or diseases in a subject in need. According to one embodiment, the present invention relates to a method of treating bone and / or dental conditions or diseases in a subject in need by using the composite material of the present invention. Example

[0318] The present invention is further illustrated by the following embodiments.

[0319] Example 1 Effect of mixing parameters on particle size of powder phase (hydraulic calcium silicate binder) components

[0320] The applicant has studied the effect of mixing parameters used in the process of manufacturing hardened cementitious materials from hydraulic calcium silicate binders on the final particle size of the binder components.

[0321] Therefore, the applicant studied the following:

[0322] - Particle size determination of powder phase A, which consists of individual calcium silicate particles.

[0323] - Particle size determination of powder phase B, which consists of individual calcium carbonate particles, and

[0324] - Particle size determination of powder phase C, which consists of 15% tricalcium silicate particles and 85% calcium carbonate particles by weight of the total powder phase.

[0325] Then, without any liquid phase, each powder phase was stirred for 30 seconds under vibration at a frequency of 3000 rpm to 3500 rpm, i.e., under the mixing conditions typically used to mix powder phases with aqueous liquid phases.

[0326] Then, the d of each powder phase after mixing was determined by laser diffraction. 10 d 50 and d 90 Granularity, and their initial d 10 d 50 and d 90 Particle size comparison.

[0327] The results are shown in Table 1 below.

[0328]

[0329] *Particle size determination based on the refractoriness index of calcium carbonate.

[0330] Table 1

[0331] The results show that the mixing parameters used in the manufacturing process of composites from hydraulic binders lead to the self-grinding of calcium silicate and calcium carbonate particles when applied only to powder binders. However, compared to calcium silicate particles, calcium carbonate particles exhibit higher d... 10 d 50 and d 90 The particle size is reduced even more.

[0332] Self-grinding was also observed when calcium silicate and calcium carbonate particles were mixed together.

[0333] Example 2 Method for manufacturing the hardened composite material of the present invention

[0334] The applicant then manufactured a hardened cementitious material using a hydraulic calcium silicate binder, which is the powder phase C defined in Example 1.

[0335] To this end, the applicant used a vibratory mixer with a vibration frequency of 3000 rpm to 3500 rpm to mix powder phase C with aqueous liquid phase at a mass ratio of 2 to 4.5 within 30 seconds.

[0336] Surprisingly, even with a small amount (15%) of tricalcium silicate linkers in the powder phase, powder phase C can achieve effective solidification and a short solidification time (approximately 30 minutes).

[0337] The material obtained by microscopic observation is characterized by a composite structure comprising:

[0338] - A solid dispersion of hydrated calcium silicate (CSH);

[0339] - Tricalcium silicate particles dispersed in a solid dispersion phase; and

[0340] - Porous intergranular regions located between and around tricalcium silicate particles; these porous intergranular regions contain insoluble calcium carbonate particles, which, along with the initial d of the calcium carbonate particles introduced into the powder phase... 10 d 50 and d 90 Compared to particle size, insoluble calcium carbonate particles have a lower d... 10 d 50 and d 90 Particle size is reduced.

[0341] Therefore, when the powder phase is mixed with the liquid phase by vibration to produce a hardened binder, the same self-grinding mechanism as demonstrated in Example 1 occurs on the powder.

[0342] Example 3 Manual mixing of ground powders

[0343] Example 3 illustrates the advantageous property that the particle size of the binder can be obtained by mixing the powders, providing a sufficient particle size to obtain the particle size of the hydraulic binder according to the invention.

[0344] Two compositions were prepared by manual mixing according to Table 2.

[0345]

[0346] Table 2

[0347] Of these, 50% are micronized tricalcium silicate particles, expressed as 50% by volume of particles, with a size of less than 8 μm.

[0348] The particle size (in micrometers) of calcium carbonate is:

[0349] - 10% by volume of the particles have a size of less than 0.588 μm;

[0350] - 50% by volume of the particles have a size of less than 2.54 μm; and

[0351] - 40% by volume of the particles have a size ranging from 2.54 μm to 23.96 μm;

[0352] The particle size (nanometers) of calcium carbonate is as follows:

[0353] - 10% by volume of the particles have a size of less than 0.581 μm;

[0354] - 50% by volume of the particles have a size of less than 1.89 μm; and

[0355] - 40% by volume of the particles have a size ranging from 1.89 μm to 8.71 μm;

[0356] According to Table 2, the calcium carbonate mixture in composition D exhibits the following particle sizes:

[0357] - 10% by volume of the particles have a size of less than 0.586 μm;

[0358] - 50% by volume of the particles have a size of less than 2.35 μm; and

[0359] - 40% by volume of the particles have a size ranging from 2.35 μm to 19.34 μm;

[0360] Example 4 Effect of the effect on the porosity of hardened materials obtained by artificially mixing powders

[0361] Hardened materials were obtained by mixing each of the control composition of Example 3 and each of Composition D with 190 μL and 202 μL of aqueous liquid phases containing water, calcium chloride and modified polycarboxylate, respectively.

[0362] The porosity of the obtained material is evaluated according to the following scheme:

[0363] 1. Dry the hardened sample in an oven at 105±5℃ for two hours;

[0364] 2. Then allow the sample to cool and weigh it (dry weight);

[0365] 3. Immerse the sample in a beaker containing 50 mL of distilled water and place it under a decompression bell jar;

[0366] 4. Wipe the surface of the sample and weigh the sample again (wet weight).

[0367] The porosity was then calculated based on the dry weight to wet weight ratio. The results are shown in Table 3 below.

[0368]

[0369] Table 3

[0370] The results show that the particle size of composition D according to the invention leads to a significant reduction in the porosity of the hardened material, which is advantageous for its dental applications.

[0371] Example 5 Evaluation of the compressive strength of hardened adhesives

[0372] Example 5 shows that by mixing fine powders and then further reducing the particle size through vibration, a favorable effect on the particle size of the binder can be obtained, thereby achieving the particle size of the hydraulic binder of the present invention. Two compositions were prepared according to Table 4.

[0373]

[0374] Table 4

[0375] The particle sizes of micronized tricalcium silicate, calcium carbonate (micron), and calcium carbonate (nano) are the same as in Example 3.

[0376] Then, without any liquid phase, the control composition and the powdered compositions of compositions E and F were stirred under vibration at a frequency of 3000 rpm to 3500 rpm for 30 s, i.e. under the mixing conditions usually used to mix the powder phase with the aqueous liquid phase.

[0377] The amount of zirconium oxide is increased in compositions E and F because its abrasive properties do not affect the suitability of compositions E and F in dental applications. In fact, zirconium oxide has a Mohs hardness of 8 to 8.5, while CaCO3 has a hardness of 3. Calcium carbonate (nano) is added according to the same calcium carbonate (micron) / calcium carbonate (nano) ratio as composition D of Example 3. It should be understood that the mixing parameters associated with the abrasive properties of zirconium oxide result in the calcium carbonate particle size according to the invention.

[0378] Example 6 The effect on the mechanical properties of hardened materials obtained by mixing fine powders and then vibrating.

[0379] The mechanical properties of the hardened material obtained from the composition of Example 5 are evaluated as follows.

[0380] Hardened material samples were obtained by mixing the control composition of Example 5 and each of compositions E and F with 173 μl, 137 μl and 140 μl of an aqueous liquid phase containing water, calcium chloride and modified polycarboxylate, respectively.

[0381] The compressive strength of the obtained material was evaluated according to the following scheme:

[0382] The compressive strength was tested on a universal pressure testing machine (Model 2 / M, MTS system, Eden Prairie 1400, Minneapolis, USA), which measures the maximum force that the adhesive can withstand.

[0383] The test involved compressing two metal plates approximately 5 mm high and 4 mm in diameter. The maximum stress (N / s) before the specimens fractured was measured. The compression rate was 0.5 mm / s. The results are shown in Table 5 below.

[0384] Hardened control composition Hardened composition E Hardened composition F Test 1 291.882 270.183 314.65 Test 2 226.956 293.331 296.5 Test 3 278.994 262.054 300.172 Test 4 277.106 276.466 300.719 Test 5 256.235 265.493 297.725 Test 6 307.036 313.466 277.24 Test 7 282.116 224.258 Test 8 318.362 average value 273.0348333 285.183875 287.3234286 Standard deviation 28.17401062 21.38157868 29.89591553

[0385] Table 5

[0386] The results of Example 6 show that the compressive strength of specimens obtained from compositions E and F is significantly increased compared to specimens obtained from the control composition. These results highlight the influence on the mechanical properties of hardened specimens obtained from compositions having a fine calcium carbonate particle distribution according to the invention.

Claims

1. A hydraulic adhesive comprising: - Calcium silicate particles comprising 15% to 98% by weight of the total binder, wherein 50% by volume of the total volume of the calcium silicate particles has a size of 1µm to 10µm; and - Calcium carbonate particles comprising 0.5% to 85% by weight of the total binder, wherein: The total volume percentage of calcium carbonate particles is less than 0.59 µm. 50% by volume of the total calcium carbonate particles have a size of less than 2.5 µm; and 40% by volume of the total calcium carbonate particles have a size ranging from 2.5 µm to 20 µm.

2. The hydraulic binder according to claim 1, wherein: 10% by volume of the total calcium carbonate particles have a size of less than 0.55 µm; 50% by volume of the total calcium carbonate particles have a size of less than 1.5 µm; and 40% by volume of the total calcium carbonate particles have a size ranging from 1.5 µm to 5.5 µm.

3. The hydraulic binder according to claim 1 or 2, wherein the calcium silicate particles are selected from tricalcium silicate (C3S), dicalcium silicate (C2S), and any combination thereof.

4. The hydraulic binder according to claim 1 or 2, wherein the calcium silicate particles are in a silicate binder or mineral trioxide aggregate (MTA).

5. The hydraulic binder according to claim 1, further comprising at least one additive.

6. The hydraulic binder according to claim 5, wherein at least one additive is a radiation-impermeable agent selected from zirconium oxide, bismuth oxide, cerium oxide, barium sulfate, calcium tungstate, titanium dioxide, ytterbium oxide, and mixtures thereof.

7. A method for manufacturing a hydraulic adhesive according to any one of claims 1 to 6, comprising mixing -Calcium silicate particles comprising 15% to 98% by weight of the total binder, and - 0.5% to 85% by weight of calcium carbonate particles, which constitute the total weight of the binder.

8. A method for manufacturing a hydraulic adhesive according to any one of claims 1 to 6, comprising a mixing step of at least one powder phase, and simultaneous and / or sequential vibration steps, thereby obtaining a hydraulic adhesive according to any one of claims 1 to 6, wherein the powder phase comprises: -Calcium silicate particles comprising 15% to 98% by weight of the total binder, and -0.5% to 85% by weight of calcium carbonate particles.

9. The method of claim 8, wherein the vibration step is performed at a vibration frequency of 1 rpm to 15000 rpm and a vibration time of 1 s to 3600 s.

10. The method of claim 8 or 9, wherein mixing of the powder phase comprises mixing by three-dimensional motion.

11. A method for manufacturing a composite material, comprising at least one step of mixing a hydraulic binder according to any one of claims 1 to 6 with an aqueous phase; wherein the mass ratio of the hydraulic binder to the aqueous phase is 2 to 4.

5.

12. A composite material obtained by the method according to claim 11, comprising: - A solid dispersion phase comprising or consisting of hydrated calcium silicate (CSH); - Calcium silicate particles dispersed in a solid dispersion phase; - A porous intergranular region located between calcium silicate particles; said porous intergranular region contains insoluble calcium carbonate particles having a di of 1 nm to 1500 nm. 50 granularity.

13. A kit for preparing composite materials, the kit comprising: - A powder phase comprising the hydraulic binder according to any one of claims 1 to 6; and -Aqueous liquid phase; The weight ratio of the powder phase to the aqueous liquid phase in the complete set of supplies is 2 to 5.

14. Use of the hydraulic adhesive according to any one of claims 1 to 6 in the manufacture of composite materials as reinforcing materials in the field of non-therapeutic adhesives.

15. A hydraulic adhesive according to claim 1, used in the medical field to form repair materials and / or filler materials.

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