CN-117062791-B - Hydraulic binders based on calcium silicate for forming composite materials with reinforcing properties

Abstract

The present invention relates to the field of hydraulic binders and hardened materials obtained after hydration of said hydraulic binders, in particular binders useful in the medical field, such as dental binders. In particular, the present invention provides a hydraulic binder comprising calcium silicate particles and calcium carbonate particles having a specific particle size. The hydration of the hydraulic binder of the present invention is able to provide a hardened composite material with reinforcing properties comprising calcium silicate particles dispersed in a solid dispersed phase comprising Calcium Silicate Hydrate (CSH) and porous inter-particulate regions comprising insoluble calcium carbonate particles having a d 50 particle size of 1nm to 1500 nm.

Inventors

• Munir Judy
• GILLES RICHARD
• Lauren Alto

Assignees

• 塞普托东专业股份有限公司

Dates

Publication Date

20260512

Application Date

20220304

Priority Date

20210304

Claims (15)

1. 1. A hydraulic binder comprising: 15 to 98% by weight of calcium silicate particles, based on the total weight of the binder, wherein 50% by volume of the total volume of the calcium silicate particles has a size of 1 to 10 μm, and -0.5 To 85 wt% of calcium carbonate particles, based on the total weight of the binder, wherein: 10% by volume of the total volume of the calcium carbonate particles has a size of less than 0.59 μm; 50% by volume of the total volume of the calcium carbonate particles has a size of less than 2.5 μm, and 40% By volume of the total volume of the calcium carbonate particles has a size of 2.5 μm to 20 μm.
2. 2. The hydraulic binder of claim 1, wherein: 10% by volume of the total volume of the calcium carbonate particles has a size of less than 0.55 μm; 50% by volume of the total volume of the calcium carbonate particles has a size of less than 1.5 μm, and 40% By volume of the total volume of the calcium carbonate particles has a size of 1.5 μm to 5.5 μm.
3. 3. The hydraulic binder of claim 1 or 2, wherein the calcium silicate particles are selected from the group consisting of tricalcium silicate (C3S), dicalcium silicate (C2S), and any combination thereof.
4. 4. The hydraulic binder of claim 1 or 2, wherein the calcium silicate particles are in a silicate binder or a Mineral Trioxide Agglomerate (MTA).
5. 5. The hydraulic binder of claim 1, further comprising at least one additive.
6. 6. The hydraulic binder of claim 5, wherein at least one additive is a radiopacifier selected from the group consisting of zirconia, bismuth oxide, ceria, barium sulfate, calcium tungstate, titania, ytterbia, and mixtures thereof.
7. 7. A method for manufacturing the hydraulic binder according to any one of claims 1 to 6, comprising mixing 15 To 98% by weight of calcium silicate particles, based on the total weight of the binder, and 0.5 To 85% by weight of calcium carbonate particles, based on the total weight of the binder.
8. 8. A process for manufacturing a hydraulic binder according to any one of claims 1 to 6, comprising at least one mixing step of a powder phase, and a simultaneous and/or sequential vibration step, resulting in a hydraulic binder according to any one of claims 1 to 6, wherein the powder phase comprises: 15 to 98% by weight of calcium silicate particles, based on the total weight of the binder, and 0.5 To 85% by weight of calcium carbonate particles.
9. 9. The method of claim 8, wherein the vibrating step is performed at a vibration frequency of 1rpm to 15000rpm and a vibration time of 1s to 3600 s.
10. 10. The method of claim 8 or 9, wherein mixing of the powder phases comprises mixing by three-dimensional motion.
11. 11. A process for manufacturing a composite material comprising at least one step of mixing the hydraulic binder according to any one of claims 1 to 6 with an aqueous phase, the mass ratio of hydraulic binder to aqueous phase being from 2 to 4.5.
12. 12. A composite material obtained by the method of claim 11, comprising: -a solid dispersed phase comprising or consisting of Calcium Silicate Hydrate (CSH); -calcium silicate particles dispersed in a solid dispersed phase; porous inter-particulate regions between the calcium silicate particles, the porous inter-particulate regions containing insoluble calcium carbonate particles having a d 50 particle size of 1nm to 1500 nm.
13. 13. A kit for preparing a composite material, the kit comprising: -a powder phase comprising a hydraulic binder according to any one of claims 1 to 6, and -An aqueous liquid phase; wherein the weight ratio of the powder phase present in the kit to the aqueous liquid phase present in the kit is from 2 to 5.
14. 14. Use of a hydraulic binder according to any one of claims 1 to 6 for the manufacture of a composite material as reinforcement material in the field of non-therapeutic binders.
15. 15. A hydraulic binder according to claim 1 for use in the medical field to form repair and/or filler materials.

Description

Hydraulic binders based on calcium silicate for forming composite materials with reinforcing properties Technical Field The present invention relates to the field of hydraulic binders and hardened materials obtained after hydration of hydraulic binders. In particular, the present invention relates to hydraulic binders comprising calcium silicate particles and calcium carbonate particles of a specific particle size. The hydration of the hydraulic binder of the invention can provide a hardened composite material with enhanced mechanical properties. The invention also relates to a method for producing a composite material and to the use thereof in the medical field or in the field of non-therapeutic adhesives. Background High performance cementitious materials prepared from hydraulic calcium silicate binders, such as silicate binders, are increasingly used worldwide in medical and non-therapeutic fields (e.g., construction). In either field, there is always a need to provide hardened cementitious materials with enhanced mechanical properties, such as higher compressive strength. Furthermore, there is always a need to provide processes for manufacturing said materials, which are less time consuming and therefore more economical. The applicant has shown that the incorporation of calcium carbonate particles having a specific particle size group in a hydraulic binder based on calcium silicate is able to provide, after hydration, a hardened cement with enhanced mechanical properties. Without wishing to be bound by any theory, the applicant believes that the particular particle size distribution of the calcium carbonate used in the hydraulic binder of the invention results in the formation of porous inter-particulate areas with submicron calcium carbonate particles upon hydration, which provides improved mechanical properties to the hardened cementitious material. The applicant has also demonstrated that it is possible to provide a hardened material with the same type of reinforcing mechanical properties when the manufacture of the hardened cement comprises at least one mixing step of a powder phase comprising calcium silicate particles and calcium carbonate particles with an aqueous phase by vibration. Without wishing to be bound by any theory, the applicant proposes that the mixing step by vibration provides for self-grinding of at least a portion of the calcium carbonate particles contained in the hydraulic binder, resulting in a population of calcium carbonate particles having a specific particle size according to the invention, such that the final hardened cementitious material comprises reinforcing inter-particulate regions with submicron calcium carbonate particles. SUMMARY The present invention thus provides a hydraulic binder comprising: 15 to 98% by weight of calcium silicate particles, based on the total weight of the binder, wherein 50% by volume of the total volume of the calcium silicate particles has a size of 1 to 10 μm, preferably 1 to 8 μm, and -0.5 To 85 wt% of calcium carbonate particles, based on the total weight of the binder, wherein: 10% by volume of the total volume of the calcium carbonate particles has a size of less than 0.59 μm; 50% by volume of the total volume of the calcium carbonate particles has a size of less than 2.5 μm, and 40% By volume of the total volume of the calcium carbonate particles has a size of 2.5 μm to 20 μm. In one embodiment, the calcium carbonate particles are such that: 10% by volume of the total volume of the calcium carbonate particles has a size of less than 0.55 μm; 50% by volume of the total volume of the calcium carbonate particles has a size of less than 1.5 μm, and 40% By volume of the total volume of the calcium carbonate particles has a size of 1.5 μm to 5.5 μm. In one embodiment, the calcium silicate particles are selected from the group consisting of tricalcium silicate (C3S), dicalcium silicate (C2S), and any combinations thereof, preferably the calcium silicate particles are tricalcium silicate particles. In one embodiment, the calcium silicate particles are present in a silicate binder and/or a Mineral Trioxide Aggregate (MTA). In one embodiment, the hydraulic binder further comprises at least one additive, preferably selected from the group consisting of set accelerators, radiopacifiers, pigments, pH stabilizers, fillers, texturizers/thickeners, water reducers and mixtures thereof. In one embodiment, the radiopacifier is selected from the group consisting of zirconia, bismuth oxide, ceria, barium sulfate, calcium tungstate, titania, ytterbium oxide, and mixtures thereof, and preferably the radiopacifier is zirconia. The invention also provides a process for the manufacture of the hydraulic binder according to the invention, comprising mixing 15 To 98% by weight of calcium silicate particles, based on the total weight of the binder, wherein 50% by volume of the total volume of the calcium silicate particles has a size of 1 to 10 μm, preferably 1 to