Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/02—Alcohols; Phenols; Ethers
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
  • C04B24/122—Hydroxy amines
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
  • C04B28/06—Aluminous cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
  • C04B28/08—Slag cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
  • C04B28/26—Silicates of the alkali metals
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
  • C04B2103/308—Slump-loss preventing agents
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/40—Surface-active agents, dispersants
  • C04B2103/408—Dispersants
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
  • C04B2111/1037—Cement free compositions, e.g. hydraulically hardening mixtures based on waste materials, not containing cement as such

Definitions

• the present invention relates to hydraulic binder compositions comprising blast furnace slag or other alumino-siliceous source and a reduced amount of clinker and the maintenance of workability of the hydraulic composition obtained in particular by adding water to said hydraulic binder composition.
• the usual cementitious compositions include a variable, sometimes high proportion of clinker.
• a cementitious composition according to standard NF EN 197-1 of 2012 comprises from 5 to 95% by weight of clinker.
• the present invention which relates to the use of at least one molecule of which an aqueous solution has a dispersive part greater than 25%, to improve the maintenance of workability of a hydraulic composition based on a hydraulic binder composition comprising at least one hydraulic binder comprising alumino-silicates, and a maximum of 10% by weight of clinker, preferably from 0 to 10% by weight of clinker.
• the hydraulic binder composition may be free of clinker.
• the binder comprising alumino-silicates is chosen from blast furnace slags and/or other alumino-siliceous sources.
• the present invention therefore preferably relates to the use of at least one molecule, an aqueous solution of which has a dispersive proportion greater than 25%, to improve the maintenance of workability of a hydraulic composition based on a hydraulic binder composition.
• a hydraulic binder composition comprising blast-furnace slag and/or other alumino-siliceous sources, preferably blast-furnace slag, and a maximum of 10% by weight of clinker, preferably from 0 to 10% by weight of clinker.
• Blast furnace slag is defined in particular in parts 3.7 and 3.6 of standard NF EN 15167-1. Blast furnace slags are mostly glassy materials and are by-products of cast iron production. The blast furnace slags used in the hydraulic binder compositions are preferably finely ground to a maximum diameter of 100 to 150 ⁇ m, the diameter being measured by any method known to those skilled in the art, for example by laser granulometry. Blast furnace slags generally require calcic or sulpho-calcic activation or with the help of a strong base.
• the other alumino-siliceous sources can be part of the family of pozzolanic materials (as defined in standard Cement NF EN 197-1 (2012) paragraph 5.2.3), fly ash (as defined in standard Cement NF EN 197-1 (2012) 197-1 (2012) paragraph 5.2.4), calcined shales (as defined in standard Cement NF EN 197-1 (2012) paragraph 5.2.5), or silica fumes (as defined in standard Cement NF EN 197-1(2012) paragraph 5.2.7) or their mixtures. others minerals, not currently recognized by the standard Cement NF EN 197-1 (2012), can also be used.
• metakaolins such as type A metakaolins compliant with standard NF P 18-513 (August 2012) or calcined clays
• siliceous additions such as siliceous additions of Qz mineralogy compliant with standard NF P 18-509 (September 2012)
• alumino-silicates in particular of the inorganic geopolymer type alumino-silicates containing iron oxides such as bauxite residues, norites or aplites from excavations.
• alumino-siliceous compound means fly ash (as defined in standard Cement NF EN 197-1 (2012) paragraph 5.2.4), metakaolins, such as type A metakaolins complying with standard NF P 18-513 (March 2012) or calcined clays, alumino-silicates in particular of the inorganic geopolymer type.
• composition of the invention may comprise a mixture of alumino-siliceous compounds.
• the hydraulic binder composition comprises from 75 to 99% by weight of alumino-siliceous compound, preferably from 80 to 95% by weight, for example from 80 to 90% by weight, relative to the total weight of hydraulic binder .
• the hydraulic binder composition may be free of clinker.
• the clinker can be a clinker of Portland cement, sulpho-aluminous or sulpho-belitic cement.
• the hydraulic binder composition of the invention may additionally comprise a blast-furnace slag activator and/or other alumino-siliceous sources.
• a blast-furnace slag activator and/or other alumino-siliceous sources are known and described in particular in Alkaline activation of different aluminosilicates as an alternative to Portland circle: alkali activated cements or geopolymers. Revista Ingenieria de ConstrucciénRICVol 32 N e 22017.
• a calcium or sulpho-calcium activator or an alkaline salt preferably sodium or potassium carbonate, hydroxide, silicate, or mixtures thereof.
• This activator is used in proportions of 0 to 20% by dry weight, preferably from 0 to 10% by dry weight relative to the weight of hydraulic binder, preferably from 0.1 to 20% by dry weight relative to the weight of hydraulic binder, preferably from 1% to 20% by dry weight relative to the weight of hydraulic binder.
• the hydraulic binder composition may also comprise calcium sulphate, in particular in a proportion of 5 to 20% by weight.
• Such compositions of hydraulic binders are also called over-sulphated cement (CSS) and are in particular as defined in standard NF EN 15743+A1.
• the hydraulic binder composition consists of a blast furnace slag and/or other alumino-siliceous sources and optionally an activator.
• the hydraulic binder consists of an alumino-siliceous compound and an alkaline or sulphate activator.
• the hydraulic binder composition can also comprise mineral additions, preferably from 0 to 10% by weight relative to the weight of hydraulic binder.
• metakaolins such as type A metakaolins compliant with standard NF P 18-513 (August 2012) or calcined clays
• siliceous additions such as siliceous additions of Qz mineralogy compliant with standard NF P 18-509 (September 2012)
• alumino-silicates in particular of the inorganic geopolymer type alumino-silicates containing iron oxides such as bauxite residues, norites or aplites from excavations.
• the proportions of additions and their nature can also comply with standard prEN 197-5, which defines CEM ll/C-M cements comprising between 50 and 64% clinker and 36 to 50% blast furnace slag and cements CEM VI comprising 35 to 49% clinker, 31 to 59% blast furnace slag and 6 to 20% mineral additions as defined above.
• the expression “mineral additions” denotes pozzolanic materials (as defined in standard Cement NF EN 197-1 (2012) paragraph 5.2.3), calcined shales (as defined in standard Cement NF EN 197-1 (2012) paragraph 5.2.5), limestone (as defined in standard Cement NF EN 197-1 (2012) paragraph 5.2.6) or silica fumes (as defined in standard Cement NF EN 197-1(2012) paragraph 5.2.7) or mixtures thereof.
• Other additions, not currently recognized by the Cement standard NF EN 197-1 (2012), can also be used.
• siliceous additions such as siliceous additions of Qz mineralogy compliant with standard NF P 18-509 (September 2012)
• the proportions of additions and their nature can also comply with standard prEN 197-5, which defines CEM ll/CM cements comprising between 50 and 64% of clinker and 36 to 50% blast furnace slag and CEM VI cements comprising 35 to 49% clinker, 31 to 59% blast furnace slag and 6 to 20% mineral additions as defined above -above.
• the hydraulic binder composition comprises blast furnace slag and/or other alumino-siliceous sources, optionally an activator as defined above, optionally Portland cement clinker, sulpho-aluminous or sulpho-belitic cement and optionally mineral additions as described above.
• the hydraulic binder of the invention comprises blast furnace slag.
• total weight of hydraulic binder is understood to mean the weight of the binders comprising aluminosilicates, preferably blast-furnace slag and/or other alumino-siliceous sources, of the activator if it is present, clinker if present, and mineral additions if present.
• the improvement in workability retention measured for example by the evolution of the threshold stress of a hydraulic composition obtained from the hydraulic binder composition defined above, in particular by adding of water, over time, is preferably long-term, namely over a period greater than or equal to 45 minutes, in particular greater than 60 minutes, or even greater than 90 minutes when the composition is used at 20°C.
• threshold stresses of the order of 1 to 10 Pa during the same time intervals that is to say over a period greater than or equal to 45 minutes, in particular greater than 60 minutes, or even greater than 90 minutes. when the composition is used at 20°C.
• the improvement in workability retention is determined with respect to the same composition in the absence of said molecule.
• the threshold stress can in particular be measured using a rheometer by taking several measurements of the applied stress to obtain each corresponding strain rate value.
• the applied stress below which the strain rate becomes very low or zero can be considered as the threshold stress.
• the threshold stress obtained by the implementation of the present invention is less than 130 Pa at 120 min, preferably between 30 and 130 Pa at 120 min, it is for example between 30 and 90 Pa at 120 min.
• the dispersive part of an aqueous solution of said molecule is determined by measuring the components of the surface energy of an aqueous solution comprising said molecule (SAM).
• SAM surface energy of an aqueous solution comprising said molecule
• the aqueous solution of said molecule (SAM) is deposited on a strip of poly(tetrafluoroethylene) (PTFE), deposited on a glass slide.
• Molecules of any substance, solid or liquid interact via two classes of forces: dispersive forces (due to transient electric dipoles: London - van der Waals%) and polar forces (due to permanent electric dipoles).
• dispersive forces due to transient electric dipoles: London - van der Waals
• polar forces due to permanent electric dipoles.
• the Owens-Wendt law makes it possible to relate to the polar and dispersive components of the surface energies of the two materials the contact angle which will be formed by the deposition of a droplet of L on a surface of S:
• equation (4) With the deposit of the aqueous solution of said molecule (SAM) on the PTFE, equation (4) then becomes:
• the dispersive part corresponds to the percentage of the dispersive component relative to the sum of the dispersive component and the polar component.
• the molecule according to the invention makes it possible to produce an aqueous solution whose dispersive part is greater than that of water, preferably between 25 and 50%, preferably between 25 and 45%, for example between 25 and 45%.
• the molecule is implemented in water in a content making it possible to obtain a water+molecule mixture whose dispersive part is greater than that of water, preferably between 25 and 50%, preferably between 25 and 45%, for example between 25 and 45%, preferably the molecule content in the water is between 1 and 5% by weight, preferably between 1 and 4% by weight relative to the total weight of the solution water+molecule.
• the molecule according to the invention makes it possible to produce an aqueous solution (water+molecule solution) whose dispersive part is between 12 mN/m and 35 mN/m, preferably between 14 and 32 mN/m.
• the molecule according to the invention makes it possible to produce an aqueous solution (water+molecule solution) whose dispersive part is between 12 mN/m and 35 mN/m, preferably between 14 and 32 mN/m and a polar component comprised between 25 and 60 mN/m, preferably comprised between 25 and 55 mN/m.
• aqueous solution water+molecule solution
• dispersive part is between 12 mN/m and 35 mN/m, preferably between 14 and 32 mN/m and a polar component comprised between 25 and 60 mN/m, preferably comprised between 25 and 55 mN/m.
• the molecule according to the invention preferably comprises at least one OH function, preferably one, two or three OH functions.
• the molecule according to the invention is chosen from alcohols and alkanolamines, for example 2-methyl-2,4 pentanediol, 2,2-dimethylpropane-1,3-diol, 2-methyl-1,3-propanediol , 5-ethyl-1,3-dioxane-5-methanol, tri(isopropanol)amine, preferably 2-methyl-2,4-pentanediol, 2-methyl-1,3-propanediol, 5-ethyl-1,3- dioxane-5-methanol, tri(isopropanol)amine.
• the molecule according to the invention is used in contents of between 0.5 and 3% by weight, preferably between 1 and 2% by weight relative to the total weight of hydraulic binder.
• the molecule is added to the batch.
• the invention relates to the use of an aqueous solution of a molecule (water+molecule solution) having a dispersive proportion greater than that of water, preferably greater than 25%, preferably between 25 and 50 %, preferably between 25 and 45%, for example between 25 and 45%.
• the aqueous solution of the molecule whose dispersive part is measured comprises only water and said molecule.
• the molecule can optionally be added during the grinding of the hydraulic binder.
• a guanidine salt may additionally be used to improve workability retention.
• adjuvants can be implemented in the context of the present invention in addition to the molecules mentioned above.
• These adjuvants can be chosen by those skilled in the art from adjuvants typical of cementitious compositions and hydraulic compositions. Mention may in particular be made of alkanolamines, salts such as sodium chloride, calcium chloride, sodium thiocyanate, calcium thiocyanate, sodium nitrate and calcium nitrate and their mixtures, glycols, glycerols, water-reducing and high water-reducing adjuvants, surfactants, carboxylic acids and their salts such as acetic, adipic, gluconic, formic, oxalic, citric, maleic, lactic, tartaric, malonic acids and mixtures thereof, anti-foaming additives, air-entraining additives and/or grinding agents, set retarders.
• set retarders based on sugar, molasses or vinasse.
• the water-reducing and high-water-reducing adjuvants are chosen from:
• melamine-based superplasticizers The sulfonated salts of polycondensates of melamine and formaldehyde, commonly called melamine-based superplasticizers;
• polycarboxylic acids in particular polycarboxylate comb copolymers, which are branched polymers whose main chain bears carboxylic groups and whose side chains are composed of sequences of the polyether type, in particular polyethylene oxide, such as poly[acid (meth)acrylic - grafted - polyethylene oxide].
• polyether type in particular polyethylene oxide, such as poly[acid (meth)acrylic - grafted - polyethylene oxide].
• polyethylene oxide such as poly[acid (meth)acrylic - grafted - polyethylene oxide].
• the superplasticizers of the CHRYSO® Fluid Optima, CHRYSO® Fluid Premia and CHRYSO® Plast Omega ranges marketed by CHRYSO can in particular be used;
• the hydraulic composition may also comprise other additives known to those skilled in the art, for example a mineral addition and/or additives, for example an anti-air-entrainment additive, an antifoam agent, an accelerator or retarder , a rheology modifier, another plasticizer (plasticizer or superplasticizer), in particular a superplasticizer, for example a superplasticizer CHRYSO®Fluid Premia 180 or CHRYSO®Fluid Premia 196.
• a mineral addition and/or additives for example an anti-air-entrainment additive, an antifoam agent, an accelerator or retarder , a rheology modifier, another plasticizer (plasticizer or superplasticizer), in particular a superplasticizer, for example a superplasticizer CHRYSO®Fluid Premia 180 or CHRYSO®Fluid Premia 196.
• the present invention also relates to a method for improving the workability retention of a hydraulic composition based on a hydraulic binder composition
• a hydraulic binder composition comprising binders comprising alumino-silicates, for example blast furnace slag and/or other aluminosiliceous source, optionally an activator, and a maximum of 10% by weight of clinker, preferably from 0 to 10% by weight of clinker, comprising the addition of at least one molecule making it possible to obtain an aqueous solution having a dispersive part greater than that of water, preferably greater than 25%, preferably between 25 and 50%, preferably between 25 and 45%, for example between 25 and 45%, to said hydraulic composition.
• the improvement in the maintenance of workability is looked at compared to the same hydraulic composition comprising the molecule according to the invention.
• the invention also relates to a hydraulic composition
• a hydraulic composition comprising (or even consisting of) the hydraulic binder composition defined above, water, an aggregate and optionally one or more mineral additives, and at least one molecule making it possible to obtain a mixing water having a dispersive proportion greater than that of water, preferably greater than 25%, preferably between 25 and 50%, preferably between 25 and 45%, for example between 25 and 45%.
• a dispersive proportion greater than that of water, preferably greater than 25%, preferably between 25 and 50%, preferably between 25 and 45%, for example between 25 and 45%.
• the preferred and advantageous characteristics mentioned above for the molecule, the hydraulic binder composition, etc. also apply to the hydraulic composition.
• the hydraulic composition is preferably a concrete, mortar or screed composition.
• aggregates is meant a set of mineral grains with an average diameter of between 0 and 125 mm. Depending on their diameter, aggregates are classified into one of the following six families: fillers, sand, sand, gravel, gravel and ballast (standard XP P 18-545). The most commonly used aggregates are:
• the sands are therefore included in the definition of aggregate according to the invention.
• the fillers can in particular be of limestone or dolomitic origin.
• additives can be added to the hydraulic composition (CH) according to the invention, such as anti-air-entrainment additives, antifoam agents, a setting accelerator or retarder, a rheology modifier, another plasticizer (plasticizer or superplasticizer).
• the hydraulic compositions are prepared conventionally by mixing the aforementioned constituents.
• the molecule of the invention is added when mixing or when grinding the hydraulic binder composition.
• the mixing of the material is carried out as follows: 1.
• the water and the molecule according to the invention are weighed in the bowl of the mixer, the mixer is started at a speed of 43 revolutions/min.
• a stopwatch is started, and the binder is poured in 30 seconds.
• the speed is increased to 96 rpm and the mixture is mixed for one minute.
• the mixer is stopped for 30 seconds, the material possibly projected on the walls is scraped towards the center with a spatula.
• the suspension is mixed for one minute at 96 rpm.
• the paste obtained is poured into the cylindrical measurement cell of a Kinexus Pro rheometer (Netzsch) fitted with a fin-type measurement geometry.
• the cement mixture is subjected to pre-shearing for one minute at a strain rate of 200 s -1 .
• the sample is then subjected to a series of decreasing strain rate levels, in logarithmic jumps from 200 s -1 to 0.01 s -1 and the rheometer records the stress to be applied at each point. The whole constitutes a flow curve linking the stress applied to obtain each strain rate value.
• Example 2 Measurement of the Polar and Disoersive Components of Molecules The measurements of polar and dispersive components of different solutions of molecules are collated in the following table.
• a hydraulic composition is prepared according to the protocol of example 1 and according to the composition of table 2 below.
• the rheological results are summarized by measuring the threshold stress at 120 min after the start of mixing, which measures the capacity of the molecules to maintain high fluidity (low threshold stress) during this period. This measurement is related to the dispersive part of the surface energy of the liquid, defined as the ratio between the dispersive component and surface tension.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Environmental & Geological Engineering (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Geology (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Lubricants (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)
• Disintegrating Or Milling (AREA)

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• 2021
  • 2021-05-26 FR FR2105469A patent/FR3123350B1/fr active Active
• 2022
  • 2022-05-24 WO PCT/EP2022/063991 patent/WO2022248442A1/fr not_active Ceased
  • 2022-05-24 CN CN202280037763.6A patent/CN117396450A/zh active Pending
  • 2022-05-24 BR BR112023024643A patent/BR112023024643A2/pt unknown
  • 2022-05-24 AU AU2022281064A patent/AU2022281064A1/en active Pending
  • 2022-05-24 CA CA3220017A patent/CA3220017A1/fr active Pending
  • 2022-05-24 EP EP22730241.1A patent/EP4347526A1/de active Pending
  • 2022-05-24 US US18/563,845 patent/US20240368035A1/en active Pending
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• 2023
  • 2023-11-22 ZA ZA2023/10795A patent/ZA202310795B/en unknown

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