EP4347526A1 - Improved workability retention in low-clinker hydraulic compositions - Google Patents
Improved workability retention in low-clinker hydraulic compositionsInfo
- Publication number
- EP4347526A1 EP4347526A1 EP22730241.1A EP22730241A EP4347526A1 EP 4347526 A1 EP4347526 A1 EP 4347526A1 EP 22730241 A EP22730241 A EP 22730241A EP 4347526 A1 EP4347526 A1 EP 4347526A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- molecule
- weight
- hydraulic binder
- hydraulic
- clinker
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 230000014759 maintenance of location Effects 0.000 title claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 51
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002893 slag Substances 0.000 claims description 22
- 239000012190 activator Substances 0.000 claims description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 12
- 239000011707 mineral Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 9
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000012423 maintenance Methods 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 4
- BGFBWRWYROQISE-UHFFFAOYSA-N 5-ethyl-1,3-dioxane-5-methanol Chemical compound CCC1(CO)COCOC1 BGFBWRWYROQISE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- XOROEPUWPNHOPP-UHFFFAOYSA-N O[S-](=O)=O.[Ca+] Chemical compound O[S-](=O)=O.[Ca+] XOROEPUWPNHOPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000001175 calcium sulphate Substances 0.000 claims description 3
- 235000011132 calcium sulphate Nutrition 0.000 claims description 3
- 159000000011 group IA salts Chemical class 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 239000004568 cement Substances 0.000 description 26
- 238000007792 addition Methods 0.000 description 20
- 235000010755 mineral Nutrition 0.000 description 11
- 238000005259 measurement Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000012530 fluid Substances 0.000 description 6
- 239000002671 adjuvant Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- -1 bauxite residues Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920000876 geopolymer Polymers 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000008030 superplasticizer Substances 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- 235000015076 Shorea robusta Nutrition 0.000 description 3
- 244000166071 Shorea robusta Species 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000001595 flow curve Methods 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000009412 basement excavation Methods 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229920000090 poly(aryl ether) Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000006254 rheological additive Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- QGJDXUIYIUGQGO-UHFFFAOYSA-N 1-[2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoyl]pyrrolidine-2-carboxylic acid Chemical compound CC(C)(C)OC(=O)NC(C)C(=O)N1CCCC1C(O)=O QGJDXUIYIUGQGO-UHFFFAOYSA-N 0.000 description 1
- ALWXETURCOIGIZ-UHFFFAOYSA-N 1-nitropropylbenzene Chemical compound CCC([N+]([O-])=O)C1=CC=CC=C1 ALWXETURCOIGIZ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000004117 Lignosulphonate Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002691 malonic acids Chemical class 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000417 polynaphthalene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
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
- C04B28/08—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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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR2105469A FR3123350B1 (en) | 2021-05-26 | 2021-05-26 | Improvement in maintaining the workability of hydraulic compositions with a low clinker content |
PCT/EP2022/063991 WO2022248442A1 (en) | 2021-05-26 | 2022-05-24 | Improved workability retention in low-clinker hydraulic compositions |
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EP4347526A1 true EP4347526A1 (en) | 2024-04-10 |
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EP22730241.1A Pending EP4347526A1 (en) | 2021-05-26 | 2022-05-24 | Improved workability retention in low-clinker hydraulic compositions |
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EP (1) | EP4347526A1 (en) |
CN (1) | CN117396450A (en) |
AU (1) | AU2022281064A1 (en) |
BR (1) | BR112023024643A2 (en) |
CA (1) | CA3220017A1 (en) |
FR (1) | FR3123350B1 (en) |
MX (1) | MX2023014022A (en) |
WO (1) | WO2022248442A1 (en) |
ZA (1) | ZA202310795B (en) |
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FR2696736B1 (en) | 1992-10-12 | 1994-12-30 | Chryso | Fluidizers for aqueous suspensions of mineral particles and hydraulic binder pastes. |
CN101367631B (en) * | 2008-09-27 | 2012-11-21 | 天津水泥工业设计研究院有限公司 | Ultra-fine coal ash based composite mineral blending material and manufacturing method thereof |
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2021
- 2021-05-26 FR FR2105469A patent/FR3123350B1/en active Active
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2022
- 2022-05-24 CA CA3220017A patent/CA3220017A1/en active Pending
- 2022-05-24 EP EP22730241.1A patent/EP4347526A1/en active Pending
- 2022-05-24 WO PCT/EP2022/063991 patent/WO2022248442A1/en active Application Filing
- 2022-05-24 BR BR112023024643A patent/BR112023024643A2/en unknown
- 2022-05-24 AU AU2022281064A patent/AU2022281064A1/en active Pending
- 2022-05-24 MX MX2023014022A patent/MX2023014022A/en unknown
- 2022-05-24 CN CN202280037763.6A patent/CN117396450A/en active Pending
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FR3123350A1 (en) | 2022-12-02 |
WO2022248442A1 (en) | 2022-12-01 |
CN117396450A (en) | 2024-01-12 |
CA3220017A1 (en) | 2022-12-01 |
ZA202310795B (en) | 2024-06-26 |
MX2023014022A (en) | 2024-01-11 |
FR3123350B1 (en) | 2024-05-10 |
AU2022281064A1 (en) | 2023-12-07 |
BR112023024643A2 (en) | 2024-02-20 |
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