WO1997019032A1 - Multipurpose admixture for hydraulic cement composition - Google Patents
Multipurpose admixture for hydraulic cement composition Download PDFInfo
- Publication number
- WO1997019032A1 WO1997019032A1 PCT/US1996/018300 US9618300W WO9719032A1 WO 1997019032 A1 WO1997019032 A1 WO 1997019032A1 US 9618300 W US9618300 W US 9618300W WO 9719032 A1 WO9719032 A1 WO 9719032A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- admixture
- acid
- calcium
- cement composition
- fatty acid
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 239000011396 hydraulic cement Substances 0.000 title claims abstract description 20
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 12
- 239000000194 fatty acid Substances 0.000 claims abstract description 12
- 229930195729 fatty acid Natural products 0.000 claims abstract description 12
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 230000002708 enhancing effect Effects 0.000 claims abstract description 9
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 23
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 22
- -1 alkaline earth metal salt Chemical class 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 14
- 239000004568 cement Substances 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 7
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 7
- 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 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229940104261 taurate Drugs 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000011398 Portland cement Substances 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000004281 calcium formate Substances 0.000 claims description 3
- 229940044172 calcium formate Drugs 0.000 claims description 3
- 235000019255 calcium formate Nutrition 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 claims description 3
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229920001732 Lignosulfonate Polymers 0.000 abstract description 4
- 239000004567 concrete Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000006072 paste Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940044170 formate Drugs 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- IZWPGJFSBABFGL-GMFCBQQYSA-M sodium;2-[methyl-[(z)-octadec-9-enoyl]amino]ethanesulfonate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CCS([O-])(=O)=O IZWPGJFSBABFGL-GMFCBQQYSA-M 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000003784 tall oil Substances 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators or shrinkage compensating 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
- 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
-
- 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
- C04B24/08—Fats; Fatty oils; Ester type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
-
- 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
-
- 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
- C04B24/16—Sulfur-containing compounds
-
- 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
- C04B24/16—Sulfur-containing compounds
- C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
Definitions
- the present invention relates to admixtures for hydraulic cement compositions, and more particularly to a multifunctional admixture that combines set acceleration and air entrainment properties.
- hydraulic cement refers to a cement which hardens by a chemical interaction or reaction with water. It is publicly known that certain properties of hydraulic cements can be modified by the addition of any number of chemical additives. For example, it is known to add calcium nitrate as a set accelerator. However, calcium nitrate may beTncompatable when combined in the hydratable cement mixture with other kinds of additives, chemicals, and agents. In the present invention, the inventors have discovered a novel combination of chemical additives for simultaneously achieving a number of properties in a hydraulic cement composition.
- the present invention relates to a multifunctional hydraulic cement composition admixture which comprises a set accelerator which is an alkali or alkaline earth metal salt which is a salt of an organic or inorganic acid, and a fatty acid aminosulfonic acid surfactant.
- the set accelerator is a calcium salt, such as calcium nitrate, calcium chloride, calcium formate, or calcium nitrite, and a fatty acid aminosulfonic acid having the general formula
- M is an alkali or alkaline earth metal, ammonium, or alkyl ammonium ion
- the set accelerator comprises calcium nitrate
- Another preferred multi-functional hydraulic cement admixture of the invention further comprises, in addition to the set accelerator and surfactant, a water reducing agent, an early strength enhancing agent, and preferably both.
- the water reducing agent may comprise a lignosulfonate, such as calcium lignosulfonate.
- the early strength enhancing agent may comprise an alkanolamine, preferably a triethanolamine.
- preferred multi-functional hydraulic cement composition admixtures of the invention can comprise a set accelerator, a water reducing agent, an early strength enhancing agent, and a fatty acid aminosulfonic acid surfactant which is believed to be operative to act as an air entraining agent. While some of these functions may have been combined simultaneously within one admixture formulation, it is believed that the combination of certain of these functional components, such as the set accelerator with the surfactant agents, not to mention all four of the functional components just described, has not been disclose or suggested by the prior art.
- the present invention further relates to hydraulic cement mixes, including concrete mixes, comprising multi-functional admixtures described above and hereinafter.
- cement composition refers to pastes, mortars and concrete compositions comprising a hydraulic cement binder.
- Pastes are mixtures composed of a hydraulic cement binder, for example, Portland cement, either alone or in combination with other components such as fly ash, silica fume or blast furnace slag, and water; mortars are pastes additionally including fine aggregate, and concretes are mortars additionally including coarse aggregate.
- the cement compositions of this invention are formed by mixing certain amounts of required materials, e.g., a hydraulic cement, water, and fine or coarse aggregate, as may be applicable for the particular cement composition being formed.
- concrete includes and refers to a mixture of such hydraulic cements and inert aggregates.
- Typical aggregates include conventional "coarse” aggregates such as gravel, granite, limestone, quartz sieve, etc., as well as those materials conventionally referred to as “fine” aggregates such as sand and fly ash.
- Conventional hydraulic cement concretes e.g., Portland cement concretes, employ major amounts of such aggregates, i.e. over 50% and usually up to about 75% by volume, in the set product.
- the present invention pertains to a hydraulic cement composition admixture comprising a set accelerator component, preferably calcium nitrate, and a fatty acid aminosulfonic acid surfactant component, preferably sodium N-methyl oleoyl taurate.
- a set accelerator component preferably calcium nitrate
- a fatty acid aminosulfonic acid surfactant component preferably sodium N-methyl oleoyl taurate.
- Other preferred admixtures additionally comprise a water reducing agent, such as an alkanolamine and more preferably a triethanolamine; an early strength enhancing component, such as a lignosulfonate and preferably a calcium lignosulfonate; and, still more preferably, the admixture additionally comprises both the triethanolamine and calcium lignosulfonate.
- the admixture components can be blended into a stable solution using conventional mixing equipment.
- the set-accelerating component may be any compound which, when added to a cement composition, reduces the amount of time required for the cement composition to harden.
- an alkali or alkaline earth metal salt which is a salt of an organic or inorganic acid may be employed.
- alkali or alkaline earth metal nitrate, nitrite, and formate examples of these compounds are alkali or alkaline earth metal nitrate, nitrite, and formate; alkali or alkaline earth metal salts of Group VII halogen and pseudohalogen acids, such as alkali or alkaline earth metal chloride, bromide, iodide, cyanide, cyanate, azide, and thiocyanate; alkali or alkaline earth metal thiosulfate and perchlorate; and.alkali or alkaline earth metal aluminates, silicates, and hydroxides, e.g., sodium hydroxide.
- Calcium salts are particularly advantageous, especially calcium nitrate, calcium chloride, calcium formate, and calcium nitrite. Calcium nitrate is preferred.
- the fatty acid aminosulfonic acid which is believed to operate as an air entraining agent in a hydraulic cement composition, may be an alkali or alkali earth metal salt of an N-alkyl-N-tall oil aminosulfonic acid, having the general formula
- R is a hydrogen, alkyl group or aryl group;
- x is 1 to 10;
- M is an alkali or alkaline earth metal, ammonium, or alkyl ammonium ion; and "n" is 1 to 3.
- a preferred fatty acid aminosulfonic acid surfactant comprises sodium N-methyl-N- oleoyl taurate, which is available from Rhone-Poulenc, Cranbury, New Jersey, under the tradename Igepon T-33.
- the water reducing agent may be an alkali or alkaline earth metal salt of lignosulfonic acid, polycarboxylic acid, napthalene sulfonic acid condensate, melamine sulfonic acid condensate, hydroxylated carboxylic acids, and carbohydrates such as corn syrup.
- the water reducing agent is a lignosulfonate, such as calcium lignosulfonate.
- Early strength enhancing agents are known, as is the term “early strength,” by which is meant compressive strength at 1 - 3 days (see e.g., ASTM C-39).
- Early strength enhancing agents include alkanolamines.
- An alkanolamine is a generic term for a group of compounds in which trivalent nitrogen is attached directly to a carbon atom of an alkyl alcohol, and examples are monoethanolamine, diethanolamine, and triethanolamine.
- Alkanolamines also include methyldiethanolamine and triisopropanolamine.
- Preferred multi-functional admixtures of the invention are preferably used in an amount of 0.05-1.0% s/s based on cement in the concrete, where "% s/s" designates percent admixture solids on cement solids.
- a preferred admixture may comprise calcium nitrate in the range of 90-99.5% s/s and sodium N-methyl oleoyl taurate in the range of 0.5-10.0% s/s.
- Another preferred admixture comprises calcium nitrate (50-90% s/s); calcium lignosulfonate (5.0-40.0% s/s); triethanolamine or triisopropanolamine (0.1 -5.0% s/s); and sodium N-methyl oleoyl taurate (0.01-5.0% s/s).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Exemplary multifunctional hydraulic cement composition admixtures of the invention comprise a set accelerator, preferably a calcium salt, and a fatty acid aminosulfonic acid surfactant. Further exemplary admixtures additionally comprise a water reducing agent, such as a lignosulfonate, and/or an early strength enhancing agent, such as an alkanolamine.
Description
MULTIPURPOSE ADMIXTURE FOR HYDRAULIC CEMENT
COMPOSITION
Field of the Invention
The present invention relates to admixtures for hydraulic cement compositions, and more particularly to a multifunctional admixture that combines set acceleration and air entrainment properties. Background of the Invention
The term "hydraulic cement" refers to a cement which hardens by a chemical interaction or reaction with water. It is publicly known that certain properties of hydraulic cements can be modified by the addition of any number of chemical additives. For example, it is known to add calcium nitrate as a set accelerator. However, calcium nitrate may beTncompatable when combined in the hydratable cement mixture with other kinds of additives, chemicals, and agents. In the present invention, the inventors have discovered a novel combination of chemical additives for simultaneously achieving a number of properties in a hydraulic cement composition.
Summary of the Invention
The present invention relates to a multifunctional hydraulic cement composition admixture which comprises a set accelerator which is an alkali or alkaline earth metal salt which is a salt of an organic or inorganic acid, and a fatty acid aminosulfonic acid surfactant. In a preferred embodiments, the set accelerator is a calcium salt, such as calcium nitrate, calcium chloride, calcium formate, or calcium nitrite, and a fatty acid aminosulfonic acid having the general formula
CH3(CH2)X— CH=CH(CH2)y— CO— NR— <CH2)Z— SO3 " Mn+ wherein "R" is a hydrogen, alkyl group or aryl group;
"x" is 1 to 10; "y" is 3 - 10; "z" is 1 to 10;
"M" is an alkali or alkaline earth metal, ammonium, or alkyl ammonium ion; and
"n" is l to 3.
In a further preferred admixture formulation, the set accelerator comprises calcium nitrate, and the surfactant comprises sodium N-methyl oleoyl taurate, which is believed to have the formula CH3(CH2)7-CH=CH(CH2)7-CO-N(CH3)CH2CH2SO3 " Na+.
Another preferred multi-functional hydraulic cement admixture of the invention further comprises, in addition to the set accelerator and surfactant, a water reducing agent, an early strength enhancing agent, and preferably both. The water reducing agent may comprise a lignosulfonate, such as calcium lignosulfonate. The early strength enhancing agent may comprise an alkanolamine, preferably a triethanolamine.
Accordingly, preferred multi-functional hydraulic cement composition admixtures of the invention can comprise a set accelerator, a water reducing agent, an early strength enhancing agent, and a fatty acid aminosulfonic acid surfactant which is believed to be operative to act as an air entraining agent. While some of these functions may have been combined simultaneously within one admixture formulation,
it is believed that the combination of certain of these functional components, such as the set accelerator with the surfactant agents, not to mention all four of the functional components just described, has not been disclose or suggested by the prior art.
The present invention further relates to hydraulic cement mixes, including concrete mixes, comprising multi-functional admixtures described above and hereinafter.
Detailed Description of Exemplary Embodiments
The term "cement composition" as used herein refers to pastes, mortars and concrete compositions comprising a hydraulic cement binder. The above terms are terms of art. Pastes are mixtures composed of a hydraulic cement binder, for example, Portland cement, either alone or in combination with other components such as fly ash, silica fume or blast furnace slag, and water; mortars are pastes additionally including fine aggregate, and concretes are mortars additionally including coarse aggregate. The cement compositions of this invention are formed by mixing certain amounts of required materials, e.g., a hydraulic cement, water, and fine or coarse aggregate, as may be applicable for the particular cement composition being formed.
The term "concrete," where used herein, includes and refers to a mixture of such hydraulic cements and inert aggregates. Typical aggregates include conventional "coarse" aggregates such as gravel, granite, limestone, quartz sieve, etc., as well as those materials conventionally referred to as "fine" aggregates such as sand and fly ash. Conventional hydraulic cement concretes, e.g., Portland cement concretes, employ major amounts of such aggregates, i.e. over 50% and usually up to about 75% by volume, in the set product.
The present invention pertains to a hydraulic cement composition admixture comprising a set accelerator component, preferably calcium nitrate, and a fatty acid aminosulfonic acid surfactant component, preferably sodium N-methyl oleoyl taurate. Other preferred admixtures additionally comprise a water reducing agent, such as an alkanolamine and more preferably a triethanolamine; an early strength enhancing component, such as a lignosulfonate and preferably a calcium lignosulfonate; and, still more preferably, the admixture additionally comprises both the triethanolamine and
calcium lignosulfonate. The admixture components can be blended into a stable solution using conventional mixing equipment.
The set-accelerating component may be any compound which, when added to a cement composition, reduces the amount of time required for the cement composition to harden. For example, an alkali or alkaline earth metal salt which is a salt of an organic or inorganic acid may be employed. Although the following list is not meant to be limiting, examples of these compounds are alkali or alkaline earth metal nitrate, nitrite, and formate; alkali or alkaline earth metal salts of Group VII halogen and pseudohalogen acids, such as alkali or alkaline earth metal chloride, bromide, iodide, cyanide, cyanate, azide, and thiocyanate; alkali or alkaline earth metal thiosulfate and perchlorate; and.alkali or alkaline earth metal aluminates, silicates, and hydroxides, e.g., sodium hydroxide. Calcium salts are particularly advantageous, especially calcium nitrate, calcium chloride, calcium formate, and calcium nitrite. Calcium nitrate is preferred.
The fatty acid aminosulfonic acid, which is believed to operate as an air entraining agent in a hydraulic cement composition, may be an alkali or alkali earth metal salt of an N-alkyl-N-tall oil aminosulfonic acid, having the general formula
CH3(CH2)X— CH=CH(CH2)y— CO— NR— (CH2) — SO3 " Mn+ wherein
"R" is a hydrogen, alkyl group or aryl group; "x" is 1 to 10;
"y" is 3 - 10; "z" is 1 to 10;
"M" is an alkali or alkaline earth metal, ammonium, or alkyl ammonium ion; and "n" is 1 to 3.
A preferred fatty acid aminosulfonic acid surfactant comprises sodium N-methyl-N- oleoyl taurate, which is available from Rhone-Poulenc, Cranbury, New Jersey, under the tradename Igepon T-33.
The water reducing agent may be an alkali or alkaline earth metal salt of lignosulfonic acid, polycarboxylic acid, napthalene sulfonic acid condensate, melamine sulfonic acid condensate, hydroxylated carboxylic acids, and carbohydrates
such as corn syrup. Preferably, the water reducing agent is a lignosulfonate, such as calcium lignosulfonate.
Early strength enhancing agents are known, as is the term "early strength," by which is meant compressive strength at 1 - 3 days (see e.g., ASTM C-39). Early strength enhancing agents include alkanolamines. An alkanolamine is a generic term for a group of compounds in which trivalent nitrogen is attached directly to a carbon atom of an alkyl alcohol, and examples are monoethanolamine, diethanolamine, and triethanolamine. Alkanolamines also include methyldiethanolamine and triisopropanolamine.
Preferred multi-functional admixtures of the invention are preferably used in an amount of 0.05-1.0% s/s based on cement in the concrete, where "% s/s" designates percent admixture solids on cement solids. A preferred admixture may comprise calcium nitrate in the range of 90-99.5% s/s and sodium N-methyl oleoyl taurate in the range of 0.5-10.0% s/s. Another preferred admixture comprises calcium nitrate (50-90% s/s); calcium lignosulfonate (5.0-40.0% s/s); triethanolamine or triisopropanolamine (0.1 -5.0% s/s); and sodium N-methyl oleoyl taurate (0.01-5.0% s/s).
Claims
1. A multifunctional, hydraulic cement composition admixture comprising: a set accelerator which is an alkali or alkaline earth metal salt which is a salt of an organic or inorganic acid, and a fatty acid aminosulfonic acid surfactant.
2. The admixture of claim 1 wherein the set accelerator comprises calcium nitrate, calcium chloride, calcium formate, or calcium nitrite; and the fatty acid aminosulfonic acid has the general formula
CH3(CH2)X— CH=CH(CH2)y— CO— NR— (CH2)Z— SO3 ^ Mn+ wherein
"R" is a hydrogen, alkyl group or aryl group; "x" is 1 to 10;
"y" is 3 - 10; "z" is 1 to 10;
"M" is an alkali or alkaline earth metal, ammonium, or alkyl ammonium ion; and "n" is l to 3.
3. The admixture of claim 2 wherein said fatty acid amino sulfonic acid comprises sodium N-methyl oleoyl taurate.
4. The admixture of claim 2 further comprising a water reducing agent comprising an alkali or alkaline earth metal salt of lignosulfonic acid, polycarboxylic acid, napthalene sulfonic acid condensate, melamine sulfonic acid condensate, hydroxylated carboxylic acids, or a carbohydrate.
5. The admixture of claim 4 wherein said water reducing agent comprises calcium lignosulfonate.
6. The admixture of claim 2 further comprising an early strength enhancing agent.
7. The admixture of claim 6 wherein said early strength enhancing agent comprises an alkanolamine.
8. The admixture of claim 7 wherein said alkanolamine comprises triethanolamine or triisopropanolamine.
9. The admixture of claim 1 wherein said set accelerator comprises calcium nitrate, said fatty acid aminosulfonic acid surfactant comprises sodium N- methyl oleoyl taurate, and said admixture further comprises calcium lignosulfonate and triethanolamine.
10. A hydraulic cement composition comprising portland cement, a calcium salt set accelerator, and a fatty acid aminosulfonic acid surfactant.
11. The cement composition of claim 10 further comprising at least one aggregate.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51980097A JP4251505B2 (en) | 1995-11-17 | 1996-11-15 | Multi-purpose mixture for hydraulic cement compositions |
| KR1019980703599A KR100579778B1 (en) | 1995-11-17 | 1996-11-15 | Multipurpose Mixture for Hydraulic Cement Composition |
| AU77336/96A AU7733696A (en) | 1995-11-17 | 1996-11-15 | Multipurpose admixture for hydraulic cement composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US690095P | 1995-11-17 | 1995-11-17 | |
| US60/006,900 | 1995-11-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1997019032A1 true WO1997019032A1 (en) | 1997-05-29 |
Family
ID=21723171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1996/018300 WO1997019032A1 (en) | 1995-11-17 | 1996-11-15 | Multipurpose admixture for hydraulic cement composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4251505B2 (en) |
| KR (1) | KR100579778B1 (en) |
| AU (1) | AU7733696A (en) |
| WO (1) | WO1997019032A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999002465A1 (en) * | 1997-07-10 | 1999-01-21 | Nyfotek As | Set-accelerating mixture for concrete |
| JP2001302309A (en) * | 2000-04-25 | 2001-10-31 | Seltec Corp | Production process of instant stripping concrete product |
| US6485561B1 (en) * | 2000-03-03 | 2002-11-26 | Clinton D. Dattel | Low density cellular concrete with accelerators for rapid hardening |
| JP2003502260A (en) * | 1999-06-15 | 2003-01-21 | ダブリュ・アール・グレイス・アンド・カンパニー・コネテイカット | High initial strength cement and additive and method for producing the same |
| US20120041103A1 (en) * | 2009-02-17 | 2012-02-16 | Chryso | Fast Hydraulic Binder for Parts and Constructions Made of Concrete Containing A Calcium Salt |
| AT514510A1 (en) * | 2013-06-26 | 2015-01-15 | Baustofftechnik Gmbh | Künettenfüllmaterial |
| US9353004B2 (en) | 2011-03-15 | 2016-05-31 | Kao Corporation | Dispersant for a hydraulic composition |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100888243B1 (en) * | 2007-06-19 | 2009-03-10 | 주식회사 실크로드시앤티 | Accelerated admixture composition for increasing the miscibility of winter fly ash |
| EP2105419A1 (en) * | 2008-03-28 | 2009-09-30 | Lafarge | Additives for cement |
| JP5467588B2 (en) * | 2008-07-17 | 2014-04-09 | 原嶋 友子 | Cement admixture, mortar or concrete production method and mortar or concrete product |
| KR100911721B1 (en) * | 2008-09-30 | 2009-08-10 | 나종천 | Admixtures, Mortars and Concrete Including Admixtures |
| JP5006466B2 (en) * | 2010-11-19 | 2012-08-22 | 花王株式会社 | Dispersant for hydraulic composition |
| JP6054736B2 (en) * | 2012-12-21 | 2016-12-27 | 花王株式会社 | Hydraulic composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5316572A (en) * | 1989-12-11 | 1994-05-31 | Nmb Ltd. | Method of manufacturing concrete for placement in air not requiring consolidation |
| US5322562A (en) * | 1990-07-12 | 1994-06-21 | Sandoz Ltd. | Production of cement-mortar dry mix |
| US5352290A (en) * | 1991-06-25 | 1994-10-04 | Jdc Corporation | Concrete composition |
| US5432212A (en) * | 1993-04-05 | 1995-07-11 | W. R. Grace & Co.-Conn. | Dispersant composition for cement having excellent property in inhibition of slump-loss |
-
1996
- 1996-11-15 JP JP51980097A patent/JP4251505B2/en not_active Expired - Fee Related
- 1996-11-15 KR KR1019980703599A patent/KR100579778B1/en not_active Expired - Fee Related
- 1996-11-15 WO PCT/US1996/018300 patent/WO1997019032A1/en active IP Right Grant
- 1996-11-15 AU AU77336/96A patent/AU7733696A/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5316572A (en) * | 1989-12-11 | 1994-05-31 | Nmb Ltd. | Method of manufacturing concrete for placement in air not requiring consolidation |
| US5322562A (en) * | 1990-07-12 | 1994-06-21 | Sandoz Ltd. | Production of cement-mortar dry mix |
| US5352290A (en) * | 1991-06-25 | 1994-10-04 | Jdc Corporation | Concrete composition |
| US5432212A (en) * | 1993-04-05 | 1995-07-11 | W. R. Grace & Co.-Conn. | Dispersant composition for cement having excellent property in inhibition of slump-loss |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999002465A1 (en) * | 1997-07-10 | 1999-01-21 | Nyfotek As | Set-accelerating mixture for concrete |
| JP2003502260A (en) * | 1999-06-15 | 2003-01-21 | ダブリュ・アール・グレイス・アンド・カンパニー・コネテイカット | High initial strength cement and additive and method for producing the same |
| JP4883859B2 (en) * | 1999-06-15 | 2012-02-22 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | High initial strength cement and additive and method for producing the same |
| US6485561B1 (en) * | 2000-03-03 | 2002-11-26 | Clinton D. Dattel | Low density cellular concrete with accelerators for rapid hardening |
| JP2001302309A (en) * | 2000-04-25 | 2001-10-31 | Seltec Corp | Production process of instant stripping concrete product |
| US20120041103A1 (en) * | 2009-02-17 | 2012-02-16 | Chryso | Fast Hydraulic Binder for Parts and Constructions Made of Concrete Containing A Calcium Salt |
| US8992680B2 (en) * | 2009-02-17 | 2015-03-31 | Lafarge | Fast hydraulic binder for parts and constructions made of concrete containing a calcium salt |
| US9353004B2 (en) | 2011-03-15 | 2016-05-31 | Kao Corporation | Dispersant for a hydraulic composition |
| AT514510A1 (en) * | 2013-06-26 | 2015-01-15 | Baustofftechnik Gmbh | Künettenfüllmaterial |
| AT514510B1 (en) * | 2013-06-26 | 2018-01-15 | Baustofftechnik Gmbh | Künettenfüllmaterial |
Also Published As
| Publication number | Publication date |
|---|---|
| AU7733696A (en) | 1997-06-11 |
| KR100579778B1 (en) | 2006-10-24 |
| KR19990067576A (en) | 1999-08-25 |
| JP2000511151A (en) | 2000-08-29 |
| JP4251505B2 (en) | 2009-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0077129B1 (en) | Additive for hydraulic cement mixes | |
| USRE35194E (en) | Admixture for hydraulic cement | |
| US5211751A (en) | Hydraulic cement set-accelerating admixtures incorporating amino acid derivatives | |
| JP5140215B2 (en) | Compatible admixtures for use in hydraulic cement blends including hydraulic cements and cement substitutes | |
| KR0133274B1 (en) | Hydraulic cement set-accelerating admixtures incorporating glycols | |
| US20090050023A1 (en) | Method for accelerating the setting and hardening of hydraulic binding agents and mixtures containing the same | |
| US5348583A (en) | Hydraulic cement set-accelerating admixtures incorporating glycols | |
| WO1997019032A1 (en) | Multipurpose admixture for hydraulic cement composition | |
| AU582203B2 (en) | Additive for hydraulic cement mixes | |
| JP3339619B2 (en) | Additives for cement-based materials and cement-based materials | |
| EP0159322A1 (en) | ADDITIVE FOR HYDRAULIC CEMENT MIXTURES. | |
| US6818057B2 (en) | Retarder for calcium sulfoaluminate cements | |
| AU696359B2 (en) | Hydraulic cement set accelerators based on nitroalcohols | |
| JP3224276B2 (en) | Cement additives and defoamers | |
| JP5688069B2 (en) | Cement composition, mortar or concrete using the same | |
| JP4128300B2 (en) | Cement admixture and cement composition | |
| JPS61106449A (en) | Improvement for properties of cement mortar and concrete | |
| US4015993A (en) | Hydraulic composition with additive | |
| JP2009234890A (en) | Cement composition and mortar or concrete produced by using the same | |
| CA1275425C (en) | Set accelerating and early-strength enhancing admixtures for concrete compositions | |
| HK1017662A (en) | Multipurpose admixture for hydraulic cement composition | |
| CN1207088A (en) | Multipurpose admixture for hydraulic cement composition | |
| AU565349B2 (en) | Admixture for hydraulic cement mixes | |
| JPS6060962A (en) | Admixing agent for concrete | |
| JPS63123849A (en) | Cement admixing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WWE | Wipo information: entry into national phase |
Ref document number: 96199546.7 Country of ref document: CN |
|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DE DK EE ES FI GB GE HU IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG US UZ VN AM AZ BY KG KZ MD RU TJ TM |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF |
|
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 1019980703599 Country of ref document: KR |
|
| REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
| 122 | Ep: pct application non-entry in european phase | ||
| NENP | Non-entry into the national phase |
Ref country code: CA |
|
| WWP | Wipo information: published in national office |
Ref document number: 1019980703599 Country of ref document: KR |
|
| WWG | Wipo information: grant in national office |
Ref document number: 1019980703599 Country of ref document: KR |