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US 2013/0074736 A1Published application
Chemical Admixtures for Hydraulic Cements
OwnerIqbal Gillinventor
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Abstract
This invention relates to a new class of chemical admixtures for hydraulic cement compositions such as pastes, mortars, grouts and concretes. The cement compositions are comprised of ordinary Portland cement, blended cements, or non-Portland cements made with Supplementary Cementitious Materials. The admixtures contain complexes of metals with derivatives of hydroxycarboxylic acids, and improve properties of cement compositions, including setting, hardness, compressive strength, shrinkage, and freeze-thaw resistance. The invention discloses a method for improving the properties of hydraulic cements by adding the disclosed chemical admixtures to cement compositions, and also discloses methods of preparing said admixtures.
Claims18
1:
- A method for improving the properties of a hydraulic cement composition comprising adding a chemical admixture to said hydraulic cement composition, wherein the chemical admixture comprises complexes of metals with hydroxycarboxylic acid derived ligands, complexes of semi-metals with hydroxycarboxylic acid derived ligands, and any combination thereof, represented by the formula:
- A1a . . . AnxB1a′ . . . Bnx′[M1a″ . . . Mnx″C1a′″ . . . Cnx′″L1a″″ . . . Lnx″″] such that:
- A1 through An are a plurality of cations, wherein n is a number equal to or greater than 1;
- B1 through Bn are a plurality of anions, wherein n is a number equal to or greater than 1;
- M1 through Mn are a plurality of chelated metal or semi-metal cations, wherein n is a number equal to or greater than 1;
- C1 through Cn are a plurality of coordinating ligands, wherein n is a number equal to or greater than 1;
- L1 through Ln are a plurality of chelating hydroxycarboxylic acid derived ligands, wherein n is a number equal to or greater than 1;
- a and x are cation stoichiometries and represent numbers equal to or greater than 0;
- a′ and x′ are anion stoichiometries and represent numbers equal to or greater than 0;
- a″ and x″ are chelated metal stoichiometries and represent numbers equal to or greater than 1;
- a′″ and x′″ are coordinating ligand stoichiometries and represent numbers equal to or greater than 0;
- and
- a″″ and x″″ are chelating hydroxcarboxylic acid-derived ligand stoichiometries and represent numbers equal to or greater than 1.
10 more elements
2:
- The method of claim 1 wherein said chemical admixture includes at least one member of the group consisting of glycolatoaluminum(III), sodium glycolatoaluminate(III), lactatoaluminum(III), sodium lactatoaluminate(III), malatoalumin(III), sodium malatoaluminate(III), citratoaluminum(III), sodium citratoaluminate(III), sodium 2-hydroxybutyratoaluminate(III), sodium 3-hydroxybutyratoaluminate(III), sodium citramalatoaluminate(III), sodium tartaratoaluminate(III), sodium mucatoaluminate(III), sodium 2,3-dihydroxybenzoatoaluminate(III), sodium caffeatoaluminate(III), sodium chlorogenatoaluminate(III), sodium malatoaluminate(III), sodium chloridomalatoaluminate(III), sodium malatosulfatoaluminate(III), lithium glycolatoaluminate(III), lithium lactatoaluminate(III), lithium malatoaluminate(III), lithium citratoaluminate(III), potassium glycolatoaluminate(III), potassium lactatoaluminate(III), potassium malatoaluminate(III), potassium citratoaluminate(III), magnesium citratoaluminate(III), calcium citratoaluminate(III), sodium acetatomalatoaluminate(III), sodium acetatocitratoaluminate(III), sodium malatotartaratoaluminate(III), sodium citratotartaratoaluminate(III), sodium citratomalatoaluminate(III), sodium boromalatoaluminate(III), sodium borocitratoaluminate(III), sodium citratophosphatoaluminate(III), sodium carbonatocitratoaluminate(III), calcium carbonatocitratoaluminate(III), sodium calcium carbonatocitratoaluminate(III), magnesium carbonatocitratoaluminate(III), malatobismuth(III), sodium malatobismuthate(III), citratobismuth(III), sodium citratobismuthate(III), sodium borocitratobismuthate(III), sodium malatoaluminate(III)bismuthate(III), sodium citratoaluminate(III)bismuthate(III), sodium citratomagnesate(II), sodiumcitratocalcate(II), sodium malatoindate(III), sodium malatogallate(III), sodium malatoferrate(III), sodium malatozincate(II), sodium malatozirconate(IV), sodium malatolanthanate(III), sodiummalatoyttrate(III), sodium citratomolybdate(VI), and sodium citratotungstate(VI).
3:
- The method of claim 1 wherein said hydraulic cement composition comprises Portland cement, Portland cement and Type F fly ash, Portland cement and electric arc furnace slag, Portland cement and limestone powder, Portland cement and brucite, Type C fly ash, Type C fly ash and Type F fly ash, Basic Oxygen Furnace Slag, and Basic Oxygen Furnace Slag and Electric Arc Furnace Slag, or any combination thereof.
4:
- The method of claim 1 wherein said properties of the hydraulic cement composition comprise set time, hardness, compressive strength, shrinkage, water permeability and freeze-thaw resistance.
5:
- The method of claim 1 wherein the plurality of cations A1 through An includes at least one member of the group consisting of the hydronium ion, cations of Group IA elements, and cations of Group IIA elements.
6:
- The method of claim 1 wherein the plurality of cations A1 through An includes at least one member of the group consisting of the hydronium ion, lithium(I), sodium(I), potassium(I), magnesium(II), and calcium(II).
7:
- The method of claim 1 wherein the plurality of anions B1 through Bn includes at least one member of the group consisting of anions of Group IVA elements, anions of Group VA elements, anions of Group VIA elements, and anions of Group VIIA elements.
8:
- The method of claim 1 wherein the plurality of anions B1 through Bn includes at least one member of the group consisting of trioxocarbonate(IV), tetraoxophosphate(V), tetraoxosulfate(VI), and chloride.
9:
- The method of claim 1 wherein the plurality of chelated metal or semi-metal cations M1 through Mn includes at least one member of the group consisting of cations of Group IIA elements, cations of Group IIIA elements, cations of Group VA elements, cations of Group IIB elements, cations of Group IIIB elements, cations of Group IVB elements, cations of Group VIB elements, and cations of Group VIIIB elements.
10:
- The method of claim 1 wherein the plurality of chelated metal or semi-metal cations M1 through Mn includes at least one member of the group consisting of magnesium(II), calcium(II), yttrium(III), lanthanum(III), cerium(III), titanium(IV), zirconium(IV), molybdenum(VI), tungsten(VI), iron(III), zinc(II), boron(III), aluminum(III), gallium(III), indium(III), bismuth(III), and zirconium(IV).
11:
- The method of claim 1 wherein the plurality of coordinating ligands C1 through Cn includes at least one member of the group consisting of anions of Group IIIA elements, anions of Group IVA elements, and aliphatic carboxylic acids.
12:
- The admixture of claim 1 wherein the plurality of coordinating ligands C1 through Cn includes at least one member of the group consisting of water, trioxoborate(III), and ethanoate.
13:
- The method of claim 1 wherein the plurality of chelating hydroxycarboxylic acid-derived ligands L1 through Ln includes at least one member of the group consisting of anions of hydroxycarboxylic acids with a single hydroxyl group and a single carboxylic acid group, anions of hydroxycarboxylic acids with two or more hydroxyl groups and one carboxylic acid group, anions of hydroxycarboxylic acids with one hydroxyl group and two or more carboxylic acid groups, and anions of hydroxycarboxylic acids with two or more hydroxyl groups and two or more carboxylic acid groups.
14:
- The method of claim 1 wherein the plurality of chelating hydroxycarboxylic acid-derived ligands L1 through Ln includes at least one member of the group consisting of hydroxyacetate, 2-hydroxypropanoate, 2-hydroxybutanoate, 3-hydroxybutanoate, 2-hydroxybutane-1,4-dioate, 2-hydroxy-2-methylbutane-1,4-dioate, 3-carboxy-3-hydroxypentane-1,5-dioate, 2,3-dihydroxybutane-1,4-dioate, 2,3,4,5-tetrahydroxyhexane-1,6-dioate, 2,3-dihydroxybenzoate, 3-(3′,4′-dihydroxyphenyl)prop-2-enoate), and chlorogenate.
15:
- The method of claim 1 wherein said admixture is prepared by reacting at least one member of a group consisting of an oxide, hydroxide, carbonate or basic carbonate of a Group IIA, Group IIIA, Group VA, Group IIB, Group IIIB, Group IVB, Group VIB, and a Group VIIIB element with at least one hydroxycarboxylic acid-derived ligand.
16:
- The method of claim 1 wherein said admixture is prepared by reacting at least one member of a group consisting of an oxide, hydroxide, carbonate or basic carbonate of a Group IIA, Group IIIA, Group VA, Group IIB, Group IIIB, Group IVB, Group VIB, and a Group VIIIB element with at least one hydroxycarboxylic acid-derived ligand, and at least one member of the group consisting of an oxide, hydroxide, carbonate, and hydrogen carbonate of a Group IA or a Group IIA metal.
17:
- The method of claim 1 wherein said admixture is prepared by reacting at least one member of a group consisting of an oxometallate compound of a Group IA element and a Group IIIA element, with at least one hydroxycarboxylic acid-derived ligand.
18:
- The method of claim 1 wherein said admixture is prepared by reacting at least one member of the group consisting of an oxide, hydroxide, carbonate, basic carbonate or hydrogencarbonate of a Group IA or a Group IIA element with a salt of at least one member of the group consisting of a Group IIA, Group IIIA, Group VA, Group IIB, Group IIIB, Group IVB, Group VIB and a Group VIIIB element with at least one member of the group consisting of a Group IIIA, Group IVA, Group VA, Group VIA and Group VIIA nonmetal with at least one hydroxycarboxylic acid-derived ligand.