[go: up one dir, main page]

WO2014067721A1 - Alkali-activated aluminosilicate binder with superior freeze-thaw stability - Google Patents

Alkali-activated aluminosilicate binder with superior freeze-thaw stability Download PDF

Info

Publication number
WO2014067721A1
WO2014067721A1 PCT/EP2013/070076 EP2013070076W WO2014067721A1 WO 2014067721 A1 WO2014067721 A1 WO 2014067721A1 EP 2013070076 W EP2013070076 W EP 2013070076W WO 2014067721 A1 WO2014067721 A1 WO 2014067721A1
Authority
WO
WIPO (PCT)
Prior art keywords
salt
use according
binder
alkali
weight
Prior art date
Application number
PCT/EP2013/070076
Other languages
French (fr)
Inventor
Samuele Beraldo
Nicola MONTAGNER
Dal Bo ALESSANDRO
Original Assignee
Construction Research & Technology Gmbh
Basf Schweiz Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Construction Research & Technology Gmbh, Basf Schweiz Ag filed Critical Construction Research & Technology Gmbh
Priority to ES13766374.6T priority Critical patent/ES2659792T3/en
Priority to CA2889428A priority patent/CA2889428C/en
Priority to RU2015120460A priority patent/RU2648735C2/en
Priority to JP2015540079A priority patent/JP6305420B2/en
Priority to EP13766374.6A priority patent/EP2914562B1/en
Priority to US14/432,624 priority patent/US9242898B2/en
Priority to BR112015005433-1A priority patent/BR112015005433B1/en
Priority to AU2013339753A priority patent/AU2013339753B2/en
Priority to CN201380056756.1A priority patent/CN104854057B/en
Publication of WO2014067721A1 publication Critical patent/WO2014067721A1/en

Links

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
    • 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
    • C04B24/128—Heterocyclic nitrogen 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
    • 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
    • C04B28/021—Ash cements, e.g. fly ash cements ; Cements based on incineration residues, e.g. alkali-activated slags from waste incineration ; Kiln dust 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • 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
    • C04B24/121—Amines, polyamines
    • 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
    • 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
    • C04B24/123—Amino-carboxylic acids
    • 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
    • C04B28/18—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 mixtures of the silica-lime 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
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00146—Sprayable or pumpable mixtures
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C04B2111/00517—Coating or impregnation materials for masonry
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00637—Uses not provided for elsewhere in C04B2111/00 as glue or binder for uniting building or structural materials
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
    • C04B2111/00672—Pointing or jointing materials
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00715—Uses not provided for elsewhere in C04B2111/00 for fixing bolts or the like
    • 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
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/29—Frost-thaw resistance
    • 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
    • C04B2111/60—Flooring materials
    • C04B2111/62—Self-levelling compositions
    • 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
    • C04B2111/72—Repairing or restoring existing buildings or building materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • Alkali-activated aluminosilicate binder with superior freeze-thaw stability Alkali-activated aluminosilicate binder with superior freeze-thaw stability
  • the present invention relates to the use of at least one nitrogen-containing organic compound and/or a salt thereof in combination with at least one aromatic carboxylic acid and/or a salt thereof for improving the freeze-thaw stability of an alkali-activated aluminosilicate binder, as well as a stabilized alkali-activated aluminosilicate binder.
  • the stability of building products to external influences is generally of great importance.
  • the present invention will mainly focus on the aspect of freeze-thaw stability as this is an essential feature of building products.
  • Freeze-thaw cycles relate to the climatic change of temperatures around the freezing point of water. Particularly in mineral binders such as concrete freeze-thaw cycles constitute a mechanism of deterioration. These construction materials exhibit a capillary porous structure and are not water-tight. If a water-impregnated structure of this kind is subjected to temperatures below 0 °C the water freezes within the pores. Due to the density anomaly of water the ice now expands. This results in a deterioration of the durability of the construction material. Moreover, there is a capillary pumping effect because of the expansion and contraction of the material itself through these freeze-thaw cycles which increases water uptake and thus deterioration.
  • Portland cement was mentioned for the first time in the British Patent BP 5022 and has been continually developed further since then.
  • Modern Portland Cement contains about 70% by weight of CaO + MgO, about 20% by weight of Si0 2 and about 10% by weight of AI2O3 + Fe203. Due to its high CaO content, it hardens hydraulically. Cured Portland Cement, however, exhibits capillary pores into which water tends to migrate during warm periods and to disintegrate the cured cement during freezing periods.
  • latent hydraulic binders as additions to Portland Cement.
  • Activation by means of strong alkalis such as alkali metal hydroxides or water glasses is also possible.
  • They can be employed as mortars or concretes by mixing with fillers (e.g. silica sand having an appropriate particle size) and additives.
  • Blast furnace slag a typical latent hydraulic binder, generally comprises from 30 to 45% by weight of CaO, from about 4 to 17% by weight of MgO, from about 30 to 45% by weight of S1O2 and from about 5 to 15% by weight of AI2O3, typically about 40% by weight of CaO, about 10% by weight of MgO, about 35% by weight of S1O2 and about 12% by weight of AI2O3.
  • the cured products generally have the properties of hydraulically hardening systems.
  • Inorganic binder systems based on reactive water-insoluble compounds based on S1O2 in combination with AI2O3, which cure in aqueous alkaline medium, are likewise gener- ally known.
  • Such cured binder systems are also referred to as "alkali-activated alumi- nosilicate binders" or “geopolymers” and are described, for example, in US 4,349,386, WO 85/03699 and US 4,472,199.
  • the alkaline medium for activating the binder usually comprises aqueous solutions of alkali metal carbonates, alkali metal hydroxides, alkali metal aluminates and/or soluble water glass.
  • WO 08/012438 describes a further geopolymer cement based on low-CaO fly ash of type F, blast furnace slag and aqueous alkali metal silicate having an Si02:M20 ratio of more than 1 .28, preferably more than 1.45.
  • Si02:M20 ratio of more than 1 .28, preferably more than 1.45.
  • anhydrous oxides from about 45 to 50% by weight of S1O2, from about 20 to 26% by weight of AI2O3, from about 9 to 10% by weight of CaO and from about 3 to 4% by weight of K2O are present.
  • geopolymers can be less expensive and more stable and may have a more favorable CO2 emission balance. They generally tend to be acid-resistant but less alkali-resistant. These alkali-activated aluminosilicate binders in contrast to cement exhibit less porous surfaces and thus improved freeze-thaw stability.
  • required properties such as workability, strength development, dimensional stability, texture, etc. can often be achieved only by means of complex formulations. For instance fillers, thickeners, accelerators, water retention agents, defoaming agents, and/or pigments are often employed. By virtue of these additional components the porosity often increases, which in turn decreases the freeze-thaw stability of these products.
  • EP 1236702 A1 describes a water glass-containing building material mixture for the production of chemicals-resistant mortars based on a latent hydraulic binder, water glass and a metal salt from the group consisting of "metal hydroxide, metal oxide, carbon-containing metal salt, sulfur-containing metal salt, nitrogen-containing metal salt, phosphorus-containing metal salt, halogen-containing metal salt" as a controlling agent.
  • the latent hydraulic constituent can be granulated blast furnace slag.
  • Alkali metal salts, in particular lithium salts, are mentioned and used as the metal salt.
  • EP 1081 1 14 A1 describes a building material mixture for producing chemical-resistant mortars, where the building material mixture contains water glass powder and at least one water glass hardener. Furthermore, over 10% by weight of at least one latent hydraulic binder are present, and the building material mixture comprises at least one inorganic filler.
  • WO 1 1/064005 describes systems in which the binder cures in the form of a hybrid matrix in which a calcium silicate hydrate matrix and a geopolymer matrix are present in an appropriate ratio to one another and thus interpenetrate so that the overall matrix is both acid-resistant and alkali-resistant. However, the content of a nitrogen-containing organic compound and/or a salt thereof and an aromatic carboxylic acid and/or a salt thereof according to the present invention is absent in these binder systems.
  • a mixture of alkaline silicate solution, pulverulent latent-hydraulic material and additives is applied, for example by the dense-flow spraying process.
  • the additives comprise inert additives and/or opening materials or fillers, reinforcing agents, setting accelerators and moisture regulators.
  • the cured coating material has a high mechanical, thermal and chemical stability. Alcohols, amines and/or alkanolamines are used as moisture regulators. The inventors have set themselves the task of substantially avoiding at least some of the disadvantages of the prior art as discussed above.
  • the present invention thus provides as a first subject matter the use of at least one nitrogen-containing organic compound and/or a salt thereof in combination with at least one aromatic carboxylic acid and/or a salt thereof for improving the freeze-thaw stability of an alkali-activated aluminosilicate binder.
  • the nitrogen-containing organic compound suitable for the purpose of the present invention is suitably selected from the group consisting of amines, imidazoles, guani- dines, amides, imides, lactams, amino alcohols, amino acids, and betaines.
  • Amines can be selected from among primary, secondary and tertiary amines, and the amine salts are selected from among salts of primary, secondary and tertiary amines and also quaternary ammonium salts.
  • the amines can be aliphatic and/or aromatic amines. Tertiary amines are possible, secondary amines are preferred and primary amines are particularly preferred.
  • the system should not contain any curable epoxides. Generally the system should not contain any alkyl siliconates.
  • the molecular weight of the amines used can vary within a wide range.
  • Relatively high molecular weight compounds such as polyvinylamines and polyethylenimines, which can be obtained, for example, from BASF SE under the trade names Lupamin® and Lupasol®, respectively, are suitable.
  • the nitrogen-containing organic compound suitable for the purpose of the present invention can be selected from the group consisting of propylamine, butyl- amine, pentylamine, hexylamine, ethylenediamine, diaminopropane, diaminobutane, diaminopentane, neo-pentanediamine, diaminohexane, diethylenetriamine, tetraeth- ylenepentamine, ⁇ , ⁇ , ⁇ ', ⁇ '- tetramethyl-ethylenediamine, hexamethylenetetramine, 3- ethoxypropylamine, 2-(diethylamino)ethylamine, 3-(methylamino)propylamine, 3-(di- methylamino)propylamine, dibutylamine, 4,9-dioxadodecane-1 ,12-diamine, bis-(2-di- methylaminoethyl) ether, poly
  • ⁇ -Caprolactam is most preferred because it is in powder form and easily miscible in a powder mixture. Moreover, it is cheap and odorless. Many amines are liquid and often less miscible or stable in a high pH aluminosilicate binder.
  • the nitrogen-containing organic compound suitable for the purpose of the present invention can be selected from the group of imidazoles.
  • the molecular weight of the imidazoles used can vary within a wide range. Imidazoles having a molecular weight of less than 400 g/mol, in particular less than 200 g/mol, are particularly suitable for the purpose of the present invention.
  • an imidazole from the group consisting of imidazole, N-(3-aminopropyl)imidazole, 1 -methylimidazole, 1 -ethyl- imidazole, 1 -propylimidazole, 1 -butylimidazole, 1 -ethyl-3-methylimidazole, 1 -n-butyl-3- ethylimidazole, 1 ,3-dimethylimidazole, 1 ,2,3-trimethylimidazole, 1 -n-butyl-3-methylimid- azole, 1 ,3,4,5-tetramethylimidazole, 1 ,3,4-trimethylimidazole, 1 ,2-dimethylimidazole, 1 - butyl-2,3-dimethylimidazole, 3,4-dimethylimidazole, 2-ethyl-3,4-dimethylimidazole, 3- methyl-2-ethy
  • the nitrogen-containing organic compound suitable for the purpose of the present in- vention can also be selected from the group of guanidines.
  • the molecular weight of the guanidines used can vary within a wide range.
  • guanidines having molecular weights of less than 400 g/mol, in particular less than 150 g/mol are particularly suitable.
  • the nitrogen-containing organic compound suitable for the purpose of the present invention can also be an amide such as ⁇ , ⁇ -dimethylformamide, an imide such as male- imide, phtalimide, and succinimide, a lactam such as ⁇ -caprolactam, ⁇ -valerolactam, 2- pyrrolidone, 1 -methyl-2-pyrrolidone or an amino alcohol.
  • the molecular weight of the amino alcohols used can vary within a wide range. Amino alcohols having a molecular weight of less than 400 g/mol, in particular less than 150 g/mol, are particularly suitable for the purpose of the present invention.
  • amino alcohol from the group consisting of 3-amino-1 -propanol, monoethanolamine, triethanolamine, cho- line, trimethylaminoethylethanolamine, 1 -(2-hydroxyethyl)piperazine, 2-(2-aminoethoxy) ethanol, 3-dimethylaminopropan-1 -ol, 4-(2-hydroxyethyl)morpholine, butyldiethanol- amine, butylethanolamine, dimethylaminoethoxyethanol, N,N-dimethylethanolamine, N-methylethanolamine, diethanolamine, diisopropanolamine and N-(2-hydroxyethyl)- 2-pyrrolidone.
  • the salt of the nitrogen-containing organic compound can be a hydrogen ha- lide salt or a quaternary ammonium salt.
  • a preferred hydrogen halide would be hydrochloric acid.
  • Quaternization of the nitrogen-containing organic compound may be effected e.g. by reaction of the nitrogen-containing organic compound with methyl chloride or dimethyl sulfate.
  • Imidazolium salts, guanidinium salts and quaternary ammonium salts are highly suitable for the purpose of the present invention. Salts of this type having melting points below 100°C are also referred to as ionic liquids. The molecular weight can be varied within a wide range. Ionic liquids having a molecular weight of less than 400 g/mol, in particular less than 200 g/mol, are particularly suitable for the purpose of the present invention.
  • the ionic liquids are preferably salts having at least one cation selected from the group consisting of choline, tris-2-(hydroxyethyl)- methylammonium, methyl-tri-n-butylammonium, tetramethylammonium, tetrabutyl- ammonium, 1 -methylimidazolium, 1 -ethylimidazolium, 1 -propylimidazolium, 1 -butyl- imidazolium, 2-ethylpyridinium, 1 -ethyl-3-methylimidazolium, 1 -n-butyl-3-ethylimidazoli- um, 1 ,2-dimethylpyridinium, 1 -methyl-2-ethylpyridinium, 1 -methyl-2-ethyl-6-methylpyri- dinium, N-methylpyridinium, 1 -butyl-2-methylpyridinium, 1
  • aromatic carboxylic acid which is suitable for the purpose of the present invention can be selected from the group consisting of benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, and toluic acid.
  • the salt of the aromatic carboxylic acid is suitably selected from the group consisting of alkali metal salts, alkaline earth metal salts, aluminum salts, first row transition metal salts, and mixtures thereof.
  • first row transition metal is meant to indicate the transition metals from Sc to Zn.
  • Sodium benzoate is particularly preferred because it is relatively cheap, easily available and performs nicely.
  • the alkali-activated aluminosilicate binder comprises at least one latent hydraulic and/ or pozzolanic binder and at least one salt selected from among alkali metal oxides, al- kali metal hydroxides, alkali metal carbonates, alkali metal silicates, alkali metal alumi- nates, and mixtures thereof.
  • the latent hydraulic binder is, for example, selected from among slags, in particular blast furnace slag, granulated blast furnace slag, ground granulated blast furnace slag, electrothermal phosphorus slag, steel slag and mixtures thereof.
  • the slags can be either industrial slags, i.e. waste products from industrial processes, or synthetically pro- prised slags. The latter is advantageous since industrial slags are not always available in a constant amount and quality.
  • a “latent hydraulic binder” is preferably a bin- der in which the molar ratio of (CaO + MgO):Si02 is in the range from 0.8 to 2.5 and particularly preferably in the range from 1 .0 to 2.0.
  • Blast furnace slag is a waste product of the blast furnace process.
  • Granulated blast furnace slag is sometimes called slag sand.
  • Ground granulated blast furnace slag varies in fineness and particle size distribution depending on origin and treatment form, with the fineness having an influence on the reactivity.
  • the Blaine value which is typically in the order of from 200 to 1000, preferably from 300 to 500 m 2 kg- 1 . The more finely the blast furnace slag is milled, the higher the reactivity.
  • the typical composition of blast furnace slag has been mentioned above.
  • Electrothermal phosphorus slag is a waste product of electrothermal phosphorus production. It is less reactive than blast furnace slag and contains from about 45 to 50% by weight of CaO, from about 0.5% to 3% by weight of MgO, from about 38 to 43% by weight of S1O2, from about 2 to 5% by weight of AI2O3 and from about 0.2 to 3% by weight of Fe2C"3 and also fluoride and phosphate.
  • Steel slag is a waste product of various steel production processes and has a greatly variable composition (see Caijun Shi, Pavel V. Krivenko, Delia Roy, Alkali-Activated Cements and Concretes, Taylor & Francis, London & New York, 2006, pp. 42-51 ).
  • the pozzolanic binder is, for example, selected from among amorphous silica, preferably precipitated silica, pyrogenic silica and microsilica, glass flour, fly ash, for example brown coal fly ash and mineral coal fly ash, metakaolin, natural pozzolanas such as tuff, trass and volcanic ash, natural and synthetic zeolites and mixtures thereof.
  • amorphous silica preferably precipitated silica, pyrogenic silica and microsilica
  • glass flour for example brown coal fly ash and mineral coal fly ash, metakaolin, natural pozzolanas such as tuff, trass and volcanic ash, natural and synthetic zeolites and mixtures thereof.
  • the amorphous silica is preferably a X-ray amorphous silica, i.e. a silica which displays no crystallinity in the powder diffraction pattern.
  • glass flour should likewise be regarded as amorphous silica.
  • the amorphous silica used according to the invention suitably has an S1O2 content of at least 80% by weight, preferably at least 90% by weight.
  • Precipitated silica is obtained industrially from waterglass via precipitation processes. Depending on the production process, precipitated silica is also referred to as silica gel.
  • Pyrogenic silica is produced by reaction of chlorosilanes such as silicon tetrachloride in an oxyhydrogen flame. Pyrogenic silica is an amorphous S1O2 powder having a particle diameter of from 5 to 50 nm and a specific surface area of from 50 to 600 m 2 g -1 .
  • Microsilica is a by-product of silicon or ferrosilicon manufacture and likewise consists largely of amorphous S1O2 powder.
  • the particles have diameters in the order of about 0.1 ⁇ .
  • the specific surface area is in the order of from 15 to 30 m 2 g -1 .
  • commercial silica sand is crystalline and has comparatively large particles and a comparatively low specific surface area. It is used according to the invention as inert aggregate.
  • Fly ashes are formed, inter alia, in the combustion of coal in power stations.
  • Fly ash of class C contains, according to WO 08/012438, about 10% by weight of CaO
  • fly ashes of class F contain less than 8% by weight, preferably less than 4% by weight and typically about 2% by weight, of CaO.
  • Metakaolin is formed in the dehydration of kaolin. While kaolin gives off physically bound water at from 100 to 200°C, dehydroxylation with breakdown of the lattice structure and formation of metakaolin (AI2S12O7) takes place at from 500 to 800°C. Pure metakaolin accordingly contains about 54% by weight of S1O2 and about 46% by weight of
  • the above mentioned salt which is selected from among alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, alkali metal silicates, and alkali metal alu- minates, acts as an alkaline activator for the latent hydraulic and/or pozzolanic binder.
  • Alkali metal hydroxides and alkali metal silicates are preferred.
  • the alkali metal silicate is suitably selected from among compounds having the empirical formula m S1O2 ⁇ n M2O, wherein M is Li, Na, K or NH4, or a mixture thereof, preferably Na or K. (Ammonium is to be comprised herein although it is not an alkali metal.)
  • the molar ratio of m:n is from 0.5 to 3.6, preferably from 0.6 to 3.0 and in particular from 0.7 to 2.0.
  • the alkali metal silicate is suitably a water glass, preferably a liquid water glass and in particular a sodium or potassium water glass.
  • the ratio of m:n (also referred to as modulus) as indicated above should preferably not be exceeded since otherwise a complete reaction of the components can no longer be expected. It is also possible to employ lower moduli, e.g. about 0.2.
  • Water glasses having higher moduli should be brought to moduli in the range according to the invention by means of a suitable aqueous alkali metal hydroxide before use. Potassium water glasses in the suitable modulus range are commercially available mainly as aqueous solutions since they are highly hygroscopic; sodium water glasses in the suitable modulus range are also commercially available as solids.
  • the solids content of the aqueous water glass solutions is generally from 20% by weight to 60% by weight, preferably from 30 to 50% by weight.
  • Water glasses can be prepared industrially by melting of silica sand with the corres- ponding alkali metal carbonates. However, they can also be obtained without difficulty from mixtures of reactive silica with the corresponding aqueous alkali metal hydroxides. It is therefore possible, according to the invention, to replace at least part of the alkali metal silicate by a mixture of a reactive silica and the corresponding alkali metal hydroxide.
  • a hydraulic binder can be present.
  • the hydraulic binder is suitably selected from among cements, in particular Portland Cement, aluminate cement, and also mixtures thereof.
  • Portland Cement contains about 70% by weight of CaO + MgO, about 20% by weight of Si0 2 and about 10% by weight of Al 2 0 3 + Fe 2 0 3 .
  • Aluminate cement (high alumina cement) contains from about 20 to 40% by weight of CaO, up to about 5% by weight of S1O2, from about 40 to 80% by weight of AI2O3 and up to about 20% by weight of Fe2C"3. These types of cement are well known in the prior art.
  • the ratio of the nitrogen-containing organic compound and/or salt thereof to the aromatic carboxylic acid and/or salt thereof is suitably comprised within the range of from 1 : 1 to 1 : 10, preferably from 1 : 5 to 1 : 10.
  • a preferred alkali-activated aluminosilicate binder which is suitable for the purpose of the present invention comprises 5 to 95, preferably 20 to 80 % by weight of the latent hydraulic and/or pozzolanic binder, 5 to 50, preferably 10 to 40 % by weight of the alkali metal silicate, 0.01 to 30, preferably 0.1 to 10 and in particular 0.1 to 3 % by weight of the nitrogen-containing organic compound and/or a salt thereof, 0.01 to 30, preferab- ly 0.1 to 10 and in particular 0.5 to 5 % by weight of the aromatic carboxylic acid and/or a salt thereof, and 0 to 20, preferably 0 to 10 and in particular 0 to 5 % by weight of the hydraulic binder.
  • Possible inert fillers are e.g. gravels, sands and flours, for example those based on silica, limestone, barite or clay, in particular silica sand.
  • Lightweight fillers such as perlite, kieselguhr (diatomaceous earth), expanded mica (vermiculite) and foam sand can also be used.
  • Possible additives are e.g. plasticizers, antifoams, water retention agents, dispersants, pigments, fibers, redispersible powders, wetting agents, water proofing additives, set retarders, curing accelerators, complexing agents, and rheology modifiers. The amount of water required for setting is for the purpose of this invention not counted as a constituent of the binder.
  • alkali-activated aluminosilicate binder can be comprised in building material formulations and/or building products such as on-site concrete, finished concrete parts, concrete goods, concrete blocks and also in-situ concrete, spray concrete, ready-mixed concrete, building adhesives and thermal insulation composite system adhesives, concrete repair systems, one-component and two-component sealing slurries, screeds, knifing fillers and self-leveling compositions, tile adhesives, plasters and renders, adhesives and sealants, coating systems, in particular for tunnels, wastewater channels, spray protection and condensate lines, dry mortars, joint grouts, drainage mortars and/ or repair mortars.
  • building material formulations and/or building products such as on-site concrete, finished concrete parts, concrete goods, concrete blocks and also in-situ concrete, spray concrete, ready-mixed concrete, building adhesives and thermal insulation composite system adhesives, concrete repair systems, one-component and two-component sealing slurries, screeds, knif
  • the present invention provides as a further subject matter an alkali-activated aluminosilicate binder comprising blast furnace slag, granulated blast furnace slag and/ or ground granulated blast furnace slag as a latent hydraulic binder, microsilica, meta- kaolin and/or fly ash as a pozzolanic binder, sodium waterglass and/or potassium wa- terglass as an alkaline activator, and ⁇ -caprolactam and sodium benzoate as freeze- thaw stabilizers.
  • an alkali-activated aluminosilicate binder comprising blast furnace slag, granulated blast furnace slag and/ or ground granulated blast furnace slag as a latent hydraulic binder, microsilica, meta- kaolin and/or fly ash as a pozzolanic binder, sodium waterglass and/or potassium wa- terglass as an alkaline activator, and ⁇ -caprolactam and sodium benzoate as freeze-
  • the cycles were carried out according to ASTM C 679-92, i. e. 16 h at -19 °C and 8 h at +23 °C while the specimens were in a bath of 4 % b.w. of aqueous CaC solution.

Landscapes

  • 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)
  • Combustion & Propulsion (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

We herewith propose the use of at least one nitrogen-containing organic compound and/or a salt thereof in combination with at least one aromatic carboxylic acid and/or a salt thereof for improving the freeze-thaw stability of an alkali-activated aluminosilicate binder, and a preferred alkali-activated aluminosilicate binder comprising ε-caprolactam and sodium benzoate as freeze-thaw stabilizers.

Description

Alkali-activated aluminosilicate binder with superior freeze-thaw stability
The present invention relates to the use of at least one nitrogen-containing organic compound and/or a salt thereof in combination with at least one aromatic carboxylic acid and/or a salt thereof for improving the freeze-thaw stability of an alkali-activated aluminosilicate binder, as well as a stabilized alkali-activated aluminosilicate binder.
Similar systems are described in WO 10/130582. In particular it is stated that certain organic additives (especially amines) considerably reduce the tendency of the alkali-ac- tivated aluminosilicate binder to shrink.
The stability of building products to external influences is generally of great importance. The present invention will mainly focus on the aspect of freeze-thaw stability as this is an essential feature of building products.
Freeze-thaw cycles relate to the climatic change of temperatures around the freezing point of water. Particularly in mineral binders such as concrete freeze-thaw cycles constitute a mechanism of deterioration. These construction materials exhibit a capillary porous structure and are not water-tight. If a water-impregnated structure of this kind is subjected to temperatures below 0 °C the water freezes within the pores. Due to the density anomaly of water the ice now expands. This results in a deterioration of the durability of the construction material. Moreover, there is a capillary pumping effect because of the expansion and contraction of the material itself through these freeze-thaw cycles which increases water uptake and thus deterioration. The number of freeze- thaw cycles to which the building product is exposed during its service live is thus of great influence for this deterioration process. For that reason test methods were generated to simulate the effects done by freeze-thaw cycles to the building products (from http://de.wikipedia.org/wiki/Frost-Tau-Wechsel, retrieved October 10, 2012). These methods (e.g. ASTM C 679-92) provide an indication of the freeze-thaw stability and therefore the durability of the building product itself.
Portland cement was mentioned for the first time in the British Patent BP 5022 and has been continually developed further since then. Modern Portland Cement contains about 70% by weight of CaO + MgO, about 20% by weight of Si02 and about 10% by weight of AI2O3 + Fe203. Due to its high CaO content, it hardens hydraulically. Cured Portland Cement, however, exhibits capillary pores into which water tends to migrate during warm periods and to disintegrate the cured cement during freezing periods.
Particular slags from metallurgical processes can be used as latent hydraulic binders as additions to Portland Cement. Activation by means of strong alkalis such as alkali metal hydroxides or water glasses is also possible. They can be employed as mortars or concretes by mixing with fillers (e.g. silica sand having an appropriate particle size) and additives. Blast furnace slag, a typical latent hydraulic binder, generally comprises from 30 to 45% by weight of CaO, from about 4 to 17% by weight of MgO, from about 30 to 45% by weight of S1O2 and from about 5 to 15% by weight of AI2O3, typically about 40% by weight of CaO, about 10% by weight of MgO, about 35% by weight of S1O2 and about 12% by weight of AI2O3. The cured products generally have the properties of hydraulically hardening systems.
Inorganic binder systems based on reactive water-insoluble compounds based on S1O2 in combination with AI2O3, which cure in aqueous alkaline medium, are likewise gener- ally known. Such cured binder systems are also referred to as "alkali-activated alumi- nosilicate binders" or "geopolymers" and are described, for example, in US 4,349,386, WO 85/03699 and US 4,472,199. Such systems generally comprise from 50 to 60% by weight of S1O2, from 20 to 25% by weight of AI2O3, no or little CaO and from 15 to 30% by weight of M20 (M = Na, K).
As reactive oxide mixture, it is possible to use microsilica, metakaolin, slags, fly ashes, activated clay or mixtures thereof. The alkaline medium for activating the binder usually comprises aqueous solutions of alkali metal carbonates, alkali metal hydroxides, alkali metal aluminates and/or soluble water glass.
WO 08/012438 describes a further geopolymer cement based on low-CaO fly ash of type F, blast furnace slag and aqueous alkali metal silicate having an Si02:M20 ratio of more than 1 .28, preferably more than 1.45. In the examples calculated on the basis of the anhydrous oxides, from about 45 to 50% by weight of S1O2, from about 20 to 26% by weight of AI2O3, from about 9 to 10% by weight of CaO and from about 3 to 4% by weight of K2O are present.
Compared to cements, geopolymers can be less expensive and more stable and may have a more favorable CO2 emission balance. They generally tend to be acid-resistant but less alkali-resistant. These alkali-activated aluminosilicate binders in contrast to cement exhibit less porous surfaces and thus improved freeze-thaw stability. However, required properties such as workability, strength development, dimensional stability, texture, etc. can often be achieved only by means of complex formulations. For instance fillers, thickeners, accelerators, water retention agents, defoaming agents, and/or pigments are often employed. By virtue of these additional components the porosity often increases, which in turn decreases the freeze-thaw stability of these products.
EP 1236702 A1 describes a water glass-containing building material mixture for the production of chemicals-resistant mortars based on a latent hydraulic binder, water glass and a metal salt from the group consisting of "metal hydroxide, metal oxide, carbon-containing metal salt, sulfur-containing metal salt, nitrogen-containing metal salt, phosphorus-containing metal salt, halogen-containing metal salt" as a controlling agent. The latent hydraulic constituent can be granulated blast furnace slag. Alkali metal salts, in particular lithium salts, are mentioned and used as the metal salt.
EP 1081 1 14 A1 describes a building material mixture for producing chemical-resistant mortars, where the building material mixture contains water glass powder and at least one water glass hardener. Furthermore, over 10% by weight of at least one latent hydraulic binder are present, and the building material mixture comprises at least one inorganic filler. WO 1 1/064005 describes systems in which the binder cures in the form of a hybrid matrix in which a calcium silicate hydrate matrix and a geopolymer matrix are present in an appropriate ratio to one another and thus interpenetrate so that the overall matrix is both acid-resistant and alkali-resistant. However, the content of a nitrogen-containing organic compound and/or a salt thereof and an aromatic carboxylic acid and/or a salt thereof according to the present invention is absent in these binder systems.
According to EP 0512269 A2, for large-area coating of various substrates in the building trade, a mixture of alkaline silicate solution, pulverulent latent-hydraulic material and additives is applied, for example by the dense-flow spraying process. The additives comprise inert additives and/or opening materials or fillers, reinforcing agents, setting accelerators and moisture regulators. The cured coating material has a high mechanical, thermal and chemical stability. Alcohols, amines and/or alkanolamines are used as moisture regulators. The inventors have set themselves the task of substantially avoiding at least some of the disadvantages of the prior art as discussed above. In particular, it was an object of the invention to substantially improve the freeze-thaw stability of an alkali-activated alu- minosilicate binder. The abovementioned object is achieved by the features of the independent claims. The dependent claims relate to preferred embodiments.
It has been surprisingly found that the nitrogen-containing organic compound together with the aromatic carboxylic acid and/or their respective salts synergistically improve the freeze-thaw stability of alkali-activated aluminosilicate binders.
The present invention thus provides as a first subject matter the use of at least one nitrogen-containing organic compound and/or a salt thereof in combination with at least one aromatic carboxylic acid and/or a salt thereof for improving the freeze-thaw stability of an alkali-activated aluminosilicate binder. The nitrogen-containing organic compound suitable for the purpose of the present invention is suitably selected from the group consisting of amines, imidazoles, guani- dines, amides, imides, lactams, amino alcohols, amino acids, and betaines. Amines can be selected from among primary, secondary and tertiary amines, and the amine salts are selected from among salts of primary, secondary and tertiary amines and also quaternary ammonium salts. The amines can be aliphatic and/or aromatic amines. Tertiary amines are possible, secondary amines are preferred and primary amines are particularly preferred. In the case of amines the system should not contain any curable epoxides. Generally the system should not contain any alkyl siliconates.
The molecular weight of the amines used can vary within a wide range. Relatively high molecular weight compounds such as polyvinylamines and polyethylenimines, which can be obtained, for example, from BASF SE under the trade names Lupamin® and Lupasol®, respectively, are suitable. Low molecular weight amines having a molecular weight of less than 400 g/mol, preferably less than 300 g/mol and in particular less than 200 g/mol, are particularly suitable for the purpose of the present invention.
Preferably, the nitrogen-containing organic compound suitable for the purpose of the present invention can be selected from the group consisting of propylamine, butyl- amine, pentylamine, hexylamine, ethylenediamine, diaminopropane, diaminobutane, diaminopentane, neo-pentanediamine, diaminohexane, diethylenetriamine, tetraeth- ylenepentamine, Ν,Ν,Ν',Ν'- tetramethyl-ethylenediamine, hexamethylenetetramine, 3- ethoxypropylamine, 2-(diethylamino)ethylamine, 3-(methylamino)propylamine, 3-(di- methylamino)propylamine, dibutylamine, 4,9-dioxadodecane-1 ,12-diamine, bis-(2-di- methylaminoethyl) ether, polyetheramines (such as Polyetheramine D 230 from BASF SE), morpholine, N-ethylmorpholine, 2-pyrrolidone, N-methylpyrrolidone, imidazoli- done, imidazolidone hemihydrate, 2-piperidone, Ν,Ν'-dimethylpiperazine, melamine, 1 ,3,5-triazine, 2,4-diamino-1 ,3,5-triazine, ε-caprolactam, urea, and betaine. ε-Caprolactam is most preferred because it is in powder form and easily miscible in a powder mixture. Moreover, it is cheap and odorless. Many amines are liquid and often less miscible or stable in a high pH aluminosilicate binder. Furthermore, the nitrogen-containing organic compound suitable for the purpose of the present invention can be selected from the group of imidazoles. The molecular weight of the imidazoles used can vary within a wide range. Imidazoles having a molecular weight of less than 400 g/mol, in particular less than 200 g/mol, are particularly suitable for the purpose of the present invention. Preference is given to an imidazole from the group consisting of imidazole, N-(3-aminopropyl)imidazole, 1 -methylimidazole, 1 -ethyl- imidazole, 1 -propylimidazole, 1 -butylimidazole, 1 -ethyl-3-methylimidazole, 1 -n-butyl-3- ethylimidazole, 1 ,3-dimethylimidazole, 1 ,2,3-trimethylimidazole, 1 -n-butyl-3-methylimid- azole, 1 ,3,4,5-tetramethylimidazole, 1 ,3,4-trimethylimidazole, 1 ,2-dimethylimidazole, 1 - butyl-2,3-dimethylimidazole, 3,4-dimethylimidazole, 2-ethyl-3,4-dimethylimidazole, 3- methyl-2-ethylimidazole, 3-butyl-1 -methylimidazole, 3-butyl-1 -ethylimidazole, 3-butyl- 1 ,2-dimethylimidazole, 1 ,3-di-n-butylimidazole, 3-butyl-1 ,4,5-trimethylimidazole, 3-butyl- 1 ,4-dimethylimidazole, 3-butyl-2-methylimidazole, 1 ,3-dibutyl-2-methylimidazole, 3-bu- tyl-4-methylimidazole, 3-butyl-2-ethyl-4-methylimidazole, 3-butyl-2-ethylimidazole, 1 -methyl-3-octylimidazole and 1 -decyl-3-methylimidazole.
The nitrogen-containing organic compound suitable for the purpose of the present in- vention can also be selected from the group of guanidines. The molecular weight of the guanidines used can vary within a wide range. For the purpose of the present invention, guanidines having molecular weights of less than 400 g/mol, in particular less than 150 g/mol, are particularly suitable. Preference is given to at least one guanidine from the group consisting of 1 ,1 ,3,3-tetramethylguanidine, 1 ,1 -dimethylguandine and 1 ,1 - diethylguanidine.
The nitrogen-containing organic compound suitable for the purpose of the present invention can also be an amide such as Ν,Ν-dimethylformamide, an imide such as male- imide, phtalimide, and succinimide, a lactam such as ε-caprolactam, δ-valerolactam, 2- pyrrolidone, 1 -methyl-2-pyrrolidone or an amino alcohol. The molecular weight of the amino alcohols used can vary within a wide range. Amino alcohols having a molecular weight of less than 400 g/mol, in particular less than 150 g/mol, are particularly suitable for the purpose of the present invention. Preference is given to an amino alcohol from the group consisting of 3-amino-1 -propanol, monoethanolamine, triethanolamine, cho- line, trimethylaminoethylethanolamine, 1 -(2-hydroxyethyl)piperazine, 2-(2-aminoethoxy) ethanol, 3-dimethylaminopropan-1 -ol, 4-(2-hydroxyethyl)morpholine, butyldiethanol- amine, butylethanolamine, dimethylaminoethoxyethanol, N,N-dimethylethanolamine, N-methylethanolamine, diethanolamine, diisopropanolamine and N-(2-hydroxyethyl)- 2-pyrrolidone.
Moreover, the salt of the nitrogen-containing organic compound can be a hydrogen ha- lide salt or a quaternary ammonium salt. A preferred hydrogen halide would be hydrochloric acid. Quaternization of the nitrogen-containing organic compound may be effected e.g. by reaction of the nitrogen-containing organic compound with methyl chloride or dimethyl sulfate.
Imidazolium salts, guanidinium salts and quaternary ammonium salts are highly suitable for the purpose of the present invention. Salts of this type having melting points below 100°C are also referred to as ionic liquids. The molecular weight can be varied within a wide range. Ionic liquids having a molecular weight of less than 400 g/mol, in particular less than 200 g/mol, are particularly suitable for the purpose of the present invention. For the purpose of the present invention, the ionic liquids are preferably salts having at least one cation selected from the group consisting of choline, tris-2-(hydroxyethyl)- methylammonium, methyl-tri-n-butylammonium, tetramethylammonium, tetrabutyl- ammonium, 1 -methylimidazolium, 1 -ethylimidazolium, 1 -propylimidazolium, 1 -butyl- imidazolium, 2-ethylpyridinium, 1 -ethyl-3-methylimidazolium, 1 -n-butyl-3-ethylimidazoli- um, 1 ,2-dimethylpyridinium, 1 -methyl-2-ethylpyridinium, 1 -methyl-2-ethyl-6-methylpyri- dinium, N-methylpyridinium, 1 -butyl-2-methylpyridinium, 1 -butyl-2-ethylpyridinium, 1 - butyl-2-ethyl-6-methylpyridinium, N-butylpyridinium, 1 -butyl-4-methylpyridinium, 1 ,3- dimethylimidazolium, 1 ,2,3-trimethylimidazolium, 1-n-butyl-3-methylimidazolium,
1 ,3,4,5-tetramethylimidazolium, 1 ,3,4-trimethylimidazolium, 1 ,2-dimethylimidazolium, 1 - butyl-2,3-dimethylimidazolium, 3,4-dimethylimidazolium, 2-ethyl-3,4-dimethylimidazoli- um, 3-methyl-2-ethylimidazolium, 3-butyl-1 -methylimidazolium, 3-butyl-1 -ethylimidazo- lium, 3-butyl-1 ,2-dimethylimidazolium, 1 ,3-di-n-butylimidazolium, 3-butyl-1 ,4,5- trimeth- ylimidazolium, 3-butyl-1 ,4-dimethylimidazolium, 3-butyl-2-methylimidazolium, 1 ,3-dibu- tyl-2-methylimidazolium, 3-butyl-4-methylimidazolium, 3-butyl-2-ethyl-4-methylimidazo- lium, 3-butyl-2-ethylimidazolium, 1 -methyl-3-octylimidazolium, 1 -decyl-3-methylimidaz- olium and guanidinium and also at least one anion selected from the group consisting of chloride, bromide, iodide, acetate, methylsulfate, methanesulfonate, tosylate, sulfate, hydrogensulfate, phosphate, hydrogenphosphate, dihydrogenphosphate, dialkylphos- phate and bis(trifluoromethanesulfonyl) imide.
The aromatic carboxylic acid which is suitable for the purpose of the present invention can be selected from the group consisting of benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, and toluic acid.
Moreover, the salt of the aromatic carboxylic acid is suitably selected from the group consisting of alkali metal salts, alkaline earth metal salts, aluminum salts, first row transition metal salts, and mixtures thereof. The term "first row transition metal" is meant to indicate the transition metals from Sc to Zn. Sodium benzoate is particularly preferred because it is relatively cheap, easily available and performs nicely.
The alkali-activated aluminosilicate binder comprises at least one latent hydraulic and/ or pozzolanic binder and at least one salt selected from among alkali metal oxides, al- kali metal hydroxides, alkali metal carbonates, alkali metal silicates, alkali metal alumi- nates, and mixtures thereof.
The latent hydraulic binder is, for example, selected from among slags, in particular blast furnace slag, granulated blast furnace slag, ground granulated blast furnace slag, electrothermal phosphorus slag, steel slag and mixtures thereof. The slags can be either industrial slags, i.e. waste products from industrial processes, or synthetically pro- duced slags. The latter is advantageous since industrial slags are not always available in a constant amount and quality.
For the purpose of the present invention a "latent hydraulic binder" is preferably a bin- der in which the molar ratio of (CaO + MgO):Si02 is in the range from 0.8 to 2.5 and particularly preferably in the range from 1 .0 to 2.0.
Blast furnace slag is a waste product of the blast furnace process. Granulated blast furnace slag is sometimes called slag sand. Ground granulated blast furnace slag varies in fineness and particle size distribution depending on origin and treatment form, with the fineness having an influence on the reactivity. As a measure of the fineness, use is made of the Blaine value which is typically in the order of from 200 to 1000, preferably from 300 to 500 m2 kg-1. The more finely the blast furnace slag is milled, the higher the reactivity. The typical composition of blast furnace slag has been mentioned above.
Electrothermal phosphorus slag is a waste product of electrothermal phosphorus production. It is less reactive than blast furnace slag and contains from about 45 to 50% by weight of CaO, from about 0.5% to 3% by weight of MgO, from about 38 to 43% by weight of S1O2, from about 2 to 5% by weight of AI2O3 and from about 0.2 to 3% by weight of Fe2C"3 and also fluoride and phosphate. Steel slag is a waste product of various steel production processes and has a greatly variable composition (see Caijun Shi, Pavel V. Krivenko, Delia Roy, Alkali-Activated Cements and Concretes, Taylor & Francis, London & New York, 2006, pp. 42-51 ). The pozzolanic binder is, for example, selected from among amorphous silica, preferably precipitated silica, pyrogenic silica and microsilica, glass flour, fly ash, for example brown coal fly ash and mineral coal fly ash, metakaolin, natural pozzolanas such as tuff, trass and volcanic ash, natural and synthetic zeolites and mixtures thereof. An overview of pozzolanic binders which are suitable for the purpose of the present inven- tion may also be found in Caijun Shi, Pavel V. Krivenko, Delia Roy, pp. 51 -63.
The amorphous silica is preferably a X-ray amorphous silica, i.e. a silica which displays no crystallinity in the powder diffraction pattern. For the purpose of this invention, glass flour should likewise be regarded as amorphous silica.
The amorphous silica used according to the invention suitably has an S1O2 content of at least 80% by weight, preferably at least 90% by weight. Precipitated silica is obtained industrially from waterglass via precipitation processes. Depending on the production process, precipitated silica is also referred to as silica gel. Pyrogenic silica is produced by reaction of chlorosilanes such as silicon tetrachloride in an oxyhydrogen flame. Pyrogenic silica is an amorphous S1O2 powder having a particle diameter of from 5 to 50 nm and a specific surface area of from 50 to 600 m2 g-1. Microsilica is a by-product of silicon or ferrosilicon manufacture and likewise consists largely of amorphous S1O2 powder. The particles have diameters in the order of about 0.1 μηη. The specific surface area is in the order of from 15 to 30 m2 g-1. On the other hand, commercial silica sand is crystalline and has comparatively large particles and a comparatively low specific surface area. It is used according to the invention as inert aggregate.
Fly ashes are formed, inter alia, in the combustion of coal in power stations. Fly ash of class C contains, according to WO 08/012438, about 10% by weight of CaO, while fly ashes of class F contain less than 8% by weight, preferably less than 4% by weight and typically about 2% by weight, of CaO.
Metakaolin is formed in the dehydration of kaolin. While kaolin gives off physically bound water at from 100 to 200°C, dehydroxylation with breakdown of the lattice structure and formation of metakaolin (AI2S12O7) takes place at from 500 to 800°C. Pure metakaolin accordingly contains about 54% by weight of S1O2 and about 46% by weight of
The above mentioned salt, which is selected from among alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, alkali metal silicates, and alkali metal alu- minates, acts as an alkaline activator for the latent hydraulic and/or pozzolanic binder. Alkali metal hydroxides and alkali metal silicates are preferred. The alkali metal silicate is suitably selected from among compounds having the empirical formula m S1O2■ n M2O, wherein M is Li, Na, K or NH4, or a mixture thereof, preferably Na or K. (Ammonium is to be comprised herein although it is not an alkali metal.) The molar ratio of m:n is from 0.5 to 3.6, preferably from 0.6 to 3.0 and in particular from 0.7 to 2.0.
Moreover, the alkali metal silicate is suitably a water glass, preferably a liquid water glass and in particular a sodium or potassium water glass.
The ratio of m:n (also referred to as modulus) as indicated above should preferably not be exceeded since otherwise a complete reaction of the components can no longer be expected. It is also possible to employ lower moduli, e.g. about 0.2. Water glasses having higher moduli should be brought to moduli in the range according to the invention by means of a suitable aqueous alkali metal hydroxide before use. Potassium water glasses in the suitable modulus range are commercially available mainly as aqueous solutions since they are highly hygroscopic; sodium water glasses in the suitable modulus range are also commercially available as solids. The solids content of the aqueous water glass solutions is generally from 20% by weight to 60% by weight, preferably from 30 to 50% by weight.
Water glasses can be prepared industrially by melting of silica sand with the corres- ponding alkali metal carbonates. However, they can also be obtained without difficulty from mixtures of reactive silica with the corresponding aqueous alkali metal hydroxides. It is therefore possible, according to the invention, to replace at least part of the alkali metal silicate by a mixture of a reactive silica and the corresponding alkali metal hydroxide.
In addition, a small amount of a hydraulic binder can be present. The hydraulic binder is suitably selected from among cements, in particular Portland Cement, aluminate cement, and also mixtures thereof. As indicated hereinabove, Portland Cement contains about 70% by weight of CaO + MgO, about 20% by weight of Si02 and about 10% by weight of Al203 + Fe203. Aluminate cement (high alumina cement) contains from about 20 to 40% by weight of CaO, up to about 5% by weight of S1O2, from about 40 to 80% by weight of AI2O3 and up to about 20% by weight of Fe2C"3. These types of cement are well known in the prior art.
The ratio of the nitrogen-containing organic compound and/or salt thereof to the aromatic carboxylic acid and/or salt thereof is suitably comprised within the range of from 1 : 1 to 1 : 10, preferably from 1 : 5 to 1 : 10. A preferred alkali-activated aluminosilicate binder which is suitable for the purpose of the present invention comprises 5 to 95, preferably 20 to 80 % by weight of the latent hydraulic and/or pozzolanic binder, 5 to 50, preferably 10 to 40 % by weight of the alkali metal silicate, 0.01 to 30, preferably 0.1 to 10 and in particular 0.1 to 3 % by weight of the nitrogen-containing organic compound and/or a salt thereof, 0.01 to 30, preferab- ly 0.1 to 10 and in particular 0.5 to 5 % by weight of the aromatic carboxylic acid and/or a salt thereof, and 0 to 20, preferably 0 to 10 and in particular 0 to 5 % by weight of the hydraulic binder. Moreover, from 0 to 90%, preferably from 30 to 70% by weight of inert fillers and/or from 0 to 15% by weight of additives can be present. The above proportions are to be selected in a way that they add up to 100% by weight.
Possible inert fillers are e.g. gravels, sands and flours, for example those based on silica, limestone, barite or clay, in particular silica sand. Lightweight fillers such as perlite, kieselguhr (diatomaceous earth), expanded mica (vermiculite) and foam sand can also be used. Possible additives are e.g. plasticizers, antifoams, water retention agents, dispersants, pigments, fibers, redispersible powders, wetting agents, water proofing additives, set retarders, curing accelerators, complexing agents, and rheology modifiers. The amount of water required for setting is for the purpose of this invention not counted as a constituent of the binder. Generally from 10 to 50%, preferably from about 25 to about 35% by weight of water, based on 100 % of alkali-activated aluminosilicate binder, is required for setting. The alkali-activated aluminosilicate binder can be comprised in building material formulations and/or building products such as on-site concrete, finished concrete parts, concrete goods, concrete blocks and also in-situ concrete, spray concrete, ready-mixed concrete, building adhesives and thermal insulation composite system adhesives, concrete repair systems, one-component and two-component sealing slurries, screeds, knifing fillers and self-leveling compositions, tile adhesives, plasters and renders, adhesives and sealants, coating systems, in particular for tunnels, wastewater channels, spray protection and condensate lines, dry mortars, joint grouts, drainage mortars and/ or repair mortars. Moreover, the present invention provides as a further subject matter an alkali-activated aluminosilicate binder comprising blast furnace slag, granulated blast furnace slag and/ or ground granulated blast furnace slag as a latent hydraulic binder, microsilica, meta- kaolin and/or fly ash as a pozzolanic binder, sodium waterglass and/or potassium wa- terglass as an alkaline activator, and ε-caprolactam and sodium benzoate as freeze- thaw stabilizers.
The invention will now be illustrated by means of the following examples.
Examples 1 -12
10.0 g of ground granulated blast furnace slag (Blaine value about 3860 cm2/g) and 20.0 g of microsilica (Fumed Silica, BET value about 1 1 .6 m2/g) were homogenized and then mixed with 20.0 g of liquid aqueous potassium waterglass (modulus 1.0, solids content 52 %). The freeze-thaw stabilizers according to Table 1 , if any, and 60 g of quartz sand were added and further mixed. Prismatic test specimens (4x2x16 cm) were molded and, after 24 h, were cured for 13 days at 60 % relative humidity and 20 °C. The test specimens were subjected to 10, 15, 20 and 30 freeze-thaw cycles. The cycles were carried out according to ASTM C 679-92, i. e. 16 h at -19 °C and 8 h at +23 °C while the specimens were in a bath of 4 % b.w. of aqueous CaC solution.
The respective weight losses in percent are listed in Table 1 hereinbelow. It can be seen that, starting from a formulation without freeze-thaw stabilizers, the addition of a nitrogen-containing organic compound or sodium benzoate separately provides only a small improvement while the addition of a nitrogen-containing organic compound in combination with sodium benzoate provides an significant increase which is often higher than the sum of the improvements of the individual additions. Examples 13-18
The procedure of Examples 1 -12 was followed with varying concentrations of sodium benzoate and ε-caprolactam. The results are shown in Table 2 hereinbelow. It can be seen that, starting from a formulation without freeze-thaw stabilizers, the addition of 1 % or even 2 % b.w. of sodium benzoate or ε-caprolactam separately provided a much smaller improvement in freeze-thaw stability than the addition of 1 % sodium benzoate in combination with 1 % ε-caprolactam. This finding unambiguously proves the existence of a synergistic effect.
Table 1
Example No. Freeze-Thaw Stabilizers Weight Loss [%] vs. Number of Freeze-Thaw Cycles
10 15 20 30
1 no sodium benzoate no amine 41 .0 59.3 71 .6 89.0
2 2% sodium benzoate no amine 20.9 30.4 38.7 50.5
3 no sodium benzoate 0.4% ε-caprolactam 27.0 42.4 52.7 67.5
4 2% sodium benzoate 0.4% ε-caprolactam 5.4 6.0 6.8 16.1
5 2% sodium benzoate 0.4% bis(2-hydroxylpropyl)amine 4.3 5.3 8.4 10.2
6 2% sodium benzoate 0.4% triethanolamine 7.7 7.7 9.4 10.2
7 2% sodium benzoate 0.4% polyetylenimine 15.0 16.0 19.0 33.0
8 2% sodium benzoate 0.4% 2-[(1 -methylpropyl)amino]ethanol 14.0 16.0 17.0 28.0
9 2% sodium benzoate 0.4% betaine 1 .6 1 .6 1 .6 3.0
10 2% sodium benzoate 0.4% triisopropanolamine 1 .5 1 .5 1 .6 2.8
1 1 2% sodium benzoate 0.4% 1 -ethyl 2-pyrrolidone 5.6 5.6 12.6 18.7
12 2% sodium benzoate 0.4% N-butyl ethanolamine (>90%) 3.5 3.7 6.0 6.8
Table 2
Example No. Freeze-Thaw Stabilizers Weight Loss [%] vs. Number of Freeze-Thaw Cycles
10 15 20 30
13 no sodium benzoate no amine 41 .0 59.3 71 .6 89.0
14 1 % sodium benzoate no amine 23.4 31.7 45.9 57.8
15 2% sodium benzoate no amine 20.8 28.3 39.2 48.4
16 no sodium benzoate 1 % ε-caprolactam 19.3 24.0 35.1 42.2
17 no sodium benzoate 2% ε-caprolactam 16.4 20.9 27.1 31 .5
18 1 % sodium benzoate 1 % ε-caprolactam 7.6 8.4 10.5 16.3

Claims

Patent claims
Use of at least one nitrogen-containing organic compound and/or a salt thereof in combination with at least one aromatic carboxylic acid and/or a salt thereof for improving the freeze-thaw stability of an alkali-activated aluminosilicate binder.
Use according to claim 1 , characterized in that the nitrogen-containing organic compound is selected from the group consisting of amines, imidazoles, guani- dines, amides, imides, lactams, amino alcohols, amino acids, and betaines.
Use according to claim 1 or 2, characterized in that the nitrogen-containing organic compound is selected from the group consisting of propylamine, butylamine, pentylamine, hexylamine, ethylenediamine, diaminopropane, diaminobutane, di- aminopentane, neo-pentanediamine, diaminohexane, diethylenetriamine, tetra- ethylenepentamine, Ν,Ν,Ν',Ν'- tetramethyl-ethylenediamine, hexamethylenetet- ramine, 3-ethoxypropylamine, 2-(diethylamino)ethylamine, 3-(methylamino)propyl- amine, 3-(dimethylamino)propylamine, dibutylamine, 4,9-dioxadodecane-1 ,12-di- amine, bis-(2-dimethylaminoethyl) ether, polyetheramines, morpholine, N-ethyl- morpholine, 2-pyrrolidone, N-methylpyrrolidone, imidazolidone, imidazolidone hemihydrate, 2-piperidone, Ν,Ν'-dimethylpiperazine, melamine, 1 ,3,5-triazine, 2,4- diamino-1 ,3,5-triazine, ε-caprolactam, urea, and betaine.
Use according to any of claims 1 to 3, characterized in that the salt of the nitrogen-containing organic compound is a hydrogen halide salt or a quaternary ammonium salt.
Use according to any of claims 1 to 4, characterized in that the aromatic carboxylic acid is selected from the group consisting of benzoic acid, phthalic acid, iso- phthalic acid, terephthalic acid, salicylic acid, and toluic acid.
Use according to any of claims 1 to 5, characterized in that the salt of the aromatic carboxylic acid is selected from the group consisting of alkali metal salts, alkaline earth metal salts, aluminum salts, first row transition metal salts, and mixtures thereof.
Use according to any of claims 1 to 6, characterized in that the alkali-activated aluminosilicate binder comprises at least one latent hydraulic and/or pozzolanic binder and at least one salt selected from among alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, alkali metal silicates, alkali metal aluminates, and mixtures thereof.
8. Use according to claim 7, characterized in that the latent hydraulic binder is selected from among industrial and synthetic slags, in particular blast furnace slag, granulated blast furnace slag, ground granulated blast furnace slag, electrothermal phosphorus slag, steel slag, and mixtures thereof.
9. Use according to claim 7, characterized in that the pozzolanic binder is selected from among amorphous silica, preferably precipitated silica, pyrogenic silica and microsilica, glass flour, fly ash, preferably brown coal fly ash and mineral coal fly ash, metakaolin, natural pozzolanas such as tuff, trass and volcanic ash, natural and synthetic zeolites, and mixtures thereof.
10. Use according to claim 7, characterized in that the alkali metal silicate is selected from among compounds having the empirical formula m S1O2■ n M2O, wherein M is Li, Na, K or NH4 or a mixture thereof, preferably Na or K.
1 1 . Use according to claim 10, characterized in that the molar ratio of m:n is from 0.5 to 3.6, preferably from 0.6 to 3.0 and in particular from 0.7 to 2.5.
12. Use according to any of claims 7 to 1 1 , characterized in that a hydraulic binder selected from among cements, in particular Portland Cement, aluminate cement, and also mixtures thereof, is additionally present.
13. Use according to any of claims 7 to 12, characterized in that the ratio of the nitrogen-containing organic compound and/or salt thereof to the aromatic carboxylic acid and/or salt thereof is comprised within the range of from 1 : 1 to 1 : 10, preferably from 1 : 5 to 1 : 10.
14. Use according to any of claims 1 to 13, characterized in that the alkali-activated aluminosilicate binder comprises
5 to 95, preferably 20 to 80 % by weight of latent hydraulic and/or pozzolanic binder,
5 to 50, preferably 10 to 40 % by weight of alkali metal silicate,
0.01 to 30, preferably 0.1 to 10 and in particular 0.1 to 3 % by weight of the nitrogen-containing organic compound and/or a salt thereof,
0.01 to 30, preferably 0.1 to 10 and in particular 0.5 to 5 % by weight of the aromatic carboxylic acid and/or a salt thereof,
0 to 20, preferably 0 to 10 % by weight of hydraulic binder.
15. Use according to any of claims 1 to 14, characterized in that the alkali-activated aluminosilicate binder is comprised in building material formulations and/or building products such as on-site concrete, finished concrete parts, concrete goods, concrete blocks and also in-situ concrete, spray concrete, ready-mixed concrete, building adhesives and thermal insulation composite system adhesives, concrete repair systems, one-component and two-component sealing slurries, screeds, knifing fillers and self-leveling compositions, tile adhesives, plasters and renders, adhesives and sealants, coating systems, in particular for tunnels, wastewater channels, spray protection and condensate lines, dry mortars, joint grouts, drainage mortars and/or repair mortars.
Alkali-activated aluminosilicate binder comprising blast furnace slag, granulated blast furnace slag and/or ground granulated blast furnace slag as a latent hydraulic binder, microsilica, metakaolin and/or fly ash as a pozzolanic binder, sodium waterglass and/or potassium waterglass as an alkaline activator, and ε-caprolac- tam and sodium benzoate as freeze-thaw stabilizers.
PCT/EP2013/070076 2012-10-31 2013-09-26 Alkali-activated aluminosilicate binder with superior freeze-thaw stability WO2014067721A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
ES13766374.6T ES2659792T3 (en) 2012-10-31 2013-09-26 Alkali activated aluminosilicate binder with superior freeze-thaw stability
CA2889428A CA2889428C (en) 2012-10-31 2013-09-26 Alkali-activated aluminosilicate binder with superior freeze-thaw stability
RU2015120460A RU2648735C2 (en) 2012-10-31 2013-09-26 Alkylosilicate activated alkali with high stability during freezing and thawing
JP2015540079A JP6305420B2 (en) 2012-10-31 2013-09-26 Alkali-activated aluminosilicate binder with excellent freeze-thaw stability
EP13766374.6A EP2914562B1 (en) 2012-10-31 2013-09-26 Alkali-activated aluminosilicate binder with superior freeze-thaw stability
US14/432,624 US9242898B2 (en) 2012-10-31 2013-09-26 Alkali-activated aluminosilicate binder with superior freeze-thaw stability
BR112015005433-1A BR112015005433B1 (en) 2012-10-31 2013-09-26 use of at least one nitrogen-containing organic compound and alkaline activating aluminosilicate binder
AU2013339753A AU2013339753B2 (en) 2012-10-31 2013-09-26 Alkali-activated aluminosilicate binder with superior freeze-thaw stability
CN201380056756.1A CN104854057B (en) 2012-10-31 2013-09-26 The aluminosilicate adhesive of alkali activation with super freeze-thaw stability

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP12190780.2 2012-10-31
EP12190780 2012-10-31

Publications (1)

Publication Number Publication Date
WO2014067721A1 true WO2014067721A1 (en) 2014-05-08

Family

ID=47142978

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/070076 WO2014067721A1 (en) 2012-10-31 2013-09-26 Alkali-activated aluminosilicate binder with superior freeze-thaw stability

Country Status (10)

Country Link
US (1) US9242898B2 (en)
EP (1) EP2914562B1 (en)
JP (1) JP6305420B2 (en)
CN (1) CN104854057B (en)
AU (1) AU2013339753B2 (en)
BR (1) BR112015005433B1 (en)
CA (1) CA2889428C (en)
ES (1) ES2659792T3 (en)
RU (1) RU2648735C2 (en)
WO (1) WO2014067721A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3020692A1 (en) * 2014-11-13 2016-05-18 Colas Geosynthsesis binder comprising a calcium- alkaline activator and a silico-aluminous compound
WO2019091888A1 (en) * 2017-11-10 2019-05-16 Construction Research & Technology Gmbh Microsilica for improving the flowability of a geopolymer suspension
WO2019110280A1 (en) * 2017-12-08 2019-06-13 Ecocem Materials Limited Ground granulated blast furnace slag based binder, dry and wet formulations made therefrom and their preparation methods
CN112047666A (en) * 2020-09-03 2020-12-08 中国核工业中原建设有限公司 Alkali-activated blast furnace ferronickel slag sprayed concrete
WO2021047875A1 (en) 2019-09-13 2021-03-18 METTEN Consulting GmbH Concrete element and method for the production thereof
WO2024246424A1 (en) * 2023-05-26 2024-12-05 Geomateria Oy A method for hydrating silicate mineral material and hydrated silicate mineral material

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2732275T3 (en) * 2013-10-04 2019-11-21 Cemex Res Group Ag Casting material for construction with controllable flow or settlement
US9896379B2 (en) 2015-05-06 2018-02-20 En-Tech Corporation System and method for making and applying a non-portland cement-based material
US10995452B2 (en) 2016-02-09 2021-05-04 Bradley University Lignocellulosic composites prepared with aqueous alkaline and urea solutions in cold temperatures systems and methods
CN105503258A (en) * 2016-01-13 2016-04-20 广东惠众新材料科技股份有限公司 A kind of clay-free sintered block and its preparation method
JP6545637B2 (en) * 2016-05-26 2019-07-17 アレブリオ合同会社 Zeolite-containing hardened body and method for producing zeolite-containing hardened body
JP6778529B2 (en) * 2016-07-15 2020-11-04 株式会社竹中工務店 Cement composition
CN106477990A (en) * 2016-10-10 2017-03-08 南京工业大学 Self-leveling heat-insulation terrace material and preparation method thereof
FR3063999B1 (en) * 2017-03-16 2021-04-30 Groupe Marais HYDRAULIC BINDER FOR LOW-CARBON MORTAR AND MORTAR CONTAINING SUCH A HYDRAULIC BINDER
RU2671018C1 (en) * 2017-08-14 2018-10-29 Федеральное государственное бюджетное образовательное учреждение высшего образования "Грозненский государственный нефтяной технический университет имени акад. М.Д. Миллионщикова" Binder
RU2664083C1 (en) * 2017-08-15 2018-08-15 Федеральное государственное бюджетное образовательное учреждение высшего образования "Грозненский государственный нефтяной технический университет имени акад. М.Д. Миллионщикова" Method for obtaining the acid resistant binder
RS64498B1 (en) * 2017-08-23 2023-09-29 Basf Se Method for the preparation of lignocellulose materials in the presence of caprolactam and its oligomers
CN108269906A (en) * 2017-12-31 2018-07-10 安徽普发照明有限公司 The heat sink material of semiconductor lighting good seal performance
CN108249789A (en) * 2018-01-15 2018-07-06 三峡大学 A kind of phosphorus slag base compound cementitious matter of no first-hand datum and preparation method thereof
US20200039884A1 (en) * 2018-08-03 2020-02-06 United States Gypsum Company Geopolymer compositions and methods for making same
JP7104235B2 (en) * 2019-03-20 2022-07-20 株式会社日本触媒 Additives for hydraulic materials
KR102024583B1 (en) * 2019-05-23 2019-09-24 주식회사 위드엠텍 Micro Fine Particle Grout Composition and Soil Grouting Method Using the Same
CN110510964A (en) * 2019-10-08 2019-11-29 广东东方混凝土有限公司 A kind of ready-mixed concrete
WO2021085376A1 (en) * 2019-10-30 2021-05-06 株式会社日本触媒 Additive for hydraulic materials
CN110792180B (en) * 2019-11-15 2021-02-23 广东工程职业技术学院 Damp-proof construction method for toilet
CN110937829B (en) * 2019-12-02 2021-08-10 东南大学 Two-section type steel slag acid-alkali modification method
KR102277514B1 (en) * 2020-10-12 2021-07-15 경원케이비피 주식회사 Water-curable composition for filling block joint
US20220135482A1 (en) * 2020-11-04 2022-05-05 The Catholic University Of America High performance hybrid fly ash/calcium aluminate cementitious compositions for mortars and concretes
CN115368097B (en) * 2022-08-22 2023-05-05 湖北大学 High-capacity carbon-fixing material and preparation method thereof

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4349386A (en) 1979-09-04 1982-09-14 Joseph Davidovits Mineral polymers and methods of making them
US4472199A (en) 1980-09-03 1984-09-18 Joseph Davidovits Synthetic mineral polymer compound of the silicoaluminates family and preparation process
WO1985003699A1 (en) 1984-02-22 1985-08-29 Pyrament, Inc. Early high-strength mineral polymer
EP0512269A2 (en) 1991-04-08 1992-11-11 ECI- European Chemical Industries Ltd. Process and mixture for preparing large area coating
US5306344A (en) * 1992-12-02 1994-04-26 Edward C. Levy Company Mixture of portland cement concrete materials for freeze/thaw resistance
GB2292141A (en) * 1994-08-12 1996-02-14 Sandoz Ltd Aeration admixture for cementitious compositions
EP1081114A1 (en) 1999-09-02 2001-03-07 Heidelberger Bauchemie GmbH Marke Deitermann Building Material Mixture
EP1236702A1 (en) 2001-03-02 2002-09-04 Heidelberger Bauchemie GmbH Marke Deitermann Building material mixture containing waterglass
WO2004067471A2 (en) * 2003-01-24 2004-08-12 Handy Chemicals Ltd. Admixture for fly ash concrete
WO2008012438A2 (en) 2006-07-28 2008-01-31 Red Lion Cement Technology Limited Geopolymeric cement based on fly ash and harmless to use
WO2010130582A2 (en) 2009-05-14 2010-11-18 Construction Research & Technology Gmbh Reduction of shrinkage in alkali-activated aluminosilicate binders
WO2011064005A1 (en) 2009-11-26 2011-06-03 Construction Research & Technology Gmbh Inorganic binder system for the production of chemically resistant construction chemistry products

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6258161B1 (en) * 1998-11-04 2001-07-10 W. R. Grace & Co.-Conn. Masonry blocks and masonry concrete admixture for improved freeze-thaw durability
RU2267460C2 (en) * 2002-11-06 2006-01-10 Александр Николаевич Левичев Water resistant aluminum silicate for fireproof coating
JP4677181B2 (en) * 2002-11-07 2011-04-27 土木地質株式会社 Water glass for water glass slag concrete, method for producing the same, and water glass slag concrete
JP5693008B2 (en) * 2007-01-19 2015-04-01 セラテック インコーポレーティッド High-strength cement, mortar and concrete containing industrial by-products
JP5091519B2 (en) * 2007-03-28 2012-12-05 公益財団法人鉄道総合技術研究所 Geopolymer composition and method for producing the same
WO2011026723A1 (en) * 2009-09-02 2011-03-10 Construction Research & Technology Gmbh Sulphonic acid and aromatic groups containing hardening accelerator compositions
EP2428499A1 (en) * 2010-09-13 2012-03-14 Construction Research & Technology GmbH Use of compounds containing aluminium and silicon for producing a hydrophilic material product

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4349386A (en) 1979-09-04 1982-09-14 Joseph Davidovits Mineral polymers and methods of making them
US4472199A (en) 1980-09-03 1984-09-18 Joseph Davidovits Synthetic mineral polymer compound of the silicoaluminates family and preparation process
WO1985003699A1 (en) 1984-02-22 1985-08-29 Pyrament, Inc. Early high-strength mineral polymer
EP0512269A2 (en) 1991-04-08 1992-11-11 ECI- European Chemical Industries Ltd. Process and mixture for preparing large area coating
US5306344A (en) * 1992-12-02 1994-04-26 Edward C. Levy Company Mixture of portland cement concrete materials for freeze/thaw resistance
GB2292141A (en) * 1994-08-12 1996-02-14 Sandoz Ltd Aeration admixture for cementitious compositions
EP1081114A1 (en) 1999-09-02 2001-03-07 Heidelberger Bauchemie GmbH Marke Deitermann Building Material Mixture
EP1236702A1 (en) 2001-03-02 2002-09-04 Heidelberger Bauchemie GmbH Marke Deitermann Building material mixture containing waterglass
WO2004067471A2 (en) * 2003-01-24 2004-08-12 Handy Chemicals Ltd. Admixture for fly ash concrete
WO2008012438A2 (en) 2006-07-28 2008-01-31 Red Lion Cement Technology Limited Geopolymeric cement based on fly ash and harmless to use
WO2010130582A2 (en) 2009-05-14 2010-11-18 Construction Research & Technology Gmbh Reduction of shrinkage in alkali-activated aluminosilicate binders
WO2011064005A1 (en) 2009-11-26 2011-06-03 Construction Research & Technology Gmbh Inorganic binder system for the production of chemically resistant construction chemistry products

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CAIJUN SHI; PAVEL V. KRIVENKO, DELLA ROY, pages 51 - 63
CAIJUN SHI; PAVEL V. KRIVENKO; DELLA ROY: "Alkali-Activated Cements and Concretes", 2006, TAYLOR & FRAN- CIS, pages: 42 - 51
PETER M GIFFORD AND JACK E GILLOTT: "Freeze-Thaw Durability of Activated Blast Furnace Slag Cement Concrete", ACI MATERIALS JOURNAL, AMERICAN CONCRETE INSTITUTE, FARMINGTON HILLS, MI, US, vol. 93, no. 3, 1 May 1996 (1996-05-01), pages 242 - 245, XP009175652, ISSN: 0889-325X *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3020692A1 (en) * 2014-11-13 2016-05-18 Colas Geosynthsesis binder comprising a calcium- alkaline activator and a silico-aluminous compound
FR3028509A1 (en) * 2014-11-13 2016-05-20 Colas Sa GEOSYNTHESIS BINDER COMPRISING AN ALKALINO-CALCIUM ACTIVATOR AND A SILICO-ALUMINOUS COMPOUND
WO2019091888A1 (en) * 2017-11-10 2019-05-16 Construction Research & Technology Gmbh Microsilica for improving the flowability of a geopolymer suspension
WO2019110280A1 (en) * 2017-12-08 2019-06-13 Ecocem Materials Limited Ground granulated blast furnace slag based binder, dry and wet formulations made therefrom and their preparation methods
US11384018B2 (en) 2017-12-08 2022-07-12 Ecocem Materials Limited Ground granulated blast furnace slag based binder, dry and wet formulations made therefrom and their preparation methods
WO2021047875A1 (en) 2019-09-13 2021-03-18 METTEN Consulting GmbH Concrete element and method for the production thereof
EP4028371B1 (en) 2019-09-13 2023-09-27 METTEN Technologies GmbH & Co. KG Concrete element and method for the production thereof
EP4321317A2 (en) 2019-09-13 2024-02-14 METTEN Technologies GmbH & Co. KG Concrete element and method for its production
CN112047666A (en) * 2020-09-03 2020-12-08 中国核工业中原建设有限公司 Alkali-activated blast furnace ferronickel slag sprayed concrete
CN112047666B (en) * 2020-09-03 2021-10-29 中国核工业中原建设有限公司 Alkali-activated blast furnace ferronickel slag sprayed concrete
WO2024246424A1 (en) * 2023-05-26 2024-12-05 Geomateria Oy A method for hydrating silicate mineral material and hydrated silicate mineral material

Also Published As

Publication number Publication date
JP2015536294A (en) 2015-12-21
CN104854057A (en) 2015-08-19
US20150232385A1 (en) 2015-08-20
CN104854057B (en) 2017-09-01
US9242898B2 (en) 2016-01-26
AU2013339753B2 (en) 2016-10-06
RU2015120460A (en) 2016-12-20
JP6305420B2 (en) 2018-04-04
ES2659792T3 (en) 2018-03-19
AU2013339753A1 (en) 2015-05-28
CA2889428C (en) 2021-05-18
CA2889428A1 (en) 2014-05-08
EP2914562B1 (en) 2017-11-29
RU2648735C2 (en) 2018-03-28
EP2914562A1 (en) 2015-09-09
BR112015005433B1 (en) 2021-05-11
BR112015005433A2 (en) 2017-08-08

Similar Documents

Publication Publication Date Title
US9242898B2 (en) Alkali-activated aluminosilicate binder with superior freeze-thaw stability
RU2538570C2 (en) System of inorganic binding substance for obtaining chemically stable building chemical products
US10259949B2 (en) Corrosion resistant spray applied fire resistive materials
US20070056473A1 (en) Liquid quick-setting admixture, shotcreting material and method for shotcreting using them
EP3245171B1 (en) Method for making concrete compositions
WO2021061920A1 (en) Protective coating
JP6902643B1 (en) Cement admixture and hydraulic composition
JP7037877B2 (en) Early-strength admixture for secondary products and early-strength concrete for secondary products
JP2022142308A (en) Fast curing grout composition and fast curing grout
WO2024203776A1 (en) Ultra-quick hardening mortar material for grout, and mortar-hardened body
JP2020083697A (en) Low temperature rapid-hardening type light weight filling mortar composition for u-rib, and mortar thereof
JP2020083698A (en) Rapid-hardening type light weight filling mortar composition for u-rib, and mortar thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13766374

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2013766374

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2013766374

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 14432624

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2889428

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2015540079

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2013339753

Country of ref document: AU

Date of ref document: 20130926

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2015120460

Country of ref document: RU

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112015005433

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112015005433

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20150311