Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/24—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
  • C04B2111/00663—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
  • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
  • C04B2111/1037—Cement free compositions, e.g. hydraulically hardening mixtures based on waste materials, not containing cement as such
• • 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
  • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
• • 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
• • 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
  • C04B2111/70—Grouts, e.g. injection mixtures for cables for prestressed concrete
• • 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
  • 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

• the present invention relates to a novel inorganic binder system, the use of this binder system for the production of a hydraulically setting mortar and a mortar which contains this binder system.
• Portland cement was first mentioned in British patent BP 5022 and has since been continuously further developed. Modern 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 03. Owing to its high CaO content, it hardens hydraulically. Hardened Portland cement is alkali-resistant but not acid-resistant.
• certain slags from metallurgical processes can be activated with strong alkalis, such as, for example, waterglasses or can be used as admixtures to Portland cement.
• strong alkalis such as, for example, waterglasses
• fillers quartz sand or aggregate having a corresponding grain size
• additives they can be used as mortars or concretes.
• Blast furnace slag a typical latent hydraulic binder, has as a rule 30 to 45% by weight of CaO, about 4 to 17% by weight of MgO, about 30 to 45% by weight of Si0 2 and about 5 to 15% by weight of Al 2 0 3 , typically about 40% by weight of CaO, about 10% by weight of MgO, about 35% by weight of Si0 2 and about 12% by weight of Al 2 03.
• Hardened products generally have the properties of hydraulically hardened systems.
• Metakaolin, slag, fly ash, activated clay or mixtures thereof may be used as reactive oxide mixture.
• the alkaline medium for activating the binder usually consists of aqueous solutions of alkali metal carbonates, alkali metal fluorides, alkali metal hydroxides and/or soluble waterglass.
• the hardened binders have high mechanical stability. In comparison with cement, they may be more economical and more resistant and may have a more advantageous C0 2 emission balance. Such systems are as a rule more likely to be acid-resistant and less likely to be alkali-resistant.
• WO 08/012438 describes a further geopolymer cement based on low-CaO fly ash class F, blast furnace slag and aqueous alkali metal silicate having an Si0 2 :M 2 0 ratio of more than 1 .28, preferably of more than 1.45.
• Si0 2 :M 2 0 ratio of more than 1 .28, preferably of more than 1.45.
• anhydrous oxides about 45 to 50% by weight of Si0 2 , about 20 to 26% by weight of AI2O3, about 9 to 10% by weight of CaO and about 3 to 4% by weight of K 2 0 are present.
• the inventors have set themselves the object of substantially avoiding at least some of the disadvantages of the prior art discussed above.
• the hardened system should have these properties even at a relatively early stage, in particular after only 7 days, and should harden even at room temperature, preferably at as low as 10°C.
• EP 1236702 describes a waterglass-containing construction material mixture for the production of mortars resistant to chemicals and based on a latent hydraulic binder, waterglass and a metal salt as a control agent.
• Slag sand too, can be used as a latent hydraulic component.
• Alkali metal salts, in particular lithium salts, are mentioned and used as the metal salt.
• EP 1081 1 14 describes a construction material mixture for the production of mortars resistant to chemicals, the construction material mixture containing waterglass powder and at least one waterglass hardener. Furthermore, more than 10% by weight of at least one latent hydraulic binder are present, and the construction material mixture has at least one inorganic filler.
• the inorganic binder system according to the invention hardens in the form of a hybrid matrix which is acid-resistant, water-resistant and alkali- resistant.
• the present invention provides an inorganic binder system which comprises at least one latent hydraulic binder, at least one amorphous silica, optionally at least one reactive filler and at least one alkali metal silicate.
• the inorganic binder system of the invention preferably comprises 10 to 30 parts by weight of latent hydraulic binder, 5 to 22 parts by weight of amorphous silica, 0 to 15 parts by weight of reactive filler and 3 to 20 parts by weight of alkali metal silicate. More preferably, it comprises 10 to 30 parts by weight of latent hydraulic binder, 5 to 20 parts by weight of amorphous silica, 0 to 15 parts by weight of reactive filler and 3 to 20 parts by weight of alkali metal silicate. Particularly preferably, it comprises 15 to 25 parts by weight of the latent hydraulic binder, 5 to 17 parts by weight of amorphous silica, 0 to 10 parts by weight of the reactive filler and 4 to 15 parts by weight of alkali metal silicate.
• a latent hydraulic binder is preferably to be un- derstood as meaning a binder in which the molar (CaO + MgO):Si02 ratio is between 0.8 and 2.5 and particularly preferably between 1 .0 and 2.0.
• the latent hydraulic binder is selected from blast furnace slag, slag sand, ground slag, electrothermal phosphorus slag and steel slag.
• Blast furnace slag is a waste product of the blast furnace process.
• Slag sand is granulated blast furnace slag and ground slag is finely pulverized blast furnace slag.
• the ground slag varies in its fineness of grinding and particle size distribution according to origin and preparation form, the fineness of grinding having an influence on the reactivity.
• the so-called Blaine value which is typically of the order of magnitude of 200 to 1000, preferably between 300 and 500 m 2 kg- 1 , is used as a characteristic for the fineness of milling.
• a typical composition of blast furnace slag was mentioned hereinabove.
• Electrothermal phosphorus slag is a waste product of electrothermal phosphorus production. It is less reactive than blast furnace slag and contains about 45 to 50% by weight of CaO, about 0.5 to 3% by weight of MgO, about 38 to 43% by weight of Si0 2 , about 2 to 5% by weight of AI2O3 and about 0.2 to 3% by weight of Fe203 as well as fluoride and phosphate.
• Steel slag is a waste product of various steel production processes with strongly varying composition (cf. Caijun Shi, Pavel V. Krivenko, Delia Roy, Alkali-Activated Cements and Concretes, Taylor & Francis, London & New York, 2006, pages 42-51 ).
• the amorphous silica is preferably an X-ray-amorphous silica, i.e. a silica which shows no crystallinity in the powder diffraction method.
• it is selected from precipitated silica, pyrogenic silica and microsilica as well as glass powder, which is likewise to be considered as amorphous silica in the context of the present invention.
• the amorphous silica according to the invention suitably has a content of at least 80% by weight, preferably at least 90% by weight, of S1O2.
• Precipitated silica is obtained industrially via precipitation processes starting from waterglass.
• Precipitated silica is also referred to as silica gel, depending on the production process.
• Pyrogenic silica is produced by reacting chlorosilanes, such as, for example, silicon tetrachloride, in an oxyhydrogen flame.
• Pyrogenic silica is an amorphous S1O2 powder having a particle diameter of 5 to 50 nm and a specific surface area of 50 to 600 m 2 g- 1 .
• Microsilica (also referred to as silica fume) is a by-product of silicon or ferrosilicon production and likewise comprises for the most part amorphous S1O2 powder.
• the parti- cles have diameters of the order of magnitude of 0.1 ⁇ .
• the specific surface area is of the order of magnitude of 20 to 25 m 2 g- 1 (cf. Caijun Shi, Pavel V. Krivenko, Delia Roy, Alkali-Activated Cements and Concretes, Taylor & Francis, London & New York, 2006, pages 60-61 ).
• commercially available quartz sand is crystalline, has comparatively large particles and a comparatively small specific surface area. It serves ac- cording to the invention merely as an inert aggregate.
• the reactive filler is an optional component. It is suitably a substance having pozzo- lanic activity.
• the test for pozzolanic activity can be effected according to DIN EN 196 part 5.
• An overview of pozzolans suitable according to the invention is to be found in Caijun Shi, Pavel V. Krivenko, Delia Roy, Alkali-Activated Cements and Concretes, Taylor & Francis, London & New York, 2006, pages 51 -60, and pages 61 -63.
• the reactive filler is selected from brown coal fly ash, mineral coal fly ash, meta- kaolin, volcanic ash, tuff, trass, pozzolana and zeolites. Metakaolin and fly ashes of Classes C (brown coal fly ash) and F (mineral coal fly ash) are particularly preferred.
• Metakaolin forms in the dehydration of kaolin. While kaolin releases physically bound water at 100 to 200°C, a dehydroxylation takes place at 500 to 800°C with a collapse of the lattice structure and formation of metakaolin (AI2S12O7). Pure metakaolin accordingly contains about 54% by weight of S1O2 and about 46% by weight of AI2O3.
• Fly ashes form, inter alia, in the combustion of coal in power stations.
• fly ash of class C contains 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.
• the teaching of WO 08/012438 is hereby incorporated by reference to this extent.
• the inorganic binder system according to the invention has, as a rule the, following oxide composition, calculated on the basis of the solids:
• M 2 5 to 30% by weight of M 2 0, preferably: 30 to 65%, particularly preferably 45 to 60%, by weight of S1O2,
• the amount of water required for setting is suitably 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on the total weight of the (anhydrous) inorganic binder system.
• the amount of water required for setting is thus not counted as a constituent of the inorganic binder system.
• the alkali metal silicate is selected from compounds having the empirical formula m S1O2 n M2O, in which M represents Li, Na, K or NH4, or a mixture thereof, preferably Na or K.
• the molar ratio of m:n is suitably not more than 3.6, preferably not more than 3.0, and in particular not more than 2.0. Even more preferably it is not more than 1.70 and in particular not more than 1 .20.
• the alkali metal silicate is preferably a waterglass, particularly preferably a liquid water glass and in particular a sodium or potassium waterglass.
• a waterglass particularly preferably a liquid water glass and in particular a sodium or potassium waterglass.
• lithium or ammonium waterglasses and mixtures of said waterglasses may also be used.
• the abovementioned parts by weight are calculated on the basis of the solids contents of these waterglasses, which as a rule are 20% by weight to 60% by weight, preferably 30 to 50% by weight, of solids.
• m:n ratios should preferably not be exceeded, since otherwise complete activation of the components can no longer be expected.
• modulus such as, for example, about 0.2
• Waterglasses having higher moduli should be adjusted before use with a suitable aqueous alkali metal hydroxide. Potassium waterglasses are commercially available mostly as aqueous solutions in the suitable modulus range, since they are strongly hygroscopic; sodium waterglasses are also commercially available as solids in the suitable modulus range.
• the inorganic binder system can expediently be formulated as a one-component system, which can then be caused to harden by the addition of water.
• the latent hydraulic binder, the amorphous silica, the optional reactive filler and the alkali metal silicate are present together as one component.
• the waterglass can also be used in the form of an aqueous solution.
• the inorganic binder system is expediently formulated as a two-component system, wherein usually the latent hydraulic binder, the amorphous silica and the optional reactive filler are present as a first component and the waterglass solution, which con- tains at least the amount of water required for setting, is present as a second component. At least in the case of potassium waterglass, this embodiment is preferred.
• Inert fillers and/or further additives may additionally be present in the inorganic binder system according to the invention. These optional components can alternatively also be added only on preparation of a mortar or concrete.
• inert fillers Preferably, between 0 and 80% by weight, particularly preferably between 30 and 70% by weight, of inert fillers and/or between 0 and 15% by weight of additives may be present or may be added during the mortar or concrete preparation. These weight data are based on the total weight of the solids of the (anhydrous) inorganic binder system. The inert fillers and/or further additives are thus not counted as constituents of the inorganic binder system.
• gravels, sands and/or powders for example based on quartz, limestone, barite or clay, in particular quartz sand, are suitable as inert fillers.
• Light fillers such as perlite, kieselguhr (diatomaceous earth), exfoliated mica (vermiculite) and foamed sand, can also be used.
• Suitable additives are, for example, generally known flow agents, antifoams, water retention agents, plasticizers, pigments, fibers, dispersion powders, wetting agents, re- tardants, accelerators, complexing agents, aqueous dispersions and rheology modifiers.
• Cement may also be present or may be added during the mortar or concrete preparation as a further (hydraulic) additive.
• This cement can preferably be Portland cement and/or high-alumina cement.
• the present invention furthermore provides for the use of the inorganic binder system of the invention as or as a constituent of building material formulations and/or building products such as concrete, finished concrete parts, concrete goods, concrete blocks and also on-site 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-level- ling 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 concrete, finished concrete parts, concrete goods, concrete blocks and also on-site 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
• the inorganic binder system of the invention is often mixed with further components, such as fillers, hydraulic substances and additives.
• the addition of the alkali metal silicate in powder form is preferably effected before said components are mixed with water.
• an aqueous alkali metal silicate solution can be added to the other powder components.
• the present invention furthermore provides a mortar, in particular a dry mortar or joint grout, which contains the inorganic binder system of the invention.
• this mortar After setting, hardening for seven days and subsequent storage for three days in acid, base and/or water, this mortar has compressive strengths of more than 15 N mnr 2 , preferably more than 20 N mnr 2 and in particular more than 25 N mnr 2 , as determined according to DIN EN 13888.
• Metakaolin comprising about 56% by weight of S1O2, 41 % by weight of AI2O3 and in each case ⁇ 1 % by weight of CaO and alkali metal oxide; BET surface area > 10 000 m 2 kg- 1 ;
• Microsilica comprising > 90% by weight of SiC ⁇ and in each case ⁇ 1 % by weight of AI2O3, CaO and alkali metal oxide; BET surface area > 15 000 m 2 kg- 1 ;
• Ground blast furnace slag comprising about 34% by weight of S1O2, 12% by weight of AI2O3, 43% by weight of CaO and ⁇ 1 % by weight of alkali metal oxide; Blaine value > 380 m 2 kg- 1 ;
• Aqueous potassium waterglass having a molar Si02:K20 ratio of 1 .5 or 1 .0 and solids contents of 50% by weight or 40% by weight, respectively;
• Table 3 shows that, after a short duration of hardening of seven days under standard climatic conditions, the minimum compressive strengths of 15 N mnr 2 required accor- ding to DIN EN 13888 are achieved by M2 through M5.
• the reference systems M1 through M3 after acid, water and/or alkali treatment have low compressive strength
• very high compressive strengths can be determined in the case of the systems M4 and M5 according to the invention, even after storage in the various test media.
• the systems according to the invention are accordingly acid-, water- and alkali-resistant.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Organic Chemistry (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Sealing Material Composition (AREA)
• Soil Conditioners And Soil-Stabilizing Materials (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)

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• 2010
  • 2010-09-13 CN CN201080053310.XA patent/CN102648167B/zh active Active
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