SK500432010U1 - Antimicrobial effective cements, building binders, mixtures comprising cement and building products and materials - Google Patents

Abstract

Antimicrobial effective cements, building binders, mixtures comprising cement and building products and materials comprising from 5 to 95 % by weight of antimicrobial activated granulated blast-furnace slag.

Description

Technical field

The technical solution relates to antimicrobially effective cements, construction binders, cement-containing mixtures and construction products and materials.

BACKGROUND OF THE INVENTION

Problem of occurrence of microorganisms such as bacteria, yeasts (unicellular fungi), molds (filamentous fungi), fungi, mosses, lichens on exteriors and interiors of buildings and various constructions, event. cyanobacteria, algae (simple plants) on waterworks, water and sewer pipes, is not only important in terms of hygiene, health and aesthetics, but also in terms of biodegradation of building materials. Their occurrence is conditioned by suitable temperature-humidity conditions, depends on the pH of the environment, the presence of oxygen, radiation, etc.

Biological corrosion of concretes and mortars is caused by organic and inorganic acids, which are caused mainly by bacteria, namely sulfur and nitrifying (oxidative) acids, whose effect on H2S produces sulfuric acid H2SO4 and on ammonia NH3 nitric acid HNO3, which are among the strongest inorganic acids. . Other types of bacteria produce high molecular weight organic acids such as humic or pyruvic acid, and low molecular weight organic acids such as formic, acetic, propionic, butyric, lactic, oxalic, malic, citric, and others. In concretes and mortars, these acidic metabolites react primarily with the calcium constituents of the cement and mortar stones to form their non-binding calcium salts, thereby breaking the stone up to its depth. In some cases, they can also react with the aggregate components, possibly with admixtures and additives.

The risk of attack of concrete and mortars by microorganisms increases with the use of organic additives (polyvinyl acetate, casein, methylcellulose, lignosulfonates, etc.) or admixtures (shives, sawdust, wood meal, chips, wood wool, wood fibers, wood chips and wood chips). In addition to biochemical disruption, in the case of molds, mechanical disruption, e.g. by growing them into their volume of hardened stone. The stone structure breaks down or even breaks down.

Antimicrobial protection of buildings and structures resp. places with the presence of microorganisms (wet masonry, building foundations, etc.) or places with their potential occurrence (hospitals, schools, kitchens, swimming pools, laundries, sanitary facilities, shops, food, meat processing, distillery, pharmaceutical, cosmetic, chemical, woodworking industries, various organic products, agriculture, rendering plants, water supply companies, sewerage systems, sewage treatment plants, cooling towers) are therefore very important.

To prevent the occurrence, growth and multiplication of microorganisms, they are added to concrete, mortar, plaster, cementitious adhesives, etc. biocidal additives (Bajza, A. and Rouseková, I., Concrete Technology, Jaga, Bratislava, pp. 70 and 156, 2006), which provide building materials with bactericidal, bacteriostatic, fungicidal and fungistatic properties.

Most biocidal ingredients contain organic compounds as an antimicrobial active ingredient. A large number of antibacterial and antifungal preparations are available on the market, but these are not the object of this technical solution.

The disadvantage of the biocidal additives used hitherto is that most of them have only a selective antimicrobial effect, not covering a wide range of microorganisms, most are unstable and have only short-term efficacy and the biggest disadvantage is their cost because these preparations are very expensive. In addition to this, investment costs for equipment for their storage, dosing, mixing and homogenization in cements and cement-containing mixtures, as well as operating costs, are added. The effectiveness of biocidal additives is influenced by their solubility in water and the manner of their application. The water-soluble additives are easily washed out of the concrete or cement-containing mortar after the addition of the mixing water and the efficiency is lost relatively quickly. Poorly water-soluble additives can diffuse out of the hydrated stone to the surface over a long period of time and also lose efficiency relatively quickly.

Most biocidal additives decompose due to the alkaline environment of the hydrating concrete or mortar. Conventionally available biocidal additives are mostly neither suitable for building materials. However, there are exceptions to US 7223443, US 4556426, RO 000000120968, JP 2005255551, JP 11012017, JP 03271206.

Another possibility seems to be the use of metal ion-bound organic compounds such as Cu 2+, Zn 2+, Ca 2+, Ba 2+, dosed in an amount of 0.025 - 2% (w / w) per mixture of WO 2006065259. The biocide can be dosed either as a powder or bonded to a porous glass, ceramic, mineral or polymer with a sustained release biocide. It is also possible to use a combined organic-inorganic composite material composed of an organic polymer with an antibacterial and antifungal functional group, to which is bound an inorganic moiety containing divalent metal ions according to JP 2002235008. Other carriers of antibacterial agents may also be metal, glass, glass ceramic particles, WO 2006064060 on which an oxide, oxynitride, oxycarbide, nitride, carbide layer is deposited containing the antibacterial agent Ag +, Cu 2+ and Zn 2+ in the form of inorganic compounds or metals. In addition to the powdered glass containing Ag +, Zn2 + and Cu2 +, the carriers of Ag +, Zn2 + and Cu2 + antimicrobial agents can also be zeolites US 6924325, zeolite mineral mordenite (Ca, Na2, K2) Al2Si10O24.7H2O according to JP 08109108, Ca3 PO4) 2 and feldspars according to JP 08259298, calcium phosphate compounds according to JP 06024919, crystalline or amorphous TiO2 according to JP 2001106607. Even pure ΊΊ02 with photocatalitic ability in the form of crystalline, amorphous, like fibrous, monoclinic, rutile, anatase can be used as antibacterial cementitious agent according to JP 2000219564. The antimicrobial cementitious agent may also be based on a nickel Ni amorphous alloy deposited on organic or inorganic nano and microparticles according to JP 09221347. The antimicrobial cementitious agent may also be based on ammonium salts according to JP 2003292358. Fungicidal composite material suitable for fungicidal cements other than silicate gray and white, it can also be based on minerals of alkaline metal, alkaline earth metal, non-metallic minerals and rare minerals in combination with zeolites, boron minerals, clays, kaolin, bentonite, acidic clays, apatites, aluminum sulphates, zinc, calcium , barium, strontium carbonate, zirconium, sodium, lanthanum, cerium and neodymium oxides in which rare mineral ions exert fungicidal activity and are added to cements in an amount of 3 to 20% according to JP 11302058.

However, all of these prior art solutions are very costly due to the high purchase prices of biocidal ingredients, requiring investment in production facilities such as e.g. storage tanks, dosing devices, mixing cores, etc., are associated with high operating costs, the risk of inhomogeneous distribution of the antimicrobial additive within the cement or cement containing bulk matrix of building material, since the amount of antimicrobial additive is several times lower and gasses and especially in the water mixture during the application of the building material at the place of its realization.

The aim of this technical solution is to produce affordable commercially available cements, construction binders, cement containing mixtures and construction products and materials with increased antimicrobial effects, without investment costs and without increasing operating costs, with good homogeneity, without the possibility of mixing in fresh cement mixtures with water .

It is also an object of the present invention to provide cements, building binders, cement-containing mixtures and construction products and materials with antimicrobial effects that are substantially longer than those of conventional biocidal agents in these materials.

The essence of the technical solution

It has been found that a suitable substance to make available commercially available cements, building binders, cement containing mixtures and construction products and materials with enhanced antimicrobial effects, without investment costs and without increasing operating costs, with good homogeneity, without the possibility of mixing in blast furnace slag is fresh granular cement mixtures with water and which would have substantially longer-lasting antimicrobial effects than using conventional biocidal agents in said materials.

Granulated blast furnace slag is a by-product of pig iron production. Its use in cements, construction binders, cement-containing mixtures and construction products and materials is prescribed by the applicable European and national standards.

Granulated blast furnace slag suitable for cement is defined according to European Standard EN 197-1: 2000 and ground granulated blast furnace slag for use in concrete, mortar and grout according to European Standard EN 15167-1: 2006 as a glassy material resulting from rapid cooling of a suitably composed slag melt obtained by melting iron ore in a blast furnace, which consists of at least two-thirds by weight of a vitreous phase with a chemical composition consisting of at least two-thirds by weight of the sum of calcium oxide (CaO), magnesium oxide (MgO) and silica (SiO2). The residue must contain alumina (Al 2 O 3) along with a small amount of other compounds. The weight fraction (CaO + MgO) / (SiO2) must be greater than 1.0. Rapid cooling includes rapid cooling in water (granulation) and spraying through water and air (pelletization).

The use of granulated blast furnace slag suitable as a constituent for mortar and plaster mortars is defined according to EN 413-1: 2004, for low hydration heat cements is defined according to EN 197-1: 2000 / A1: 2004, for very low cements hydration heat is defined according to EN 14216: 2004, for blast furnace cements with low initial strength is defined according to EN 197-4: 2004, for blast furnace sulphate resistant cements is defined according to STN 72 2103.

According to EN 206-1: 2000, finely ground granulated blast furnace slag can be classified as an additive to concrete II. type - pozzolanic or latent hydraulic.

In the normal use of granulated blast furnace slag, it increases long-term compressive and tensile bending strengths compared to pure cement, reduces hydration heat, improves processability and stability of the mixture, reduces permeability by creating a compact cement stone structure, increases resistance to sulphate and aggressive waters, chemical corrosion, against chlorides, ensures the prevention of an alkali - silica reaction. For concrete, it is advantageous to extend the setting time of the concrete and to optimize the grain size curve of the aggregate until the start of setting as a filler.

In the prior art antimicrobial cement containing compositions, ground blast furnace granulated slag was used as a latent hydraulic additive or filler, regardless of its other application possibilities. By way of example, mention may be made of a cement composition based on aluminous cement, finely ground blast furnace granulated slag and an antibacterial additive based on Ag + and / or Cu + according to JP 2006327866, a cement composition based on calcium aluminate compounds and coloanite (coloanite is hydrated calcium triborite Ca [B3O4 (OH) 3] .H2O), which further comprises one or more finely ground blast furnace slag, fly ash, silica drift and inorganic salts according to JP 2005139010, antibacterial penetration curing agent penetration curing agent for penetration curing agent Remediation of stone structures containing 1 to 12% antibacterial organic compounds and inorganic fillers consisting of ground natural powder powder, water-granulated blast furnace slag particles, Portland cement, gypsum and inorganic pigments according to JP 10025175, concrete algae and mold resistant mixture consisting of cement, aggregate and containing at least one material such as silica fume, ash and finely ground blast furnace granulated slag to which a selective organic herbicide and / or inorganic agent containing an antibacterial metal ion is added 0 3 to 6 kg / m 3 of the concrete mixture according to JP 09002859.

The aforementioned objects of the invention meet the antimicrobially effective cements, building binders, cement containing mixtures and construction products and materials, which consist in that they contain 5 to 95 wt. antimicrobially activated granulated blast furnace slag.

Additions of antimicrobially activated granulated blast furnace slag to cements, building binders, cement-containing mixtures and construction products and materials ensure their antimicrobial resistance. This results in building composite materials with increased antimicrobial resistance to microorganisms.

The slag to achieve antimicrobial effects is activated either by mechanical activation and / or by chemical activation, and also a silica aluminate beep itself. sulfoaluminate clinker, cement, solidification regulator, additives, admixtures and components used in the manufacture of cements, building binders, cement-containing mixtures and construction products and materials can cause, increase antibacterial activation of metallurgical debris.

Mechanical activation is accomplished by crushing and / or grinding and / or spreading and / or screening and / or mixing. The slags are dosed either into crushing units in the crushing process and / or into the milling aggregates in the grinding process and / or into the sorting aggregates in the sorting process and / or into the mixing aggregates in the mixing process of either the slags alone and / or in the preparation of cements and / or binders and / or cement-containing mixtures and / or building materials and / or building materials. By mechanical treatment, the slag is activated by changing the particle size, the particle size granulometry, the particle size distribution, the specific surface, the surface charge of the particles, the surface tension, or the surface energy forces. After mechanical activation, the amount of particles larger than 500 µm is at most 99% by weight. of total granulometry.

Chemical activation is accomplished by the addition of activators to debris such as inorganic and / or organic compounds e.g. compounds with bound ions of alkali metals (Na ⁺ , K ⁺ ...) and alkaline earth metals (Ca ²⁺ , Ba ²⁺ ...), cement clinkers, cements, additives and admixtures used in the production of cements e.g. grinding intensifiers, solidification regulators, additives used in the production of concrete, mortars, dry plaster mixtures e.g. plasticizers, aerating additives, accelerating additives, retarding additives, lime, lime hydrate, limestone, dolomite, gypsum, anhydrite, gypsum and / or steaming and / or steaming and / or autoclaving and / or heat treatment by drying and / or heating and / or burn. By chemical treatment, the slag is activated either by modifying its chemical composition and / or its mineralogical composition and / or by destroying the slag structure and / or by stimulating hydration reactions and / or by binding processes and / or by excretion of ions and complex compounds from the slag structure including heavy metals and / or by changing the pH and / or by changing the surface charge and / or by phase changes due to hydration changes and / or phase changes due to temperature changes.

Further details of the antimicrobial activation of the debris are described in patent application SK PP 50043-2009, on which the technical solution is based.

Additions of antimicrobially activated granulated blast furnace slag to cements, building binders, cement-containing mixtures and building materials can be realized either by mixing in different types of mixing aggregates (mixing core for homogenization, cement production, dry plaster mixtures, concrete, mortars, mixers, etc.) and / or by crushing in the crushing process by addition to the crushing aggregates and / or to the milling aggregates in the milling process and / or to the sorting aggregates in the sorting process.

Activated granulated blast furnace slag with antimicrobial effects as a latent hydraulic admixture is suitable for the production of Portland cement, Portland slag cements, Portland mix cements with granulated blast furnace slag as the main component, blast furnace cements, mixed cements and all granulated blast furnace cements. cements such as sulphate resistant cements, low hydration heat cements, low initial strength cements, mortar cements for mortar and plaster with the addition of granular blast furnace slag, road cements, cement for concrete and various cement containing mixtures with the addition of granular blast furnace slag. The proportion of blast furnace granulated slag in cements can range from 5 to 95% by weight. to the amount of Portland clinker, depending on the type of cement, which range includes the use of granulated blast furnace slag as either the main component or the supplementary component and / or the special component.

Cement-containing mixtures are common concrete mixtures, concrete mixtures for the production of blocks and prefabricates, concrete mixtures for cement concrete pavements, tunnels, bridges, viaducts, cement containing mixtures for stabilizing substrates, cement-reinforced aggregates, concretes for massive and high-volume buildings, shotcrete, screeds, cement adhesives for wall and floor tiles, cement adhesives for thermal insulation systems, heat-insulating mortars, waterproofing mixtures, jointing materials, masonry mortars, plastering mortars, screeds, stuccoes, dry plaster mixtures, leveling mixtures, grouting mixtures, sealing suspensions, mixtures for protection and repair of concrete structures, remediation mixtures, mixtures based on aluminous cement and other special types of cements and binders and the like.

Building binders and specialty cements can be made up of binders such as calcium aluminate based aluminate cements, calcium aluminate based refractory cements and other phases, C2S-based belite cements, 3CA sulphonaluminate cements .CaSO4 and C2S, white cements, colored cements, hydrophobic cements, alkaline activated slag cements, geopolymer binders, slag-sulphate and slag-lime binders, roman cement, hydraulic lime, air-lime or lime hydrate binders, calcium sulphate sulphate binders, anhydrite binders, magnesium binders and others.

Construction products and materials are commonly commercially available construction products applied to sites with a potential presence of microorganisms such as e.g. cladding boards, boards based on cement and wood wool, wood fibers, concrete blocks based on cement and wood chips, load-bearing elements, ceiling elements, structural elements, panels, etc.

Cements, building binders, cement containing mixtures and construction products and materials with the addition of antimicrobially activated granulated blast furnace slag reduce the overall cost of creating an antimicrobial clean environment. They are particularly suitable for the construction of new buildings, where still wet unrendered plasters in a confined environment tend to be covered with mold. They are also suitable for the reconstruction of buildings, housing units, remediation of microbiologically damaged areas.

The antimicrobial effects of cements, construction binders, cement-containing mixtures and construction products and materials containing antimicrobially activated granulated blast furnace slag decrease with time, depending on the aging of the hydrating building binder, the recrystallization of the hydration phases and the incorporation of the active antimicrobial particles of composite however, they are considerably longer than with conventional biocidal agents.

EXAMPLES

Various antimicrobially active cements, building binders, cement containing mixtures and construction products and materials having different contents of antimicrobially activated granulated blast furnace slag were prepared. Testing of their resistance to molds was determined according to ČSN 72 431: 1977.

A mixture of Aspergillus niger (CCM 8155), Chaetomium globosum (CCM 8156), Penicillium funiculosum (CCM F-161), Paecilomyces variotii (CCM F-566) and Gliocladium virens (CCM 8042) - cultures supplied from the Czech Collection microorganisms.

Test conditions:

Sample size: 0 5.5 cm

Incubator temperature: 28 ± 1 ° C

Rel. incubator humidity: 95%

Incubation time: 3 months

Table no. 1 Scale of evaluation of resistance of building materials and products to mold according to ČSN 72 4310: 1977.

The degree of mold growth Verbal description 0 Mold does not grow 1 Growth is slight (scattered colonies of mold) 2 Growth is gradual (numerous small colonies of fungi or continuous light cover that covers less than 25% of the sample surface) 3 Growth is intense (mold cover covers up to 50% of the surface samples) 4 Growth is very intense (mold growth covers 75% surface samples) 5 Mold growth is complete (mold growth covers 100% surface samples)

Table no. 2 Examples for some tested antimicrobial effective cements, building binders, cement containing mixtures and construction products and materials suitable for eliminating and inhibiting mold growth according to ČSN 72 43 10: 1977

The degree of mold growth Suitable for eliminating or inhibiting mold growth 0 CEM III / C 32.5 N, CEM III / B 32.5 N, CEM III / A 32.5 N, Geopolymer binder with 70% slag content, Cement for mortars and masonry MC 5 with 65% slag content CEM III / C 32.5 N SV and CEM III / B sulphate-resistant cements 32,5 N NE 1 CEM II / B-S 32,5 R, Mortar cement for plastering and plastering MC 12,5 X with 45% slag content, Geopolymer binder with a slag content of 40% by weight, 2 CEM II / A-S 42.5 R 3 - 4 - 5 -

The results show that the higher the proportion of antimicrobially activated finely ground granulated blast furnace slag, the more effective the given cement containing antimicrobial mixture will be. Blast-furnace cements of classes CEM III / B 32.5 N (content of granulated blast furnace slag 66 to 80 wt%) and CEM III / C 32.5 N (content of granulated blast furnace slag 81 to 95 wt%) with higher content of granulated blast furnace slag they will therefore be the most effective antimicrobial and may have a potential to fungistatic effect.

Table no. 3 Common environments with the required degree of resistance to mold according to ČSN 72 4310; 1977 suitable for application of cements and binders according to the technical solution.

The degree of mold growth Examples of environments suitable for application of products according to the technical solution 0 Hospital halls, food industry, schools, kitchens, swimming pools, flats, etc. 1 Wood-processing industry, animal production, agriculture, etc. 2 Wine cellars, sewage treatment plants, sewers, dikes etc.

3 - 4 - 5 -

It is not possible to estimate what type of mold can occur at the construction site, so it is prevented by building and antimicrobially the best choice of cements, building binders, cement-containing mixtures and construction products and materials.

Table no. 4 Practical application of OEM lll / A 32.5 N cement for individual applications.

Guide Recipes * CEM III / A 32,5 N ** limy hydrate Sand / gravel Handmade core plaster 10 6 84 Inner stucco plaster 3 17 80 External stucco plaster 10 7 83 Masonry mortar 8 6 86 Lime spatula 4 10 86 Grout 52 - 48 Concrete C 16/20 16 - 84 Concrete C 20/25 18 - 82 Concrete C 25/30 20 - 80

* Ratios in% wt. The individual components are calculated on a dry basis without the addition of additives.

** The amount of cement CEM III / A 32.5 N is selected according to the desired properties of plasters, mortars and concretes such as strength, setting speed, adhesion, consistency, chemical resistance, etc.

The examples given are illustrative only and do not exhaust all variants of the types and compositions of antimicrobially effective cements, building binders, cement-containing mixtures and construction products and materials with different contents of antimicrobially activated granulated blast furnace slag.

Industrial usability

Cements, construction binders, cement-containing mixtures and construction products and materials containing antimicrobially activated granulated blast furnace slag have a wide range of applications, ranging from preventive use to remediation. They are suitable for achieving a microbial clean environment such as e.g. pharmaceutical production, operating theaters, biochemical laboratories, freezers, kitchens, laundry, food production, fruit and vegetable stores, livestock production, public swimming pools, swimming pools, sanitary facilities and wherever water, increased humidity, resp. water vapor. The application is particularly beneficial for the rehabilitation of old damp walls, for the repair of houses in areas affected by floods, for the repair of various accidents associated with water seepage or sewerage. They can also be used successfully in housing construction, they are suitable for the production of antibacterial and antifungal concrete mixtures, masonry mortars and plaster mortars, dry plaster mixtures, cement adhesives, floor mixtures, sanitation cement coatings and other antimicrobially activated granulated blast furnace slag containing construction products.

Claims (1)

PROTECTION REQUIREMENTS Antimicrobially effective cements, building binders, cement containing mixtures and construction products and materials, characterized in that they contain from 5 to 95% by weight of the composition. antimicrobially activated granulated blast furnace slag.