CN111807793A - Cement-based compositions having fast developing tensile adhesion strength - Google Patents

Cement-based compositions having fast developing tensile adhesion strength Download PDF

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Publication number
CN111807793A
CN111807793A CN202010277456.8A CN202010277456A CN111807793A CN 111807793 A CN111807793 A CN 111807793A CN 202010277456 A CN202010277456 A CN 202010277456A CN 111807793 A CN111807793 A CN 111807793A
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cement
weight
composition according
composition
water
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刘晴
岑志杰
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Sika Technology AG
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Sika Technology AG
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    • 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
    • C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
    • E04F13/0885—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements specially adapted for being adhesively fixed to the wall; Fastening means therefor; Fixing by means of plastics materials hardening after application
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
    • E04G21/00—Preparing, conveying, or working-up building materials or building elements in situ; Other devices or measures for constructional work
    • 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
    • C04B2111/70—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
    • 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
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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

Abstract

The present invention relates to a cement-based composition having a rapidly developing tensile adhesive strength. The composition comprises a belite sulphoaluminate cement and is suitable for use as, for example, a tile adhesive for rapid tiling and repair. The invention also provides a method for quickly paving bricks.

Description

Cement-based compositions having fast developing tensile adhesion strength
Technical Field
The present invention relates to a cement-based (cementious) composition having a rapidly developing tensile adhesion strength. The composition is suitable for use as an adhesive, particularly as a tile adhesive for rapid tiling and repair. Furthermore, the invention relates to a structure, in particular a floor, a wall or a ceiling, comprising a covering element, in particular a tile, wherein the covering element is fixed to the structure with a cement-based composition.
Background
Cementitious compositions such as cement-based tile adhesives or grouts (grout) can be distinguished as having a fast or regular hardening material, e.g. measurable and distinguished as a fast or regular developing tensile adhesion strength. The rapid development of tensile adhesion strength, for example, of brick adhesives, allows for more rapid post-application to workable times. Faster time to feasibility is desirable because it results in faster build and less downtime.
The properties and hardening characteristics are directly related to the formulation of such cement-based compositions. Most cement-based compositions based on conventional portland cement (OPC) produce materials with regular hardening properties. Cement-based compositions based on Calcium Aluminate Cement (CAC) and/or Calcium Sulphoaluminate (CSA) cements produce materials with faster hardening characteristics and therefore faster time to go through.
Furthermore, during OPC production, high energy consumption is required for sintering and grinding, and thus significant amounts of CO are released per ton of cement2. CO reduction for cement producers2Efforts to discharge include the use of an alternative to OPC, which is based on clinker requiring less production energy. One such alternative is the use of CSA cement.
Conventional CSA cements exhibit rapid development of strength. However, to produce conventional CSA cement, high quality raw materials such as bauxite, gypsum, and limestone are required. An alternative is the gazeite CSA cement, which can be manufactured from low quality raw materials such as fly ash and FGD gypsum. However, the hypercalcite CSA cement does not exhibit the same rapid development strength as conventional CSAs.
CN106396563 discloses a composition based on a white quick-drying low-alkali cement, which may be selected from aluminate cements, sulphoaluminate cements and belite cements. One disadvantage is that while aluminate and sulfoaluminate cements exhibit rapid hardening and high early strength, conventional CSA cements with high content of belite exhibit slower hydration and lower early strength and higher long-term rate of volume change, all similar to the OPC described above.
US10029944 discloses a mortar composition based on CAC slurry which can be used with Li2CO3Supersaturated NaOH solution. One problem is that the applicator has to handle NaOH solutions, which are highly alkaline and risk occupational health and safety aspects.
CN108675734 discloses a brick binder based on a two-component binder system, comprising fast-setting cement and gypsum. One problem is that such binary binder systems are difficult to produce with sufficient consistency because their performance is very dependent on the exact quality of the build binder material used.
CN106277981 discloses a composition suitable as a brick binder comprising cement with fast setting properties and fly ash as filler. However, the type of cement is not further specified, and the use of fly ash as a filler entails problems associated with the rapid development of tensile adhesive strength, as required for example by the Chinese standard JC/T547-2005 or the European standard EN1348 for brick adhesives.
There is therefore a need for a cementitious composition useful as a tile adhesive which has a rapidly developed strength and which overcomes the problems of the prior art described above.
Disclosure of Invention
It is an object of the present invention to provide a cement-based composition having a rapidly developed tensile adhesion strength.
It is another object of the present invention to provide a cement-based composition useful as a binder for tiles, particularly ceramic tiles.
It is a further object of the present invention to provide a method of rapid tiling.
A final object of the invention is to provide a structure, in particular a floor, wall or ceiling, comprising covering elements, in particular tiles, wherein the covering elements are fixed to the above structure with a cement-based composition.
Surprisingly, it has been found that the composition according to claim 1 can solve the problem of rapidly developing tensile adhesion strength.
The object of the present invention is therefore a cement-based composition comprising:
1)20-64.5 w-%, preferably 25-49.5 w-%, in particular 30-40.5 w-% of at least one monetite CSA cement,
2)35-79.5 w%, preferably 50-74.5 w%, especially 59-69.5 w% of an aggregate, preferably sand,
3)0.5 to 15% by weight, preferably 1 to 10% by weight, in particular 1.2 to 5% by weight, of at least one synthetic organic polymer,
4)0-5.0 w% of further additives selected from plasticizers, superplasticizers, rheology modifiers, thickeners, air-entraining agents, degassing agents, defoamers, corrosion inhibitors, fibers, swell-generating additives, pigments, accelerators, retarders, strength enhancers, in particular early strength enhancers, waterproofing additives, alkali-aggregate reaction inhibitors, chromate reducing agents and/or antibacterial agents, each based on the total weight of the dry composition.
It has been found that the cementitious composition according to the invention can be used as a tile adhesive, in particular a ceramic tile adhesive, having a rapidly developed tensile adhesion strength for the laying and/or repairing of tiles. The cement-based composition according to the invention thus forms a tensile adhesion strength of >0.5MPa within the first 24h, preferably within the first 6h, after addition of the mixing water, when measured according to the Chinese standard JC/T547-2017. This rapidly developed tensile adhesion strength allows for faster release of the tiled surface for further work and/or traffic.
Furthermore, the tensile adhesion strength of the composition of the invention was >0.5MPa also after heat ageing and water immersion according to the Chinese standard JC/T547-2017. Such performance is evidence of good durability and long service life.
The preparation of the tile adhesive composition is quite easy and safe: the cement-based composition, especially in the dry state, is mixed with a suitable amount of water. Thereafter, the tile adhesive can be ready for use in a tile or other application.
It has further been found that a cement-based composition according to the invention applied with an open time of 20min has a tensile adhesion strength after 28 days of curing which is at least 60% of the tensile adhesion strength of the same composition measured after 10min of open time and subsequent 28 days of curing under the same conditions. Such properties are important for reasonable application, especially tile methods.
Further advantages of the compositions of the invention are excellent processability, adjustable open time, reduced efflorescence, good slip resistance and low shrinkage. Low shrinkage is an advantage because higher shrinkage will lead to cracking of the cured cement-based material.
The cement-based composition of the invention is therefore suitable as a mortar in construction applications. It is particularly suitable as a tile adhesive for laying and/or repairing tiles, in particular ceramic tiles. It may further be suitable as a quick repair mortar, for grouting applications, as a self-leveling product for flooring applications, as a levelling material (screened), render or water plug material (water plug) and for water-or fire-proofing applications.
Modes for carrying out the invention
The cement-based composition, preferably the tile adhesive, of the present invention comprises at least one Calcium Sulfoaluminosilicate (CSA) cement of the mullite. The hypercalcite CSA cement is present in 20-64.5 w%, preferably 25-49.5 w%, especially 30-40.5 w%, each based on the total weight of the dry composition.
In the context of the present invention, a hypercalcite CSA cement is a cement comprising clinker consisting essentially of: clinoptilolite C of predominant phase2S(2CaO·SiO2) Calcium sulphoaluminate C4(A3-xFx)3$(4CaO·3-x Al2O3·x Fe2O3·CaSO4Where x is an integer of 0 to 3), ferrites such as C2F(2CaO·Fe2O3)，C2AF(2CaO·Al2O3·Fe2O3)，C4AF(4CaO·Al2O3·Fe2O3) Preferably C4AF, and calcium oxide.
According to the embodimentsA CSA cement comprising clinkers, which clinker comprises 37-47 w% of clinoptilolite, 20-35 w% of calcium sulphoaluminate, 3-9 w% of ferrite, in particular C4AF, and 0.5-4.6 w% CaO, each relative to the total weight of the clinker. The clinker of the CSA cement used in the present invention may contain other minor phases such as aluminates (CA, C)3A，C12A7) And/or ternesite (C)5S2$)。
In a particularly advantageous embodiment of the invention, the hypercalcemic CSA cement additionally comprises at most 35 w%, preferably at most 27 w%, in particular at most 15 w% of calcium sulphate, each based on the total dry weight of the cement. The calcium sulfate may be present in the form of calcium sulfate hemihydrate, calcium sulfate dihydrate and/or anhydrite. In a most preferred embodiment, CaSO4Is present as part of the clinker.
A suitable one in the context of the present invention is for example disclosed in EP 3081546.
Furthermore, the cement of the present invention may comprise a cement improver selected from the group consisting of: grinding aids, strength modifiers, activators, accelerators, fibers, plasticizers and/or superplasticizers. The cement improver may be interground with the clinker during grinding. They can likewise be mixed into the ground clinker.
In addition to the clinker described above, the hypercalcite CSA cement of the invention may contain other binders. They are in particular latent hydraulic binders and/or pozzolanic (pozzolanic) binders. Suitable latent hydraulic and/or pozzolanic binders are, for example, natural pozzolans, slag, fly ash, silica fume, calcined slate and/or limestone. According to an embodiment, the cement-based binder may comprise at most 35 w%, preferably at most 20 w%, in particular at most 10 w% of latent hydraulic and/or pozzolanic binder, each based on the total dry weight of the cement. Too low amounts of clinker in the inventive high belite CSA cement may result in less rapid development of tensile adhesion strength.
Preferably, the hypercalcite CSA cement used in the context of the present invention belongs to a strength grade according to DIN EN197-1 of 32.5, 42.5 or 52.5. It is particularly preferred that the hypercalcite CSA cement used belongs to a strength grade of 42.5 according to DIN EN 197-1.
The cementitious composition (preferably a brick binder) of the present invention comprises an aggregate, preferably sand. Sand is a naturally occurring granular material comprising finely divided rock or mineral particles. It is available in different forms and sizes. Examples of suitable sands are quartz sand, limestone sand, river sand or crushed aggregates. Suitable sands are described, for example, in the standard ASTM C778 or EN 196-1.
According to an embodiment, at least a portion of the sand used in the cement-based composition of the invention is quartz sand, river sand, sand made of, for example, granite or limestone, or a mixture thereof. According to a preferred embodiment, river sand is used in the cement-based composition of the invention, since it is chemically inert, strong, available in different sizes, and the workability of the composition can be advantageously set.
Sand is typically provided in different fractions of particles passing through a sieve having through holes. Suitable methods for sieve analysis are described, for example, in ASTM C136/136M. Sand can thus be characterized by its particle size distribution and corresponding D value. For example, the D50 value is the diameter of the particle for which 50% of the sample mass is smaller and 50% of the sample mass is larger. The D99 value is, for example, the diameter at which 99% of the sample mass contains particles having a diameter smaller than this value. The D1 value is, for example, the diameter at which 1% of the sample mass contains particles having a diameter smaller than this value.
According to an embodiment, sand having a D99 value of 1mm, preferably 0.8mm, even more preferably 0.6mm is used in the cement-based composition of the invention. Larger particles may result in improper mixing.
According to an embodiment, the particle size D50 of the sand is 0.04-1mm, more preferably 0.05-0.8mm and even more preferably 0.05-0.6 mm. Preferably, at least part of the sand has a particle size D50 of at least 100 μm, more preferably at least 200 μm.
According to a particularly preferred embodiment, sand having a bimodal particle size distribution is used. This may be achieved by mixing two sands having different particle size distributions and thus different values of D99 and D1. For example, the aggregate used in the cementitious composition of the invention may consist of 50-70 w% sand with a D99 of 0.3mm and a D1 of 0.1mm and 30-50 w% sand with a D99 of 0.5mm and a D1 of 0.3mm, each based on the total dry weight of the aggregate. Such a granulometry allows to optimize the overall granulometric distribution to achieve homogeneous mixing, good rheology of the fresh mortar and high strength of the hardened mortar.
The cement-based composition of the invention comprises 35-79.5 w-%, preferably 50-74.5 w-%, especially 59-69.5 w-% sand, each based on the total weight of the dry composition.
The cement-based composition of the invention, in particular a tile adhesive, comprises 0.5-15 w%, preferably 1.0-10 w%, in particular 1.2-5 w%, of a synthetic organic polymer, each based on the total weight of the dry composition.
Synthetic organic polymers in the context of the present invention may be produced by free radical polymerization of monomers selected from the group consisting of: ethylene, propylene, butylene, isoprene, butadiene, styrene, acrylonitrile, acrylic acid, methacrylic acid, esters of acrylic acid, esters of methacrylic acid, vinyl esters, vinyl chloride. Preferably, the synthetic polymer is a copolymer synthesized from two or more, preferably two, different monomers. The order of the copolymers may be alternating, block or random. Preferred synthetic organic polymers are copolymers of vinyl acetate and ethylene, vinyl acetate and ethylene and methyl methacrylate, vinyl acetate and ethylene and vinyl ester, vinyl acetate and ethylene and acrylic acid esters, vinyl chloride and ethylene and vinyl laurate, vinyl acetate and vinyl valerate, acrylic acid esters and styrene and butadiene, acrylic acid esters and acrylonitrile, styrene and butadiene, acrylic acid and styrene, methacrylic acid and styrene, styrene and acrylic acid esters, styrene and methacrylic acid esters.
The glass transition temperature (Tg) of the synthetic organic polymers can vary over a wide range. Suitable synthetic organic polymers may have a Tg of, for example, -50 ℃ to +60 ℃, preferably-45 ℃ to +35 ℃, more preferably-25 ℃ to +15 ℃.
It is possible and in some cases preferred to use a mixture of more than one of said synthetic polymers in the composition of the invention.
According to a particularly preferred embodiment, the synthetic organic polymer is used in solid form, for example as a redispersible polymer powder. Such redispersible polymer powders can be produced, for example, by spray drying the polymer dispersions, as described, for example, in patent application EP 1042391. Suitable redispersible powders are available, for example, under the trade name Vinnapas from wacker chemie AG. The use of redispersible powders of synthetic organic polymers is preferred in the context of the present invention. Particular preference is given to redispersible powders comprising vinyl acetate-ethylene copolymers having a Tg of from-10 ℃ to 20 ℃, preferably from 10 to 20 ℃.
The cement-based composition of the invention, in particular the tile adhesive, may comprise up to 5 w% of other additives, based on the total weight of the dry composition. Such further additives are selected from plasticizers, superplasticizers, rheology modifiers, thickeners, air entraining agents, air release agents, defoamers, corrosion inhibitors, fibers, swell-generating additives, pigments, accelerators, retarders, strength enhancers, in particular early strength enhancers, water-proofing additives, alkali-aggregate reaction inhibitors, chromate reducing agents and/or antibacterial agents.
According to a preferred embodiment, the cementitious composition of the invention therefore additionally comprises:
1)0.1-3 w% of at least one thickener selected from the group consisting of: starch, modified starch, cellulose, modified cellulose, casein, guar gum, xanthan gum, alginates, tragacanth, pectin, pullulan, dextran, polydextrose, polyvinyl alcohol, poly (meth) acrylic acid, polyacrylamide, polyvinylpyrrolidone and polyethylene glycol,
2)0.01-1 w% of at least one retarder selected from the group consisting of: sugar acids, sugars, sugar alcohols, hydroxycarboxylic acids or their salts, phosphoric esters, phosphonic esters, boric esters and amines,
3)0.1-2 w% of at least one early strength enhancing agent selected from the group consisting of salts of formic acid, bicarbonates and carbonates,
each based on the total weight of the dry composition.
According to a preferred embodiment, the at least one thickener is a modified cellulose, in particular methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxyethylhydroxypropylcellulose, ethylhydroxyethylcellulose, sodium carboxymethylcellulose, in particular hydroxypropylcellulose, and the at least one retarder is a hydroxycarboxylic acid or a salt thereof, in particular sodium citrate, and the at least one early strength enhancer is an alkali metal or alkaline earth metal salt of an alkali metal or alkaline earth metal carbonate and/or formic acid, in particular lithium carbonate and/or calcium formate.
A particularly preferred cementitious composition, in particular a tile adhesive, of the present invention therefore comprises:
1)20-64.5 w-%, preferably 25-49.5 w-%, in particular 30-40.5 w-% of at least one monetite CSA cement,
2)35-79.5 w%, preferably 50-74.5 w%, especially 59-69.5 w% of an aggregate, preferably sand,
3)0.5 to 15% by weight, preferably 1.0 to 10% by weight, in particular 1.2 to 5% by weight, of at least one synthetic organic polymer,
4)0.1-3 w% of at least one thickener selected from the group consisting of modified celluloses,
5)0.01 to 1% by weight of at least one retarder which is a hydroxycarboxylic acid or a salt thereof, in particular sodium citrate,
6)0.1-2 w% of at least one early strength enhancing agent selected from lithium carbonate and/or calcium formate,
each based on the total weight of the dry composition.
The cementitious compositions of the present invention, particularly tile adhesives, can be made by mixing the above materials by any method known to those skilled in the art. There is no particular limitation on the order of mixing and addition. According to certain embodiments, the cement-based compositions of the invention, particularly tile adhesives, may be made by mixing the above materials in a horizontal single axis mixer, a dual axis paddle mixer, a vertical axis mixer, a ribbon blender, an orbital mixer, a change can mixer, a rotating drum vessel, a vertical mixing chamber, or an air mixing operation. The mixing may be continuous or batch.
According to a preferred embodiment, the cement-based composition of the invention is a one-component mixture. That means that all individual materials and/or substances are intermixed. One-component compositions are particularly easy to handle and exclude the risk of mixing or mis-metering of the individual components by the user.
However, in principle the cement-based composition of the invention may be provided as a two-component or even multi-component composition. The first component may for example be present in a first container comprising a hydraulic binder and a polymer. The second component present in the second container may comprise aggregate. Other allocations are also possible. The two or more component compositions allow for adjustment of the cement-based composition, for example, depending on the particular application.
The cement-based compositions of the present invention exhibit a tensile adhesive strength that develops rapidly upon mixing with water.
Water may be added to the cement-based composition of the invention in a water/cement ratio of from 0.1 to 2.0, preferably from 0.2 to 1.0, more preferably from 0.4 to 0.9, especially from 0.7 to 0.9. The water can be any available water such as distilled water, purified water, tap water, mineral water, spring water, and well water. Wastewater is used only in situations where the composition of such wastewater is known and where the impurities contained therein do not affect the function of any other component of the composition of the present invention. The use of brine is not preferred due to its high chloride content and the risk of corrosion of the steel reinforcement to which it is attached.
The cement-based composition of the invention is easy to process after mixing with water. In particular, the mixed composition has a consistency that allows application to vertical surfaces and overhanging areas without dripping.
The cement-based composition according to the invention, when measured according to the Chinese standard JC/T547-2017, develops a tensile adhesion strength of ≥ 0.5MPa within the first 24h, preferably within the first 6h, after addition of the mixing water. Furthermore, according to the Chinese Standard JC/T547-2017, also after heat ageing, water immersion and/or freeze-thaw cycles, the tensile adhesion strength of the composition of the invention is ≥ 0.5MPa, in particular ≥ 1.0 MPa. Furthermore, the cement-based composition according to the invention forms a tensile adhesion strength of ≥ 0.5MPa, preferably ≥ 1MPa, after an extended open time of 10 minutes, in particular 20 minutes, preferably 30 minutes. In particular, the tensile adhesion strength of the cementitious composition according to the invention after application at an open time of 20 minutes and after 28 days of curing is at least 60% of the tensile adhesion strength of the same composition as measured after 10min of open time and subsequent 28 days of curing under the same conditions.
The rapid development of tensile adhesion strength of the present cementitious compositions significantly reduces the waiting time required before a surface, particularly a tile surface, can be released for further work or traffic. By using the cement-based composition of the invention, this waiting time can be reduced to <48h, preferably <24 h.
As can be shown, the cement-based composition has good adhesion to different kinds of materials, in particular to mortar, concrete, ceramics, wood and metals. In particular, the cement-based composition is characterized by a highly beneficial adhesion to different types of bricks and sheets (veneer). In particular, it can be realized according to the Chinese standard
JC/T547-2017 meets the performance of standard C2E S2.
The cement-based composition according to the invention is therefore particularly useful as a brick binder.
According to a preferred embodiment, the cement-based composition according to the invention is used for bonding ceramic tiles (which may be water-absorbing or non-water-absorbing), such as for example ceramic tiles, terracotta tiles, fully vitrified tiles, glazed tiles, stoneware tiles (stoneware) or ceramic tiles, as well as cement-based tiles and stone tiles, in particular natural stone tiles. Preferably the tile adhesives of the present invention are not used to bond artificial tiles (which are based on organic polymeric binders).
According to a particularly preferred embodiment, the cementitious composition according to the invention is used for bonding ceramic tiles with a water absorption of < 0.5%, measured according to ASTM C373-18 or EN ISO 10545-3.
The cementitious composition of the present invention may thus be used in a surface tiling process. Such a method comprises the steps of:
1) preparing the surface of the workpiece to be processed,
2) the cement-based composition of the invention is mixed with water,
3) applying the water-mixed cementitious composition to the substrate and/or tile,
4) and laying bricks.
According to an embodiment, step 1) of the process of the invention comprises at least one of the following steps: leveling, drying, cleaning of e.g. oil, dirt, loose parts of the surface, and/or applying a primer to the surface.
According to an embodiment, step 2) of the process of the invention comprises mixing the cement-based composition of the invention with water in a water/cement ratio of 0.1 to 2.0, preferably 0.2 to 1.0, more preferably 0.4 to 0.9, in particular 0.7 to 0.9. The water can be any available water such as distilled water, purified water, tap water, mineral water, spring water, and well water. Mixing can be continuous or intermittent, for example by hand-held mixers, Hobart mixers, portable concrete mixers, mixing trucks, mixing drums, paddle mixers, jet mixers, screw mixers or screw mixers.
According to an embodiment, step 3) of the method of the invention comprises applying the cement-based composition of the invention by means of a doctor blade, a trowel, preferably a notch trowel, a brush or as a spray. The thickness of the layer to which the cement-based composition of the invention is applied may vary between 1 and 15mm, preferably between 3 and 10 mm. Preferably, the layer thickness is selected according to the type of tile to be bonded.
According to an embodiment, step 4) of the method of the invention is carried out during a certain open time from the application of the cement-based composition of the invention. The open time can vary between 1 and 120min, preferably between 5 and 90min, in particular between 10 and 50 min.
The cementitious compositions of the present invention may also be used in a method of repairing a tile surface. Such repair may involve replacing the damaged brick, injecting the cement-based composition of the invention under the damaged brick, and grouting the joint.
Another aspect of the invention is a hardened cementitious composition obtainable or obtainable by adding water to the above-mentioned cementitious composition.
Another aspect of the invention relates to a structure, in particular a floor, wall or ceiling, comprising a support element and a covering element, in particular a tile, wherein the covering element is fixed to the support element with the above cement-based composition. In particular, the cement-based composition is arranged between a support element and a covering element of the structure.
Preferably, the thickness of the adhesive composition in the structure is 1 to 15mm, in particular 3 to 10 mm.
Optionally, there may be additional primer layers and/or intermediate layers between the support element and the cementitious composition and/or between the cementitious composition and the cover element. This may further increase the adhesion between the support element and the cover element and/or help to achieve an even better noise or vibration damping effect.
In particular, the support element is a floor, wall or ceiling, which is essentially made of mortar, concrete, brick, plaster, metal, plastic and/or wood. Preferably the covering element is a tile in the form of a ceramic tile, stone and/or sheet.
The following working examples illustrate the invention. These examples are not intended to limit the scope of the present invention in any way.
Working examples
A summary of the chemicals used is given in table 1 below. The chemicals were used as supplied without further purification.
TABLE 1
Figure BDA0002445330790000121
The dry blends given in tables 2 and 3 below were prepared at 23 ℃ and 50% relative humidity. To prepare a dry blend, the ingredients were weighed into a Hobart N50 mixer and mixed on low speed for 2 min. The dry blend is used without storage.
Water in an amount to achieve a w/p (water: powder) ratio of 0.27 was weighed into the mixing pan. The dry blend is added over 5-10s while stirring at low speed. Mixing was continued at low speed for 30 s. Mixing was then stopped and the disc and paddle cleaned within 60 s. Mixing was then continued at low speed for 60 s. Mixing was then stopped and the mixture was left to cure for 3min and then remixed for 15 s. The resulting mixture was smooth and free of any lumps.
The slip (slip) was measured according to the Chinese standard JC/T547-2017.
Initial and final set times were measured using a Vicat apparatus according to ASTM C191-04.
The tensile adhesion strength was measured after a curing time of 6h and 28 days, respectively, according to the Chinese standard JC/T547-2017. Tensile adhesion strength was also measured after 7 days of cure and subsequent 21 days of immersion in water at 23 ℃. Furthermore, tensile strength was measured after 14 days of cure and subsequent heat aging at 70 ℃ for 14 days.
Finally, the tensile adhesion strength was measured after 28 days curing according to the Chinese standard JC/T547-2017, which used bricks (P1 ceramic bricks, water absorption 12-18%) for the brick binders of Table 1 within 10min and 20min, respectively, after the addition of mixing water. This time of 10min and 20min is referred to as the open time in table 1.
TABLE 2
Figure BDA0002445330790000131
Figure BDA0002445330790000141
n.m.: not measured
As can be seen from table 2, the cement-based composition according to the invention shows a fast development of tensile adhesive strength. In fact, values of ≧ 0.5MPa have been achieved during 6 hours of curing, which are required by the relevant standard JC/T547-2017. The performance after 28 days of curing and after subsequent water immersion and heat ageing is also better than that required for the C2E S2 rating according to the relevant standard. The same is true for tensile adhesion strength after 10min and 20min open time. On the other hand, comparative example 1 (which is not according to the invention) does not show sufficient tensile strength after water immersion and heat aging as required by the relevant standard JC/T547-2017. In addition, comparative example 1 did not exhibit sufficient tensile strength after 10min open time, and strength was not measurable after 20min open time.
It can also be seen from table 2 that inventive example 2 shows significantly higher set times (initial and final) than non-inventive comparative example 1. Such a higher setting time may be advantageous as it provides more time for the applicator to install the tile adhesive and subsequently install the tile.

Claims (15)

1. A cement-based composition comprising:
1)20 to 64.5% by weight, preferably 25 to 49.5% by weight, in particular 30 to 40.5% by weight, of at least one high belite calcium sulphoaluminate cement,
2)35-79.5 w%, preferably 50-74.5 w%, especially 59-69.5 w% of an aggregate, preferably sand,
3)0.5 to 15% by weight, preferably 1 to 10% by weight, in particular 1.2 to 5% by weight, of a synthetic organic polymer,
4)0-5 w% of other additives selected from plasticizers, superplasticizers, rheology modifiers, thickeners, air-entraining agents, deaerators, defoamers, corrosion inhibitors, fibers, swell-producing additives, pigments, accelerators, retarders, strength enhancers, in particular early strength enhancers, waterproofing additives, alkali-aggregate reaction inhibitors, chromate reducing agents and/or antibacterial agents,
each based on the total weight of the dry composition.
2. The cement-based composition according to claim 1, characterized in that said hypercalcemic calciumsulfoaluminate cement comprises clinker, which comprises 37-47 w% of clinoptilolite, 20-35 w% of calcium sulfoaluminate, 3-9 w% of ferrites and 0.5-4.6 w% of CaO, each relative to the total dry weight of the clinker.
3. Cementitious composition according to claim 2, characterized in that said clinker further comprises at most 35 w%, preferably at most 27 w%, in particular at most 15 w% of calcium sulphate, each based on the total dry weight of said cement.
4. Cement-based composition according to claim 2 or 3, characterized in that said clinker further comprises aluminates (CA, C)3A、C12A7) And/or xonotlite (C)5S2$)。
5. Cement-based composition according to claim 1, characterized in that said at least one gazelite CSA cement belongs to a strength grade according to DIN EN197-1 of 32.5, 42.5 or 52.5, preferably to a strength grade of 42.5.
6. A composition according to claim 1, characterized in that the aggregate is a mixture of at least two sands having different particle size distributions, wherein the mixture comprises 50-70 w% of a first sand with D99 of 0.3mm and D1 of 0.1mm and 30-50 w% of a second sand with D99 of 0.5mm and D1 of 0.3mm, each based on the total dry weight of the aggregate.
7. Composition according to claim 1, characterized in that the synthetic organic polymer is a redispersible polymer powder.
8. Composition according to any one of the preceding claims, characterized in that it comprises:
1)20-64.5 w-%, preferably 25-49.5 w-%, in particular 30-40.5 w-% of at least one monetite CSA cement,
2)35-79.5 w%, preferably 50-74.5 w%, especially 59-69.5 w% of an aggregate, preferably sand,
3)0.5 to 15% by weight, preferably 1 to 10% by weight, in particular 1.2 to 5% by weight, of at least one synthetic organic polymer,
4)0.1-3 w% of at least one thickener selected from the group consisting of modified celluloses,
5)0.01 to 1% by weight of at least one retarder which is a hydroxycarboxylic acid or a salt thereof, in particular sodium citrate,
6)0.1-2 w% of at least one early strength enhancing agent selected from lithium carbonate and/or calcium formate,
each based on the total weight of the dry composition.
9. Use of a cementitious composition according to any of the preceding claims for the installation, repair and/or grouting of tiles.
10. Use according to claim 9, characterized in that the brick is a ceramic brick, a cement-based brick or a stone brick.
11. Use according to claim 10, characterized in that the tile is a ceramic tile with water absorption < 0.5% according to ASTM C373-18.
12. A method of tiling a surface comprising the steps of:
a) the surface is prepared in such a way that,
b) mixing a cement-based composition according to any one of claims 1 to 8 with water in a water/cement ratio of 0.1 to 2.0, preferably 0.2 to 1.0, more preferably 0.4 to 0.9, especially 0.7 to 0.9,
c) applying the water-mixed cementitious composition to a substrate and/or tile,
d) and laying bricks.
13. Method according to claim 10, characterized in that the layer thickness of the cement-based composition applied in step c) varies between 1 and 15mm, preferably between 3 and 10 mm.
14. The process according to claim 10, characterized in that step d) is carried out within 1 to 120min, preferably 5 to 90min, in particular 10 to 50min, after the completion of step b).
15. A structure, in particular a floor, wall or ceiling, comprising a support element and a covering element, in particular a tile, wherein the covering element is fixed to the support element with a cementitious composition according to any one of claims 1 to 8.
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