EP2523921A1 - Granulat revêtu pour la préparation de béton - Google Patents

Granulat revêtu pour la préparation de béton

Info

Publication number
EP2523921A1
EP2523921A1 EP11700644A EP11700644A EP2523921A1 EP 2523921 A1 EP2523921 A1 EP 2523921A1 EP 11700644 A EP11700644 A EP 11700644A EP 11700644 A EP11700644 A EP 11700644A EP 2523921 A1 EP2523921 A1 EP 2523921A1
Authority
EP
European Patent Office
Prior art keywords
concrete
aggregate
coating
polymer
coated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP11700644A
Other languages
German (de)
English (en)
Inventor
Dieter Honert
Hans Knauber
Julia Hillenbrand
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sika Technology AG
Original Assignee
Sika Technology AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Priority to EP11700644A priority Critical patent/EP2523921A1/fr
Publication of EP2523921A1 publication Critical patent/EP2523921A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10Coating or impregnating
    • C04B20/1018Coating or impregnating with organic materials
    • C04B20/1029Macromolecular compounds
    • C04B20/1033Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10Coating or impregnating
    • C04B20/1018Coating or impregnating with organic materials
    • C04B20/1029Macromolecular compounds
    • C04B20/1037Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60Agents for protection against chemical, physical or biological attack
    • C04B2103/603Agents for controlling alkali-aggregate reactions

Definitions

  • the invention relates to coated aggregates for concrete production and to processes for their production.
  • the aggregates are generally mineral additives in particulate form, such as sand, gravel, greywacke or opal sandstone. Such surcharges are also referred to as aggregate.
  • a particular problem in the production of concrete with aggregates is the occurrence of the alkali-silica reaction (AKR, also referred to as alkali reaction or concrete cancer).
  • a reaction refers to a chemical reaction in the hardened concrete between alkalis of the cement, alkali-soluble silica and water in concrete aggregates. The reaction may cause cracks and other damage to concrete components, especially in humid environments.
  • additives which have amorphous or finely crystalline silicates, such as, for example, opaline sandstone or flint are considered alkali-sensitive.
  • lithium nitrate may be added to the prior art concrete. It is believed that the diffusion of sodium or potassium ions into the aggregates is responsible for the AKR. The added lithium ions migrate because of their better diffusion properties in place of sodium and potassium ions in the supplements. There form aqueous lithium silicates, which have a relatively small crystal volume and do not lead to an expansion of the concrete. In contrast, the AKR is based on the higher volume of potassium and sodium silicates leading to expansion of the concrete and formation of cracks and fissures further damage. The use of lithium compounds to inhibit AKR is disclosed, for example, in WO 97/09282.
  • lithium compounds are disadvantageous because they are relatively expensive. Generally, global lithium resources are limited. There is a great need for this, including for use in batteries.
  • Another problem with the use of lithium nitrate is that in a concrete concrete mixture is not known exactly what amount of lithium nitrate is to be used. The lithium requirement depends on the concrete properties of the cement and the deposit, such as silicate content, porosity and pH, but above all on the percentage of alkali ions, especially potassium and sodium ions, which is given as Na 2 O equivalent , For the users, however, it is generally too time-consuming to carry out test series prior to the production of the concrete. In JP62-288146 it is proposed to provide the additives with a polymer coating to prevent the AKR.
  • the coating is carried out with mixtures containing relatively low polymer content of 10% and partially organic additives such as asphalt or petroleum, which is not economically desirable and environmentally undesirable. It is also not shown that with the surcharges thus processed an inhibition of the AKR is achieved and that the surcharges are stable over a longer period of time.
  • EP 2 067 753 A1 discloses polymer-coated additives. The coating is intended to stabilize the concrete against mechanical stress.
  • US Pat. No. 6,143,808 discloses powders containing microparticles which are provided with polymers and impart insulating properties to a building material.
  • the invention is based on the problem of providing uses, methods and compositions which overcome the disadvantages described above. the.
  • a process for the production of concrete is to be provided, in which the alkali-silica reaction is prevented, without the addition of lithium compounds is required as concrete admixture.
  • the concrete should have good stability and, even in the long term and in the presence of moisture, should not show any unwanted changes such as cracks or other material damage caused by alkaline reactions in the concrete interior.
  • the method should be used in a simple manner for various cements and surcharges.
  • the problem underlying the invention is surprisingly solved by uses, coated aggregates, concrete compositions and concrete, as well as manufacturing method according to the claims.
  • the invention relates to the use of concrete aggregates which have a coating with organic polymers to improve the stability of concrete against the alkali-silica reaction.
  • the aggregates are prepared by contacting and mixing a mineral aggregate with a polymer dispersion so that the surface of the aggregate is coated with a polymer film, after which the polymer film is cured.
  • Aggregates for concrete are mixtures of grains from natural or artificial sources. In general, mineral additives are used. Aggregates for concrete must have sufficient weathering resistance and must not swell, disintegrate or chemically react in a concrete composition. Aggregates for concrete and their properties are defined and measured according to EN 12620.
  • the aggregate is selected from sand, gravel and grit (eg consisting of flint, greywacke, sandstone, gravel and / or limestone).
  • sand, gravel and grit eg consisting of flint, greywacke, sandstone, gravel and / or limestone.
  • the choice of concrete aggregate is made so that the concrete has the required strength.
  • lightweight aggregates or heavy aggregates can be used according to the invention. Normal additions are those having a bulk density of 2200 to 3200 kg / m 3 , as lightweight aggregates those having a bulk density of less than 2200 kg / m 3 and as heavy aggregate those having a bulk density of more than 3200 kg / m 3 .
  • the mean grain size of the aggregate is between 0.5 and 100 mm, in particular between 2 and 50 mm, between 5 and 50 mm or between 8 and 40 mm, determined according to EN 12620.
  • the mean grain size of the aggregate is between 8 and 40 mm, in particular between 8 to 32 mm or between 8 and 22 mm.
  • chippings from 8 to 22 mm are often used and in the other concrete structures gravel from 8 to 32 mm.
  • the AKR can be prevented particularly efficiently when such aggregate fractions are coated.
  • the concrete additional additives can be added, which are not alkali-sensitive and thus require no coating.
  • additives which are not coated according to the invention may be added outside the preferred ranges mentioned above. Nevertheless, stabilization of the concrete against AKR can surprisingly be achieved.
  • On the aggregate a polymer film is produced, which is cured.
  • the film can be produced by known methods, for example by spraying and dipping in polymers or compositions containing the polymers.
  • the polymer film thus produced on the aggregate is cured, for example by drying.
  • the coating can consist of any desired polymers, for example thermoplastic polymers or chemically curing polymers, such as epoxy resins and polyurethane resins.
  • the coating is particularly preferably carried out with a polymer dispersion (polymer latex).
  • polymer latex refers to a colloidally stable dispersion of polymer particles in an aqueous phase.
  • the diameter of the polymer particles can be, for example, between 10 nm and 5 ⁇ m.
  • the colloidal stability of a polymer dispersion is often caused by surfactants, such as surfactants or protective colloids.
  • Polymer dispersions are commercially available and are used, for example, as adhesives and binders.
  • Suitable polymer dispersions for coating are those which are usually used for modifying mineral building materials.
  • the polymer dispersion used according to the invention is a film former. According to the invention, an aqueous dispersion is preferably used.
  • Polymer dispersions which form thin films on solid surfaces are known in the art.
  • the polymer dispersion should no longer be redispersible on the aggregates after film formation. It is selected so that a uniform thin film is formed on the grains of the aggregate with as few or no gaps as possible.
  • alkali-sensitive aggregates for example having average particle sizes between 8 and 22 mm, can be provided with a very thin polymer layer. This prevents the penetration of sodium and potassium ions in the supplement.
  • the layer according to the invention is stable even at high pH values which are achieved in the concrete.
  • the alkali-silica reaction can be completely prevented by the polymer coating.
  • the coating does not occur in the presence of an organic solvent.
  • other inert coating agents or binders such as waxes or asphalt, is not required.
  • a polymer dispersion preferably an aqueous polymer dispersion is used, which has a polymer content of 5-60 wt .-%, in particular 8 to 40 wt .-% or 10-25 wt .-%.
  • the polymer dispersion should be sufficiently thin in order to achieve a uniform and simple surface coating.
  • the polymer dispersion should not be too be thin so that the drying process does not take too much energy and takes too long, and thus the polymer film is formed as uniformly and seamlessly.
  • a suitable consistency is generally readily adjustable with known polymer dispersions.
  • the dispersion is preferably an aqueous polymer dispersion. It has been found that the coating can be carried out particularly efficiently if the coating takes place in an aqueous polymer dispersion having a polymer content of more than 10% by weight, more than 20% by weight, in particular more than 25% by weight or more than 30 % By weight.
  • the polymer content is, for example, between 10 and 60% by weight, between 20 and 60% by weight, between 25 and 60% by weight or between 30 and 60% by weight. At these concentrations, a permanently stable and effective coating is obtained, while at the same time the removal of the water in the process takes little time and energy.
  • Aqueous polymer dispersions generally contain for stabilization a small proportion of a dispersing agent, in particular an emulsifier, for example in an amount of 0.1 to 5 wt.% Or 0.5 to 2 wt.%.
  • Copolymers of styrene, butadiene, ethylene, acrylate, methacrylate, crotonate, vinyl acetate, vinyl versatate, vinyl laurate, methacrylamide and / or acrylamide and also epoxides and polyurethanes are particularly suitable.
  • the polymers may optionally be chemically modified, for example by carboxylation.
  • the polymer is a styrene-butadiene copolymer or a styrene-acrylate copolymer, which may also be carboxylated.
  • Such polymers can be obtained by emulsion polymerization of ethylenically unsaturated monomers such as styrene and butadiene, or (meth) acrylates.
  • Styrene-butadiene copolymers have, for example, a monomer composition of 50 to 90% by weight of styrene and 10 to 50% by weight of butadiene and may optionally still contain small amounts, eg. B. 1 to 5 wt.%, Based on all monomers, acrylic acid, methacrylic acid, acrylamide or methacrylamide. Suitable polymers and dispersions are described for example in EP-A-754657.
  • Suitable examples are polymer dispersions which contain a copolymer containing as monomer esters of acrylic acid with C 2 -C 12 -alkanols, such as ethyl acrylate, n-butyl acrylate or 2-ethylhexyl acrylate, vinylaromatic monomers, such as styrene, or esters of methacrylic acid, in particular with C 1 -C 4 Alkanols such as methyl acrylate.
  • the copolymers may optionally contain monomers with urea or thiourea groups, such as ureidoethylene methacrylate or hydrolyzable silicon groups, such as 3-methacryloxypropyltrimethyoxysilane.
  • Suitable polymer dispersions and their preparation processes are, for. B also described in EP-A 1 180530 or EP 1 182 179.
  • a method for applying the polymer solution or polymer dispersion to the aggregate are particularly suitable spraying, dipping and drumming.
  • the application and the mixing are done so that the particle surfaces are coated as completely as possible.
  • the amount to be applied depends on the type of polymer film and the aggregate.
  • a coating amount (dry) of from 1 to 100 g / kg supplement, preferably from 5 to 50 g / kg, particularly preferably from 5 to 30 g / kg, is generally sufficient for an efficient action.
  • the coating is cured.
  • Polymer dispersions can usually be cured easily by drying. This can be done, for example, if the surcharge is applied to a foil or a metal grid.
  • the drying time is for example 10 minutes to 3 hours, in particular about one hour, and can additionally be accelerated by air supply and / or elevated temperature.
  • the average thickness of the polymer film is less than 100 ⁇ m, preferably less than 50 ⁇ m or less than 20 ⁇ m, more preferably less than 10 ⁇ m or less than 5 ⁇ m.
  • the polymer film must have sufficient thickness to prevent diffusion of the sodium and potassium ions into the aggregate.
  • the polymer film has an average thickness of at least 2 ⁇ , at least 5 ⁇ or at least 10 ⁇ on.
  • the layer thickness is between 10 and 20 ⁇ . It has been found that in this area a particularly efficient stabilization of an aggregate against AKR can take place, in particular for aggregates with a mean grain size between 8 and 40 mm, in particular between 8 to 32 mm or between 8 and 22 mm.
  • the average layer thickness of the coated aggregate can be controlled by the solids content of the dispersion used.
  • the layer thickness is preferably determined by preliminary tests on a metal sheet. For determination according to DIN EN ISO 2178 the DUALSCOPE MP0 from Fischer is used.
  • the coating contains at least one additive which imparts at least one functionality to the coating.
  • the coating can be used not only as a barrier against the AKR, but also as a carrier layer.
  • the functionality is an additional functionality that would not have the supplement without the additive.
  • the functionality acts in the concrete or in the concrete composition.
  • the aggregate can thus be provided with special properties, for example those which are otherwise caused by constituents of the concrete composition.
  • the additives can thus be specifically positioned in the immediate vicinity of the aggregates and unfold their effect there. In a particular embodiment, the additive diffuses out of the coating and unfolds its effect outside the coating.
  • the additive can be incorporated into the coating if it is homogeneously mixed with the polymer dispersion prior to curing.
  • the polymer and the polymer dispersion are selected so that homogeneous mixing is possible, for example taking into account the surface charge and / or hydrophilicity of the polymers.
  • the at least one additive is selected from a dye, a lithium salt and a crown ether.
  • a dye in the coating has the advantage that a simple, in particular visual, control of the coating is possible.
  • the polymer coatings described are generally thin and colorless or whitish. If a dye is added, it may be checked during the coating process or after the coating has been uniform and complete. In addition, can be checked at a later date, for example, after storage or during further processing in a simple manner by the user, whether the coating is stable.
  • the incorporation of lithium salts, especially in the form of lithium nitrate, into the coating is done to assist in the inhibition of AKR.
  • the addition of lithium ions to concrete compositions for preventing AKR is known.
  • the incorporation into the polymer coating according to the invention is advantageous, however, since the lithium ions are specifically positioned on the aggregate and are not distributed throughout the concrete composition.
  • the diffusion of ions is easier to control and adjust than in the cured concrete. As a result, a significant reduction in the amount of lithium can be achieved, which is of great advantage in view of the relatively high price and the large quantities required for concrete processing.
  • crown ethers are selected, which fix ions such as potassium or sodium ions, which cause the AKR in the aggregates.
  • the invention also provides a concrete composition containing
  • cements inorganic finely ground substances are referred to, which solidify after stirring with water due to chemical reactions independently and harden. According to the invention, it is possible to use any cements which are customarily used for the production of concrete.
  • the term "concrete composition” refers to a curable composition in powder form or in the form of a suspension which is suitable for further processing into a solid concrete molding.
  • the cement may still be largely dry or already partially or completely mixed with water.
  • the cement may be completely or partially set.
  • Concrete additives are powdery or liquid additives that affect certain properties of the concrete.
  • Typical concrete additives are, for example, mineral fines, inert fines, fly ash, color pigments, fibers and organic substances, such as synthetic resin dispersions. Concrete additives are usually taken into account when preparing the recipe of the concrete as volume components. Concrete additives are substances dissolved or suspended in water which are admixed with the concrete in order to change the properties of the fresh or hardened concrete, such as workability, setting behavior, hardening or durability.
  • Conventional concrete admixtures are those according to EN 934, for example concrete plasticizers, flow agents, stabilizers, solidification accelerators, hardening accelerators, retarders, sealants, plasticizers and superplasticizers.
  • a lithium salt in particular lithium nitrate
  • the use of lithium nitrate is not absolutely necessary since the coating according to the invention prevents the AKR.
  • the concrete composition and / or the polymer dispersion contain a crown ether.
  • the crown ether may be copolymerized in a preferred embodiment in the polymer layer.
  • Crown ethers are cyclic ethers that form stable complexes with alkali or alkaline earth ions. Crown ethers are preferably used which form stable complexes with sodium and potassium ions.
  • dicyclohexano [18] crown-6 is particularly suitable for fixing potassium ions in concrete or in the polymer layer.
  • sodium and potassium ions can be fixed in the concrete or in the polymer layer, so that the AKR is additionally hindered.
  • the invention also provides a process for producing concrete, comprising the steps
  • step (B) means that the composition is processed into any three-dimensional shape, for example a pavement, a filling or a molded part. Shaping can take place with the aid of sheathing parts or a casting mold, but also by filling, etc.
  • additives can be used which are not coated. For example, in the concrete composition only those additives can be coated, which tend to AKR due to their nature.
  • the invention also provides a concrete obtainable by curing a concrete composition according to the invention or by a method according to the invention.
  • Concrete is a versatile building material made from mixtures of cements, aggregates and water.
  • the aggregate can be used in any known type of concrete.
  • the aggregate according to the invention is particularly suitable for concrete compositions which have a high effective alkali content.
  • the effective alkali content may be greater than 1%, in particular greater than 1, 5% or greater than 2.5% (Na 2 O equivalent according to DIN 1 164-10).
  • the uses and supplements according to the invention solve the problems underlying the invention.
  • the AKR can be prevented or at least significantly impaired.
  • the use of lithium compounds is no longer necessary.
  • the coating prevents AKR, regardless of the cement used and the overall composition. Regardless, the concrete has good, consistent material properties. Material damage caused by AKR, such as cracks or embrittlement, does not occur or is significantly suppressed, even in humidity and over long periods of time.
  • Example 1 Coating of an aggregate
  • the aggregate for the coating is gravel 8/1 1, 1 1/16 and 16/22 from Mittel Weg Baustoffe GmbH, Harzer Grauwacke Rieder plant or grit (Muschelkalk) granulation 8/16 from the company Schotterwerk Gfrörer & Sohn, Schotterwerk Fischingen or high grade chippings 8/1 1 and 1 1/16 from the Oberrhein area.
  • 8-1 1 mm surcharge, 1 1 -16 mm surcharge and 16-22 mm surcharge are coated separately. In each case, 25 kg of a surcharge are filled into a so-called freefall mixer type LESCHA SM 145 S.
  • Example 2 Production of a Concrete
  • a road concrete is produced with the coated aggregates prepared according to Example 1.
  • the following road concrete recipe is used and mixed as follows: 542 kg / m 3 0-2 mm surcharge (Rhine sand from KVB Kies-Vertrieb GmbH & Co. KG, Karlsdorf-Neuthard, Waghausel plant), 217 kg / m 3 2-8 mm surcharge (Rheinkies from KVB Kies-Vertrieb GmbH & Co.
  • Air entraining agents 0.2% of Z.-wt.
  • Plasticizer 0.6% of theory Z.-wt.
  • Air content 5.0 vol. -%
  • Table 1 Length changes in mm / m after different time intervals.
  • A Measured values for beams with uncoated chippings (comparative experiment).
  • B Measured values for beams with coated grit according to the invention.
  • C Difference amounts of A and B. 1 d 7 d 14 d 28 d 2 m 3 m 4 m 5 m
  • Table 1 shows that the difference in elongation between treated and untreated samples increases over time. This shows that the coating of the grain in the selected size range protects against AKR.
  • Example 4 Testing of bending tensile strength
  • beams (700 x 150 x 1 50 mm) were prepared to determine the bending tensile strength.
  • the bending tensile strength is tested according to DIN EN 12390-5 (02/2001) after 28 days of water storage.
  • a bending tensile strength of 6.6 N / mm 2 was measured in the comparative experiment, while a bending tensile strength of 7.1 was measured for a beam with coated grit.
  • the coating of the aggregate thus does not significantly affect the flexural strength of the concrete.
  • the test was carried out by CDF method. Also according to the same recipe, however, instead of the 8/1 1 and 1 1/16 grains, 8/16 chalk (once dried and once wet, both coated and uncoated) was used and twice the amount Plasticizer, specimens were prepared for the CDF process. The procedure is carried out in accordance with DIN CEN / TS 12390-9 (08/2006).
  • the coating of the aggregate thus has no significant influence on the weathering of the concrete.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention concerne des granulats revêtus pour la préparation de béton et des procédés de préparation de ces granulats. L'invention concerne également des compositions de béton pour la préparation de béton, du béton pourvu de granulats, des procédés de préparation et l'utilisation de polymères organiques pour améliorer la stabilité de béton.
EP11700644A 2010-01-15 2011-01-12 Granulat revêtu pour la préparation de béton Ceased EP2523921A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11700644A EP2523921A1 (fr) 2010-01-15 2011-01-12 Granulat revêtu pour la préparation de béton

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10150873A EP2345626A1 (fr) 2010-01-15 2010-01-15 Supplément revêtu destiné à la fabrication de béton
PCT/EP2011/050340 WO2011086095A1 (fr) 2010-01-15 2011-01-12 Granulat revêtu pour la préparation de béton
EP11700644A EP2523921A1 (fr) 2010-01-15 2011-01-12 Granulat revêtu pour la préparation de béton

Publications (1)

Publication Number Publication Date
EP2523921A1 true EP2523921A1 (fr) 2012-11-21

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EP11700644A Ceased EP2523921A1 (fr) 2010-01-15 2011-01-12 Granulat revêtu pour la préparation de béton

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US (1) US8653163B2 (fr)
EP (2) EP2345626A1 (fr)
WO (1) WO2011086095A1 (fr)

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EP2067753A1 (fr) * 2007-12-03 2009-06-10 Lafarge SA Mélange de béton

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
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See also references of WO2011086095A1 *

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US20130005865A1 (en) 2013-01-03
US8653163B2 (en) 2014-02-18
WO2011086095A1 (fr) 2011-07-21
EP2345626A1 (fr) 2011-07-20

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