Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/001—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 unburned clay
• • 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
• • 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

Definitions

• the invention relates to the field of binders, in particular binders for construction products such as concretes and mortars.
• binders can be organic, in particular based on resins, but are most often mineral, hydraulic or non-hydraulic binders.
• Hydraulic mineral binders that is to say binders which set irreversibly in contact with water and which can harden underwater
• cements such as Portland cements (possibly added with at least one other product chosen from granulated blast furnace slag or pozzolanic compounds such as fly ash), aluminous cements, tallow-aluminous cements.
• Non-hydraulic mineral binders include, in particular, air lime and gypsum binders (based on calcium sulphate).
• binders that are both low carbon footprint and non-irritant.
• the subject of the present invention is a binder comprising:
• At least one raw clay comprising at least one clay mineral, the total weight content of clay mineral ranging from 1 to 60% relative to the weight of binder, at least one calcareous or dolomitic filler,
• At least one additive chosen from flocculating agents, water-repellent agents, latexes, hydraulic binders, tackifying agents and cationic surfactants,
• the binder comprises a hydraulic binder
• the total weight content of hydraulic binder is less than the total weight content of clay mineral.
• the contents indicated for the constituents of the binder, respectively of the mortar are contents by weight expressed relative to the total weight of the binder composition, respectively of the mortar composition.
• clay is understood to mean a pulverulent material mainly comprising at least one clay mineral.
• the clay can consist of a clay mineral or several clay minerals.
• the clay may contain, in addition to one or more clay minerals, other minerals, such as for example quartz, feldspar, mica etc ... This is particularly the case when the clay is obtained by grinding a clay rock.
• Clay can also come from excavated soil, especially during construction activities.
• Clay minerals are hydrated aluminosilicates of the phyllosilicate family. At least one clay mineral is preferably chosen from kaolinite, smectites (in particular montmorillonite, saponite or beidellite), illite, sepiolite, attapulgite (also called palygorskite), hectorite and laponite. The clay preferably does not include a fibrous clay mineral.
• the clay minerals have a structure in two-dimensional sheets made up of two types of layers (tetrahedral and octahedral) connected by their vertices.
• the silicon atoms are surrounded by four oxygen atoms
• atoms of a metal such as aluminum are surrounded by six oxygen atoms. Due to their structure with a very large specific surface, clays have the capacity to admit numerous exchanges of cations or anions by insertion into the interfoliar network or by adsorption on the surface of the sheets.
• the ion exchange capacity remains low and the interfoliar space is occupied by water molecules and maintained by hydrogen bonds between the hydroxyl groups of the octahedral sheets and the oxygen of the tetrahedral sheets.
• the ion exchange capacity is higher because the aluminum cation in the octahedral layer of the sheet is partially substituted by a divalent cation of the magnesium type.
• the overall negative charge is counterbalanced by sodium and / or calcium ions in the interfoliar space.
• the layers being held together by relatively weak forces, water and other polar molecules can penetrate into the interfoliar space, most often causing a dimensional variation of the entire material.
• At least one raw clay is preferably chosen from kaolins and bentonites, in particular sodium, calcium or magnesium bentonites. Bentonites mainly contain montmorillonite.
• the binder can contain several clays or several clay minerals. In all cases, it is the total weight content of clay mineral that must be considered, that is to say the sum of the respective weight contents of each of the clay minerals included in the binder composition.
• the total content by weight of clay mineral in the binder is preferably at least 2%, in particular at least 3% or at least 4%, or even at least 5%. Contents of at least 10%, in particular at least 12% and even at least 14% are preferred. It is preferably at most 50%, in particular at most 40%, or even at most 30% or at most 25%. It has for example been observed that good values of adhesion by traction, useful when the binder is used in the composition of a tile adhesive, were obtained even for low contents of clay mineral, of the order for example of 10 to 30%, which demonstrates a surprisingly high capacity of raw clays to bind aggregates.
• filler is meant a pulverulent material having a particle size distribution by volume such that the value of d90 is less than 250 ⁇ m.
• the value of d50 is less than 20 ⁇ m, especially 10 ⁇ m.
• the particle size distribution can be determined by laser particle size.
• Limestone is mainly composed of calcium carbonate (calcite) and dolomite of calcium and magnesium carbonate (dolomite).
• the limestone filler, respectively dolomite comprises at least 80% by weight, in particular at least 90% by weight, of calcite, respectively of dolomite.
• the content by weight of limestone and / or dolomitic fillers in the binder is preferably between 10 and 90%, in particular between 20 and 80%, or even between 30 and 75%, limits included.
• the water retaining agent is preferably a cellulose ether or a starch ether. It improves the consistency, in particular the workability, of the concrete or final mortar before application. The water retaining agent also makes it possible to avoid too rapid drying of the clay. Cellulose ether is also a thickening agent and improves the adhesion properties of the final mortar.
• the total weight content of water-retaining agent in the binder is preferably between 0.01 and 10%, in particular between 0.05 and 5%, or even between 0.1 and 3%, limits included.
• the binder also comprises at least one additive chosen from flocculating agents, water-repellent agents, latexes, hydraulic binders, tackifying agents and cationic surfactants. It can comprise a mixture of several of these additives, for example a mixture of one or more flocculating agents and one or more water-repellent agents, a mixture of one or more flocculating agents and one or more latexes, a mixture of one or more water repellents and one or more latexes, or a mixture of these six additives.
• the total weight content of these additives in the binder is preferably between 0.05 and 40%, in particular between 1 and 30%, or even between 2 and 20% or between 3 and 10%, limits included.
• the flocculating agent by promoting the aggregation of clay particles, improves the cohesion of the clay binder, and therefore the mechanical properties of the concrete or final mortar.
• the flocculating agent is preferably a polycationic polymer, in particular a quaternary polyammonium. This agent is particularly effective when at least one raw clay is a bentonite, probably because the latter is relatively charged. Without wishing to be bound by any scientific theory, it would seem that the polycationic polymer is capable, by adsorbing on the sheets, of bridging several particles between them.
• the quaternary polyammonium preferably has a molecular mass of between 10,000 and 1,000,000. It can be obtained by polycondensation reaction between epichlorohydrin and a primary or secondary amine, for example dimethylamine. The quaternary ammonium function (cation site) is then located on the main chain of the polymer. Alternatively, the quaternary ammonium function can be located on side chains. The quaternary polyammonium can in this case be obtained by reaction of an allyl chloride and dimethylamine.
• the content by weight of polycationic polymer in the binder is preferably between 0.05 and 30%, in particular between 0.2 and 15%, or even between 0.5 and 5%.
• the flocculating agent can also be a source of polyvalent cations.
• the polyvalent cation is preferably an alkaline earth cation, preferably calcium, or even magnesium. Other versatile cations include aluminum, zinc and iron.
• the source of polyvalent cations is preferably a hydroxide (for example calcium hydroxide) or a salt, in particular an inorganic salt, such as a sulfate, a nitrate or even a chloride.
• the total content by weight of source of polyvalent cations in the binder, in particular in salt or in calcium hydroxide, is preferably between 0.05 and 30%, in particular between 1 and 20%, even between 2 and 10%, limits included. .
• Multipurpose cation sources are particularly effective when at least one raw clay contains kaolinite.
• the water-repellent agent makes it possible to improve the water resistance, and in particular the adhesion by traction of the mortar after immersion in water, which is particularly advantageous for applications as a tile adhesive.
• It is preferably chosen from waxes, silicones (for example polydimethylsiloxane), silanes, and zinc, calcium, magnesium or sodium stearates and oleates.
• the wax is preferably in the form of a micronized powder, with a d50 of 2 to 50 ⁇ m.
• the wax is for example a paraffin wax.
• the total weight content of water-repellent agent in the binder is preferably between 0.05 and 30%, in particular between 1 and 25%, or even between 2 and 20 or between 3 and 15%, limits included.
• latex is meant a polymeric aqueous dispersion or a powder capable of forming such a dispersion (redispersible powder).
• the latex is preferably based on a copolymer of ethylene and acetate vinyl, a copolymer of ethylene and vinyl versatate or a copolymer of styrene and butadiene.
• Latex has a film-forming effect which improves the flexibility in the hardened state of the mortar or final concrete as well as its adhesion properties.
• the weight content of latex in the binder is preferably between 0.05 and 30%, in particular between 0.5 and 20%, or even between 1 and 10%, or between 2 and 5%, limits included.
• hydraulic binder within the meaning of the invention means a binder chosen from:
• Portland cement means not only CEM I cements but also Portland compound cements (CEM II, including Portlands cements with slag, silica smoke, pozzolan, fly ash, calcined shales, limestone), blast furnace cements (CEM III), pozzolanic cements (CEM IV) and compound cements (CEM V), within the meaning of standard EN 197-1.
• Ground granulated blast furnace slags are only considered as hydraulic binders in the presence of activators, for example alkaline activators such as sodium silicate or sodium carbonate.
• activators for example alkaline activators such as sodium silicate or sodium carbonate.
• a preferred activator mixture contains alkaline silicate, alkaline tripolyphosphate and a source of alkaline earth, for example lime.
• the total weight content of hydraulic binder in the binder corresponds to the sum of the respective weight contents in each of these compounds or mixtures of compounds (including, where appropriate, the activator of the blast furnace slag).
• the total weight content of hydraulic binder may be zero.
• the binder advantageously comprises at least one of the above-mentioned hydraulic binders, or a mixture of several of the above-mentioned hydraulic binders.
• the presence of aluminous cement is particularly beneficial.
• the total weight content of hydraulic binder in the binder is preferably at most 25% or at most 20%, in particular at most 15% or at most 10%, or even at most 4% or not more than 2%. It can advantageously be at least 1%, in particular at least 2%, or even at least 4%.
• the ratio between the total weight content of hydraulic binder and the total weight content of clay mineral is preferably at most 0.9, in particular at most 0.8 and even at most 0.7 or at least plus 0.6. It can advantageously be at least 0.1, in particular at least 0.2.
• the binder is either free of Portland cement, or contains it, but in a weight content of at most 2%, in particular at most 1%, in order to reduce the irritant properties.
• This content can advantageously be zero.
• a content of at least 0.2%, in particular at least 0.4%, for example between 0.6 and 2% is however beneficial from the point of view of the properties of the mortar or final concrete after immersion in the water without excessively negatively impacting the irritant nature of the mortar or concrete.
• the tackifiers are preferably chosen from amylose, amylopectin and their derivatives.
• starch for example wheat, provides these two agents. It can be modified starch in order to change its gelatinization temperature and its impact on viscosity.
• the starch may have undergone a pre-gelatinization step.
• the adhesive agents make it possible to improve the mechanical performance and the water resistance of the binders.
• Cationic surfactants make it possible to stabilize the binder in a humid medium, in particular by intercalation between the sheets of charged clays or by adsorption on the surface of the sheets, rendering the clay exchange surfaces hydrophobic.
• the cationic surfactants are preferably salts (in particular iodides or bromides) of quaternary ammonium or phosphonium. Mention may in particular be made of the tetraethylphosphonium salts, of tetrabutylphosphonium, of tetrahexylphosphonium, of tetraoctylphosphonium, of cetyltrimethylammonium bromide, of tetradecyltrimethylammonium bromide, of butyldiammonium dichloride, methyl brimide dichloride, tetramethylammonium acetate, benzyltriethylammonium chloride, tetraethylammonium bromide, tetra-n-butylammonium chloride.
• the binder can be in the form of a mixture of dry powders, ready to mix, possibly with the addition of aggregates during or before mixing.
• the latex is present in the mixture in the form of a redispersible powder.
• the invention also relates to a construction product, in particular a concrete or a mortar comprising a binder according to the invention, and optionally aggregates.
• the construction product can also be a prefabricated product.
• the mortar is preferably a mortar for facade plaster, an adhesive mortar, a screed, a mortar for the base layer of an exterior insulation system or a jointing mortar.
• the mortar according to the invention is preferably an adhesive mortar, more precisely a tile adhesive.
• the mortar is preferably in the form of a mixture of dry powders, ready to mix with a mixing liquid, in particular water.
• the mixing ratio is preferably between 5 and 40%, especially between 10 and 30%, limits included.
• the concrete or the mortar does not comprise any other binder than the binder according to the invention.
• the concrete or the mortar consists of the binder according to the invention and of aggregates.
• the aggregates are preferably sands, in particular of a siliceous or calcareous nature.
• the total content by weight of aggregates in mortar or concrete is preferably between 5 and 85%, especially between 10 and 70%, limits included.
• Limestone sands are preferred because they allow a much better adhesion by traction after immersion in water in the context of an adhesive mortar application. Without wishing to be bound by any scientific theory, it would seem that the calcium ions brought in by the limestone sands could influence the compactness of the clay and that the absorption of water by the limestone particles could strengthen the clay network due to hydrogen bonds caused by absorbed water.
• the mortar is preferably a dry mortar.
• the mortar in particular dry mortar, preferably comprises from 2 to 10%, in particular from 3 to 8%, of clay mineral, from 10 to 30%, in particular from 12 to 25% of calcareous or dolomitic filler and from 50 to 85% , in particular from 55 to 80% of sand, in particular limestone.
• the content of water-retaining agent is preferably between 0.1 and 1%.
• the mortar preferably comprises a latex in a weight content of between 1 and 5%.
• the mortar preferably comprises a water-repellent agent in a content of between 2 and 8%.
• the binder or the concrete or mortar may comprise other additives, for example fibers (mineral or organic, for example glass fibers, cellulose fibers, natural fibers, such as flax or hemp fibers), aggregates light (for example perlite, vermiculite, expanded calcined clay, expanded glass), water reducing agents (in particular plasticizers or superplasticizers, such as lignosulfonates, polycarboxylates, polymelaminesulfonates, polynaphthalene sulfonates), pigments, biocides, surfactants, superabsorbents (for example based on sodium polyacrylates).
• fibers mineral or organic, for example glass fibers, cellulose fibers, natural fibers, such as flax or hemp fibers
• aggregates light for example perlite, vermiculite, expanded calcined clay, expanded glass
• water reducing agents in particular plasticizers or superplasticizers, such as lignosulfonates, polycarboxylates, polymelaminesulfonates, poly
• the fiber content by weight in the concrete or mortar is preferably at most 10%, in particular 5%.
• the binder according to the invention by the good performance it gives mortars in terms of traction adhesion, is particularly well suited to the production of tile adhesives.
• the invention therefore also relates to a method of producing a tiling on a support, comprising a step in which at least one layer of a paste obtained by mixing with a mixing liquid of an adhesive mortar according to the invention or of a coating is applied to the tiles of said tile and / or to said support.
• adhesive mortar comprising a binder according to the invention.
• the invention also relates to the use of an adhesive mortar according to the invention or an adhesive mortar comprising a binder according to the invention as a tile adhesive, for bonding tiles or tiles of a tile on a support. .
• the support is typically a wall or a partition, or a floor, for example a screed.
• the tiles can be made of various materials, such as ceramic, sandstone, cement, stone, marble, etc.
• the glue can for example be applied by means of a glue comb, a trowel, a trowel or a notched spatula.
• the binder is also well suited for producing a base layer of an insulation system from the outside.
• a system comprises from the wall to be insulated - typically a masonry wall, an insulating panel (for example made of mineral wool or polystyrene) glued or mechanically fixed to said wall, a base layer incorporating a frame typically made of glass fibers, then at least one finish plaster.
• the tables indicate dry mortar compositions obtained by mixing binders according to the invention with aggregates (in this case silica or limestone sands). The contents are therefore expressed as percentages by weight relative to the total weight of the mortar composition.
• the dry mortar composition is then mixed with water, the mixing ratio corresponding to the amount of water added relative to the weight of the dry mortar composition.
• the mortars exemplified are particularly suitable as tile adhesives.
• the adhesion by traction is measured according to standard EN 12004-2, after 7 days unless otherwise indicated.
• the tile used is a Bla type tile within the meaning of standard EN 14411, therefore having a water absorption of at most 0.5%.
• Wax 1 is a micronized Ceretan MX 2919 wax sold by the company Münzig.
• Wax 2 is a wax marketed under the reference HydroWax 170 by the company Sasol Wax.
• Latex 1 based on a copolymer of ethylene and vinyl acetate, is sold under the reference Vinnapas 5010 N by the company Wacker.
• Latex 2 based on a copolymer of styrene and acrylate, is sold under the reference Acronal S735P by the company BASF. These two latexes are in the form of a redispersible powder.
• Polycation is a flocculating agent of the quaternary polyammonium type sold under the reference Floset EVA 45P by the company SNF.
• Portland cement is a CEM I 52.5 R cement from Heidelberg. Aluminous cement is marketed by Kerneos under the reference Ternal White.
• Na bentonite is sodium bentonite and “Mg bentonite” is magnesium bentonite.
• the limestone filler 1 has a dlO of 1.8 ⁇ m, a d50 of 8.8 ⁇ m and a d90 of 34 ⁇ m.
• the limestone filler 2 has a dlO of 1.6 ⁇ m, a d50 of 5.2 ⁇ m and a d90 of 21 ⁇ m.
• the silica sands are distinguished by their particle size.
• Sand 1 has a dlO of 260 ym, a d50 of 520 ym and a d90 of 820 ym.
• Sand 2 has a dlO of 180 ym, a d50 of 280 ym and a d90 of 450 ym.
• Sand 3 has an dlO of 85 ym, a d50 of 154 ym and a d90 of 273 ym.
• Sand 1 is therefore the coarsest and sand 3 the finest.
• Limestone sand has a dlO of 11 ym, a d50 of
• Comparative examples C1 to C4 do not make it possible to achieve the performance required in terms of traction adhesion for tile adhesives (minimum of 0.5 N / mm 2 ), unlike the examples according to the invention.
• Example Cl In the absence of clay (example Cl) or cellulose ether (example C2), the mortar has no adhesive properties. Adhesion is almost nonexistent in the case of Example C3, which contains a very large quantity of raw clay and no calcareous filler. The absence of an additive does not allow Example C4 to achieve good performance.
• the resistance to indentation is zero.
• the resistance to indentation is 0.3 N / mm 2 after 3, 7 and 14 days of immersion.
• the resistance to indentation after 3 days of immersion is 0.6 N / mm 2 in the case of Example 13.
• the addition of hydraulic binder therefore considerably improves the mechanical properties after immersion in the water. Table 6
• Table 6 show the beneficial effect of limestone sands compared to silica sands on traction adhesion after immersion in water.
• Table 7 compares different clays to each other.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Structural Engineering (AREA)
• Inorganic Chemistry (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Sealing Material Composition (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2018
  • 2018-07-30 FR FR1857071A patent/FR3084357B1/fr active Active
• 2019
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  • 2019-07-26 EP EP19742407.0A patent/EP3830050A1/de active Pending
  • 2019-07-26 WO PCT/EP2019/070277 patent/WO2020025504A1/fr unknown
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• 2021
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