WO2020025504A1 - Binder containing a clay - Google Patents

Binder containing a clay Download PDF

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Publication number
WO2020025504A1
WO2020025504A1 PCT/EP2019/070277 EP2019070277W WO2020025504A1 WO 2020025504 A1 WO2020025504 A1 WO 2020025504A1 EP 2019070277 W EP2019070277 W EP 2019070277W WO 2020025504 A1 WO2020025504 A1 WO 2020025504A1
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WO
WIPO (PCT)
Prior art keywords
binder
mortar
binder according
clay
weight content
Prior art date
Application number
PCT/EP2019/070277
Other languages
French (fr)
Inventor
Nelly BRIELLES
Joumana YAMMINE-MALESYS
Lionel BERTRAND
Frank Hesselbarth
Original Assignee
Saint-Gobain Weber
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 Saint-Gobain Weber filed Critical Saint-Gobain Weber
Priority to EP19742407.0A priority Critical patent/EP3830050A1/en
Priority to BR112020026435-0A priority patent/BR112020026435A2/en
Priority to CN201980050751.5A priority patent/CN112469681A/en
Publication of WO2020025504A1 publication Critical patent/WO2020025504A1/en

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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.

Abstract

The subject of the invention is a binder comprising: at least one raw clay comprising at least one clayey mineral, the total weight content of clayey mineral ranging from 1 to 60% relative to the weight of binder, at least one limestone or dolomite filler, at least one water-retaining agent, and at least one additive chosen from flocculating agents, water-repellent agents, latexes, hydraulic binders, bonding agents and cationic surfactants, with the proviso that, when the binder comprises a hydraulic binder, the total weight content of hydraulic binder is less than the total weight content of clayey mineral.

Description

DESCRIPTION  DESCRIPTION
TITRE : LIANT CONTENANT UNE ARGILE TITLE: BINDER CONTAINING CLAY
L' invention se rapporte au domaine des liants, notamment des liants pour produits de construction tels que des bétons et des mortiers. Traditionnellement, les bétons et mortiers comprennent des liants et des granulats. Les liants peuvent être organiques, en particulier à base de résines, mais sont le plus souvent des liants minéraux, hydrauliques ou non-hydrauliques. Les liants minéraux hydrauliques (c'est-à-dire des liants faisant prise de façon irréversible au contact de l'eau et pouvant durcir sous l'eau) sont le plus souvent des ciments tels que les ciments Portland (éventuellement additionnés d'au moins un autre produit choisi parmi les laitiers de haut fourneau granulés broyés ou les composés pouzzolaniques tels que les cendres volantes) , les ciments alumineux, les ciments suifo-alumineux . Les liants minéraux non-hydrauliques (c'est-à-dire des liants ne pouvant durcir sous l'eau) comprennent notamment la chaux aérienne et les liants gypseux (à base de sulfate de calcium) . The invention relates to the field of binders, in particular binders for construction products such as concretes and mortars. Traditionally, concrete and mortar have included binders and aggregates. The 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) are most often 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 (that is to say binders which cannot harden under water) include, in particular, air lime and gypsum binders (based on calcium sulphate).
Il existe aujourd'hui un besoin de disposer de liants à la fois à faible empreinte carbone et non- irritants. La production des ciments Portland, mais aussi des ciments alumineux et suifo-alumineux, nécessite des traitements de cuisson à très haute température qui occasionnent d'importants rejets de dioxyde de carbone. Le ciment Portland est en outre irritant pour la peau et les yeux . Afin de répondre à ce besoin, la présente invention a pour objet un liant comprenant : Today there is a need to have binders that are both low carbon footprint and non-irritant. The production of Portland cements, but also of aluminous and tallow-aluminous cements, requires very high temperature firing treatments which cause significant carbon dioxide emissions. Portland cement is also irritating to the skin and eyes. In order to meet this need, the subject of the present invention is a binder comprising:
au moins une argile crue comprenant au moins un minéral argileux, la teneur pondérale totale en minéral argileux allant de 1 à 60% par rapport au poids de liant, au moins un filler calcaire ou dolomitique,  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,
au moins un agent rétenteur d'eau,  at least one water retaining agent,
au moins un additif choisi parmi les agents floculants, les agents hydrofuges, les latex, les liants hydrauliques, les agents collants et les tensioactifs cationiques ,  at least one additive chosen from flocculating agents, water-repellent agents, latexes, hydraulic binders, tackifying agents and cationic surfactants,
à condition que, lorsque le liant comprend un liant hydraulique, la teneur pondérale totale en liant hydraulique soit inférieure à la teneur pondérale totale en minéral argileux. provided that, when the binder comprises a hydraulic binder, the total weight content of hydraulic binder is less than the total weight content of clay mineral.
Dans le présent texte, les teneurs indiquées pour les constituants du liant, respectivement du mortier, sont des teneurs pondérales exprimées relativement au poids total de la composition de liant, respectivement de la composition de mortier.  In the present text, 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.
De manière surprenante, il s'est avéré que l'utilisation d'argile crue comme liant majoritaire, avec peu ou pas de liant hydraulique, permettait d'atteindre de bonnes performances. Dans le cas par exemple des colles à carrelage, de bonnes valeurs d'adhérence par traction sont obtenues. Bien que dépourvues de propriétés d' hydraulicité, les argiles crues se sont révélées capables de lier de manière très efficace les granulats de mortier ou de béton.  Surprisingly, it turned out that the use of raw clay as the majority binder, with little or no hydraulic binder, made it possible to achieve good performance. In the case, for example, of tile adhesives, good traction adhesion values are obtained. Although lacking hydraulic properties, raw clays have been shown to be able to bind mortar or concrete aggregates very effectively.
On entend par argile un matériau pulvérulent comprenant majoritairement au moins un minéral argileux. L'argile peut être constituée d'un minéral argileux ou de plusieurs minéraux argileux. Alternativement, l'argile peut contenir, en plus d'un ou plusieurs minéraux argileux, d'autres minéraux, tels que par exemple du quartz, du feldspath, du mica etc... C'est en particulier le cas lorsque l'argile est obtenue par broyage d'une roche argileuse. L'argile peut également provenir de terres excavées, notamment au cours d'activités de construction. The term “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. Alternatively, 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.
Les minéraux argileux sont des aluminosilicates hydratés de la famille des phyllosilicates . Au moins un minéral argileux est de préférence choisi parmi la kaolinite, les smectites (notamment la montmorillonite, la saponite ou la beidellite) , l'illite, la sépiolite, 1 ' attapulgite (aussi appelée palygorskite) , l'hectorite et la laponite. L'argile ne comprend de préférence pas de minéral argileux fibreux. 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.
Les minéraux argileux présentent une structure en feuillets bidimensionnels constitués de deux types de couches (tétraédriques et octaédriques) reliées par leurs sommets. Dans les couches tétraédriques, les atomes de silicium sont entourés par quatre atomes d'oxygène, tandis que dans les couches octaédriques, des atomes d'un métal tel que l'aluminium sont entourés par six atomes d'oxygène. De par leur structure à très grande surface spécifique, les argiles présentent une capacité à admettre de nombreux échanges de cations ou anions par insertion dans le réseau interfoliaire ou par adsorption en surface des feuillets. Dans le cas de la kaolinite, la capacité d'échange ionique reste faible et l'espace interfoliaire est occupé par des molécules d'eau et maintenu par des liaisons hydrogènes entre les groupes hydroxyles des feuillets octaédriques et l'oxygène des feuillets tétraédriques. Dans le cas des smectites, la capacité d'échange ionique est plus élevée car le cation aluminium dans la couche octaédrique du feuillet est partiellement substitué par un cation divalent du type magnésium. Dans ce cas, la charge globale, négative, est contrebalancée par des ions sodium et/ou calcium dans l'espace interfoliaire. Les couches étant maintenues ensemble par des forces relativement faibles, l'eau et d'autres molécules polaires peuvent pénétrer dans l'espace interfoliaire, entraînant le plus souvent une variation dimensionnelle de l'ensemble du matériau. The clay minerals have a structure in two-dimensional sheets made up of two types of layers (tetrahedral and octahedral) connected by their vertices. In the tetrahedral layers, the silicon atoms are surrounded by four oxygen atoms, while in the octahedral layers, 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. In the case of kaolinite, 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. In the case of smectites, 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. In this case, 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.
Au moins une argile crue est de préférence choisie parmi les kaolins et les bentonites, notamment les bentonites de sodium, de calcium ou de magnésium. Les bentonites contiennent principalement de la montmorillonite .  At least one raw clay is preferably chosen from kaolins and bentonites, in particular sodium, calcium or magnesium bentonites. Bentonites mainly contain montmorillonite.
Le liant peut contenir plusieurs argiles ou plusieurs minéraux argileux. Dans tous les cas, c'est la teneur pondérale totale en minéral argileux qu' il faut considérer, c'est-à-dire la somme des teneurs pondérales respectives de chacun des minéraux argileux compris dans la composition de liant.  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.
La teneur pondérale totale en minéral argileux dans le liant est de préférence d'au moins 2%, notamment d'au moins 3% ou d'au moins 4%, voire d'au moins 5%. Des teneurs d'au moins 10%, notamment d'au moins 12% et même d'au moins 14% sont préférées. Elle est de préférence d'au plus 50%, notamment d'au plus 40%, voire d'au plus 30% ou d'au plus 25%. Il a par exemple été observé que de bonnes valeurs d'adhérence par traction, utiles lorsque le liant est utilisé dans la composition d'une colle à carrelage, étaient obtenues même pour de faibles teneurs en minéral argileux, de l'ordre par exemple de 10 à 30%, ce qui démontre une capacité étonnamment élevée des argiles crues à lier les granulats.  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.
Par « filler » on entend un matériau pulvérulent ayant une distribution granulométrique volumique telle que la valeur de d90 est inférieure à 250 ym. De préférence, la valeur de d50 est inférieure à 20 ym, notamment à 10 ym. La distribution granulométrique peut être déterminée par granulométrie laser. Le calcaire est composé principalement de carbonate de calcium (calcite) et la dolomie de carbonate de calcium et de magnésium (dolomite) . De préférence le filler calcaire, respectivement dolomitique, comprend au moins 80% en poids, notamment au moins 90% en poids, de calcite, respectivement de dolomite. By “filler” is meant a pulverulent material having a particle size distribution by volume such that the value of d90 is less than 250 μm. Preferably, the value of d50 is less than 20 µm, especially 10 µm. 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). Preferably the limestone filler, respectively dolomite, comprises at least 80% by weight, in particular at least 90% by weight, of calcite, respectively of dolomite.
Sans vouloir être lié par une quelconque théorie scientifique, il semblerait que les fillers calcaire et dolomitique aient un effet de stabilisation de l'argile, en apportant des ions alcalino-terreux qui vont compenser les charges de l'argile. Les fillers jouent donc un rôle actif dans le liant selon l'invention.  Without wishing to be bound by any scientific theory, it would seem that limestone and dolomitic fillers have a stabilizing effect on clay, by providing alkaline earth ions which will compensate for the charges of clay. The fillers therefore play an active role in the binder according to the invention.
La teneur pondérale en fillers calcaire et/ou dolomitique dans le liant est de préférence comprise entre 10 et 90%, notamment entre 20 et 80%, voire entre 30 et 75%, bornes incluses.  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.
L'agent rétenteur d'eau est de préférence un éther de cellulose ou un éther d'amidon. Il permet d'améliorer la consistance, notamment l' ouvrabilité, du béton ou mortier final avant application. L'agent rétenteur d'eau permet en outre d'éviter un dessèchement trop rapide de l'argile. L'éther de cellulose est également un agent épaississant et améliore les propriétés d'adhérence du mortier final. La teneur pondérale totale en agent rétenteur d'eau dans le liant est de préférence comprise entre 0,01 et 10% notamment entre 0,05 et 5%, voire entre 0,1 et 3%, bornes incluses .  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.
Le liant comprend en outre au moins un additif choisi parmi les agents floculants, les agents hydrofuges, les latex, les 1iants hydrauliques, les agents collants et les tensioactifs cationiques. Il peut comprendre un mélange de plusieurs de ces additifs, par exemple un mélange d'un ou plusieurs agents floculants et d'un ou plusieurs agents hydrofuges, un mélange d'un ou plusieurs agents floculants et d'un ou plusieurs latex, un mélange d'un ou plusieurs agents hydrofuges et d'un ou plusieurs latex, ou un mélange de ces six additifs. 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.
La teneur pondérale totale en ces additifs dans le liant est de préférence comprise entre 0,05 et 40%, notamment entre 1 et 30%, voire entre 2 et 20% ou entre 3 et 10%, bornes compr ses .  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.
L'agent floculant, en favorisant l' agrégation des particules d'argile, améliore la cohésion du liant argileux, et donc les propriétés mécaniques du béton ou mortier final. 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.
L'agent floculant est de préférence un polymère polycationique, notamment un polyammonium quaternaire. Cet agent est particulièrement efficace lorsqu'au moins une argile crue est une bentonite, probablement parce que cette dernière est relativement chargée. Sans vouloir être lié par une quelconque théorie scientifique, il semblerait que le polymère polycationique soit capable, en s'adsorbant sur les feuillets, de ponter plusieurs particules entre elles. 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.
Le polyammonium quaternaire possède de préférence une masse moléculaire comprise entre 10 000 et 1 000 000. Il peut être obtenu par réaction de polycondensation entre l'épichlorhydrine et une amine primaire ou secondaire, par exemple la diméthylamine . La fonction ammonium quaternaire (site cationique) est alors située sur la chaîne principale du polymère. Alternativement, la fonction ammonium quaternaire peut être située sur des chaînes latérales. Le polyammonium quaternaire peut dans ce cas être obtenu par réaction d'un chlorure d'allyle et de diméthylamine. 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.
La teneur pondérale en polymère polycationique dans le liant est de préférence comprise entre 0,05 et 30%, notamment entre 0,2 et 15%, voire entre 0,5 et 5%. L'agent floculant peut également être une source de cations polyvalents. Le cation polyvalent est de préférence un cation alcalino-terreux, de préférence le calcium, voire le magnésium . D' autres cations polyvalents sont notamment 1 ' aluminium, le zinc et le fer. La source de cations polyvalents est de préférence un hydroxyde (par exemple 1 ' hydroxyde de calcium) ou un sel, notamment un sel inorganique, tel qu'un sulfate, un nitrate ou encore un chlorure . 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.
La teneur pondérale totale en source de cations polyvalents dans le liant, notamment en sel ou en hydroxyde de calcium, est de préférence comprise entre 0,05 et 30%, notamment entre 1 et 20%, voire entre 2 et 10%, bornes comprises .  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. .
Les sources de cations polyvalents sont particulièrement efficaces lorsqu'au moins une argile crue contient de la kaolinite.  Multipurpose cation sources are particularly effective when at least one raw clay contains kaolinite.
L'agent hydrofuge permet d'améliorer la résistance à l'eau, et notamment l'adhérence par traction du mortier après immersion dans l'eau, ce qui est particulièrement avantageux pour les applications comme colle à carrelage. Il est de préférence choisi parmi les cires, les silicones (par exemple le polydiméthylsiloxane) , les silanes, et les stéarates et oléates de zinc, de calcium, de magnésium ou de sodium. La cire est de préférence sous forme de poudre micronisée, avec un d50 de 2 à 50 ym. La cire est par exemple une cire de paraffine. La teneur pondérale totale en agent hydrofuge dans le liant est de préférence comprise entre 0,05 et 30%, notamment entre 1 et 25%, voire entre 2 et 20 ou entre 3 et 15%, bornes incluses.  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 μm. 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.
Par « latex », on entend une dispersion aqueuse polymérique ou une poudre capable de former une telle dispersion (poudre redispersible) . Le latex est de préférence à base d'un copolymère d'éthylène et d'acétate de vinyle, d'un copolymère d'éthylène et de versatate de vinyle ou d'un copolymère de styrène et de butadiène. Le latex possède un effet filmogène qui améliore la flexibilité à l'état durci du mortier ou du béton final ainsi que ses propriétés d'adhésion. La teneur pondérale en latex dans le liant est de préférence comprise entre 0,05 et 30%, notamment entre 0,5 et 20%, voire entre 1 et 10%, ou entre 2 et 5%, bornes comprises. By "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.
Par liant hydraulique au sens de l'invention on entend un liant choisi parmi :  By hydraulic binder within the meaning of the invention means a binder chosen from:
- les ciments Portland,  - Portland cements,
- les laitiers de haut-fourneau granulé broyés avec activateur,  - granulated blast furnace slag with activator,
- les cendres volantes de classe C,  - class C fly ash,
les ciments alumineux,  aluminous cements,
- les ciments suifo-alumineux,  - tallow-aluminum cements,
- les ciments bélitiques,  - belitic cements,
la chaux hydraulique,  hydraulic lime,
- les ciments de phosphates (par exemple les ciments phospho-magnésiens ) .  - phosphate cements (for example phospho-magnesian cements).
Par « ciment Portland », on entend non seulement les ciments CEM I mais aussi les ciments Portland composés (CEM II, incluant les ciments Portlands au laitier, à la fumée de silice, à la pouzzolane, aux cendres volantes, aux schistes calcinées, au calcaire) , les ciments de haut fourneau (CEM III), les ciments pouzzolaniques (CEM IV) et les ciments composés (CEM V), au sens de la norme EN 197-1.  "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.
Les laitiers de haut-fourneau granulés broyés ne sont considérés comme liants hydrauliques qu'en présence d'activateurs, par exemple des activateurs alcalins tels que le silicate de sodium ou le carbonate de sodium. Un mélange activateur préféré contient du silicate alcalin, du tripolyphosphate alcalin et une source d' alcalino-terreux, par exemple de la chaux. La teneur pondérale totale en liant hydraulique dans le liant correspond à la somme des teneurs pondérales respectives en chacun de ces composés ou mélanges de composés (y compris, le cas échéant, l'activateur du laitier de haut-fourneau) . 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. 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).
La teneur pondérale totale en liant hydraulique peut être nulle.  The total weight content of hydraulic binder may be zero.
Afin d'améliorer les performances après immersion dans l'eau du mortier ou béton final, le liant comprend avantageusement au moins un des liants hydrauliques précités, ou un mélange de plusieurs des liants hydrauliques précités. A titre d'exemple, la présence de ciment alumineux est particulièrement bénéfique.  In order to improve the performance after immersion in water of the final mortar or concrete, the binder advantageously comprises at least one of the above-mentioned hydraulic binders, or a mixture of several of the above-mentioned hydraulic binders. For example, the presence of aluminous cement is particularly beneficial.
La teneur pondérale totale en liant hydraulique dans le liant est de préférence d'au plus 25% ou d'au plus 20%, notamment d'au plus 15% ou d'au plus 10%, voire d'au plus 4% ou d'au plus 2%. Elle peut être avantageusement d'au moins 1%, notamment d'au moins 2%, voire d'au moins 4%.  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%.
Le rapport entre la teneur pondérale totale en liant hydraulique et la teneur pondérale totale en minéral argileux est de préférence d'au plus 0,9, notamment d'au plus 0,8 et même d'au plus 0,7 ou d'au plus 0,6. Il peut être avantageusement d'au moins 0,1, notamment d'au moins 0,2.  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.
De préférence, le liant est soit exempt de ciment Portland, soit en contient mais en une teneur pondérale d'au plus 2%, notamment d'au plus 1%, afin de réduire les propriétés irritantes. Cette teneur peut avantageusement être nulle. Une teneur d'au moins 0,2%, notamment d'au moins 0,4%, par exemple comprise entre 0,6 et 2% est toutefois bénéfique du point de vue des propriétés du mortier ou béton final après immersion dans l'eau, sans trop impacter négativement le caractère irritant du mortier ou du béton. Preferably, 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.
Les agents collants sont de préférence choisis parmi l'amylose, 1 ' amylopectine et leurs dérivés. L'ajout d'amidon, par exemple de blé, permet d'apporter ces deux agents. Il peut s'agir d'amidon modifié afin de changer sa température de gélatinisation et son impact sur la viscosité. L'amidon peut avoir subi une étape de pré gélatinisation. Les agents collants permettent d'améliorer les performances mécaniques et la résistance à l'eau des liants .  The tackifiers are preferably chosen from amylose, amylopectin and their derivatives. The addition of 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.
Les tensioactifs cationiques permettent de stabiliser le liant en milieu humide, notamment par intercalation entre les feuillets des argiles chargées ou par adsorption en surface des feuillets, rendant hydrophobes les surfaces d'échange des argiles.  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.
Les tensioactifs cationiques sont de préférence des sels (notamment iodures ou bromures) d'ammonium quaternaire ou de phosphonium. On peut citer notamment les sels de tétraéthylphosphonium, de tétrabutylphosphonium, de tétrahexylphosphonium, de tétraoctylphosphonium, le bromure de cétyltriméthylammonium, le bromure de tétradécyltriméthylammonium, le dichlorure de butyldiammonium, le bromure d' hexadécyltriméthylammonium, le chlorure de diallyldiméthylammonium, le chlorure de dodécyltriméthylammonium, l'acétate de tétraméthylammonium, le chlorure de benzyltriéthylammonium, le bromure de tétraéthylammonium, le chlorure de tétra-n-butylammonium.  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.
Le liant peut être sous forme d'un mélange de poudres sèches, prêt à gâcher, avec éventuellement ajout de granulats pendant ou avant le gâchage. Dans ce cas le latex est présent dans le mélange sous forme d'une poudre redispersible . L'invention a aussi pour objet un produit de construction, notamment un béton ou un mortier comprenant un liant selon l'invention, et éventuellement des granulats. Le produit de construction peut également être un produit préfabriqué. 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. In this case 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.
Le mortier est de préférence un mortier pour enduit de façade, un mortier-colle, une chape, un mortier pour couche de base d'un système d'isolation par l'extérieur ou un mortier de j ointoiement . Le mortier selon l'invention est de préférence un mortier-colle, plus précisément une colle à carrelage. Le mortier est de préférence sous forme d'un mélange de poudres sèches, prêt à gâcher avec un liquide de gâchage, en particulier de l'eau. Le taux de gâchage est de préférence compris entre 5 et 40%, notamment entre 10 et 30%, bornes comprises.  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.
De préférence, le béton ou le mortier ne comprend pas d'autre liant que le liant selon l'invention. Avantageusement, le béton ou le mortier consiste en le liant selon l'invention et des granulats.  Preferably, the concrete or the mortar does not comprise any other binder than the binder according to the invention. Advantageously, the concrete or the mortar consists of the binder according to the invention and of aggregates.
Les granulats sont de préférence des sables, notamment de nature siliceuse ou calcaire. La teneur pondérale totale en granulats dans le mortier ou le béton (à l'exclusion des fillers calcaire ou dolomitiques , qui font partie du liant) est de préférence comprise entre 5 et 85%, notamment entre 10 et 70%, bornes comprises.  The aggregates are preferably sands, in particular of a siliceous or calcareous nature. The total content by weight of aggregates in mortar or concrete (excluding limestone or dolomitic fillers, which are part of the binder) is preferably between 5 and 85%, especially between 10 and 70%, limits included.
Les sables calcaire sont préférés car ils permettent d'obtenir, dans le cadre d'une application comme mortier- colle, une bien meilleure adhérence par traction après immersion dans l'eau. Sans vouloir être liés par une quelconque théorie scientifique, il semblerait que les ions calcium apportés par les sables calcaire pourraient influencer la compacité de l'argile et que l'absorption d'eau par les particules de calcaire pourrait renforcer le réseau argileux du fait des liaisons hydrogène causées par l'eau absorbée. 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.
Le mortier est de préférence un mortier sec.  The mortar is preferably a dry mortar.
Le mortier, notamment mortier sec, comprend de préférence de 2 à 10%, notamment de 3 à 8%, de minéral argileux, de 10 à 30%, notamment de 12 à 25% de filler calcaire ou dolomitique et de 50 à 85%, notamment de 55 à 80% de sable, notamment calcaire. La teneur en agent rétenteur d'eau est de préférence comprise entre 0,1 et 1%. Le mortier comprend de préférence un latex en une teneur pondérale comprise entre 1 et 5%. Le mortier comprend de préférence un agent hydrofuge en une teneur comprise entre 2 et 8% .  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%.
Le liant ou le béton ou mortier peut comprendre d'autres additifs, par exemple des fibres (minérales ou organiques, par exemple des fibres de verre, de cellulose, des fibres naturelles, telles que des fibres de lin ou de chanvre) , des granulats légers (par exemple perlite, vermiculite, argile calcinée expansée, verre expansé) , des agents réducteurs d'eau (notamment des plastifiants ou des superplastifiants, tels que lignosulfonates , polycarboxylates , polymélaminesulfonates , polynaphtalène- sulfonates) , des pigments, des biocides, des surfactants, des super-absorbants (par exemple à base de polyacrylates de sodium) .  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).
La teneur pondérale en fibres dans le béton ou mortier est de préférence d'au plus 10%, notamment 5%.  The fiber content by weight in the concrete or mortar is preferably at most 10%, in particular 5%.
Le liant selon l'invention, par les bonnes performances qu' il confère aux mortiers en termes d'adhérence par traction, est particulièrement bien adapté à la réalisation de colles à carrelage.  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.
L' invention concerne donc également un procédé de réalisation d'un carrelage sur un support, comprenant une étape dans laquelle on applique, sur les carreaux ou dalles dudit carrelage et/ou sur ledit support, au moins une couche d'une pâte obtenue par gâchage avec un liquide de gâchage d'un mortier-colle selon l'invention ou d'un mortier-colle comprenant un liant selon l'invention. L'invention concerne aussi l'utilisation d'un mortier-colle selon l'invention ou d'un mortier-colle comprenant un liant selon l'invention comme colle à carrelage, pour coller des carreaux ou dalles d'un carrelage sur un support. 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. .
Le support est typiquement un mur ou une cloison, ou un sol, par exemple une chape. The support is typically a wall or a partition, or a floor, for example a screed.
Les carreaux ou dalles du carrelage peuvent être en matériaux divers, tels que céramique, grès, ciment, pierre, marbre, etc. La colle peut par exemple être appliquée au moyen d'un peigne à colle, d'une taloche, d'une truelle ou d'une spatule crantée. 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.
Le liant est également bien adapté pour la réalisation d'une couche de base d'un système d'isolation par l'extérieur. Un tel système comprend depuis la paroi à isoler - typiquement une paroi maçonnée, un panneau isolant (par exemple en laine minérale ou en polystyrène) collé ou fixé mécaniquement à ladite paroi, une couche de base incorporant une armature typiquement en fibres de verre, puis au moins un enduit en finition. The binder is also well suited for producing a base layer of an insulation system from the outside. Such 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.
Les exemples qui suivent illustrent l'invention de manière non limitative. Les compositions ainsi que leurs propriétés sont reproduites dans les tableaux 1 à 7 ci- après. Les exemples dont la référence commence par la lettre C sont des exemples comparatifs. The examples which follow illustrate the invention in a nonlimiting manner. The compositions and their properties are reproduced in Tables 1 to 7 below. The examples whose reference begins with the letter C are comparative examples.
Les tableaux indiquent des compositions de mortiers secs obtenus en mélangeant des liants selon l'invention avec des granulats (en l'occurrence des sables siliceux ou calcaire) . Les teneurs sont donc exprimées en pourcentages pondéraux par rapport au poids total de la composition de mortier. La composition sèche de mortier est ensuite gâchée avec de l'eau, le taux de gâchage correspondant à la quantité d'eau ajoutée par rapport au poids de la composition sèche de mortier. 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.
Les mortiers exemplifiés sont particulièrement adaptés en tant que colles à carrelage. L'adhérence par traction est mesurée selon la norme EN 12004-2, après 7 jours sauf indications contraires. Le carrelage utilisé est un carreau de type Bla au sens de la norme EN 14411, présentant par conséquent une absorption d'eau d'au plus 0,5%.  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%.
La cire 1 est une cire micronisée Ceretan MX 2919 commercialisée par la société Münzig. La cire 2 est une cire commercialisée sous la référence HydroWax 170 par la société Sasol Wax.  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.
Le latex 1, à base de copolymère d'éthylène et d'acétate de vinyle, est commercialisé sous la référence Vinnapas 5010 N par la société Wacker. Le latex 2, à base de copolymère de styrène et d'acrylate, est commercialisé sous la référence Acronal S735P par la société BASF. Ces deux latex sont sous forme de poudre redispersible .  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.
Le produit appelé « Polycation » est un agent floculant de type polyammonium quaternaire commercialisé sous la référence Floset EVA 45P par la société SNF.  The product called "Polycation" is a flocculating agent of the quaternary polyammonium type sold under the reference Floset EVA 45P by the company SNF.
Le ciment Portland est un ciment CEM I 52,5 R de la société Heidelberg. Le ciment alumineux est commercialisé par la société Kerneos sous la référence Ternal White.  Portland cement is a CEM I 52.5 R cement from Heidelberg. Aluminous cement is marketed by Kerneos under the reference Ternal White.
La « bentonite Na » est une bentonite de sodium et la « bentonite Mg » une bentonite de magnésium.  “Na bentonite” is sodium bentonite and “Mg bentonite” is magnesium bentonite.
Le filler calcaire 1 possède un dlO de 1,8 ym, un d50 de 8,8 ym et un d90 de 34 ym. Le filler calcaire 2 possède un dlO de 1,6 ym, un d50 de 5,2 ym et un d90 de 21 ym. The limestone filler 1 has a dlO of 1.8 µm, a d50 of 8.8 µm and a d90 of 34 µm. The limestone filler 2 has a dlO of 1.6 µm, a d50 of 5.2 µm and a d90 of 21 µm.
Les sables siliceux se distinguent par leur granulométrie. Le sable 1 possède un dlO de 260 ym, un d50 de 520 ym et un d90 de 820 ym. Le sable 2 possède un dlO de 180 ym, un d50 de 280 ym et un d90 de 450 ym. Le sable 3 possède un dlO de 85 ym, un d50 de 154 ym et un d90 de 273 ym. Le sable 1 est donc le plus grossier et le sable 3 le plus fin.  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.
Le sable calcaire possède un dlO de 11 ym, un d50 de Limestone sand has a dlO of 11 ym, a d50 of
78 ym et un d90 de 275 ym. 78 ym and a d90 of 275 ym.
Figure imgf000016_0001
Figure imgf000016_0001
Tableau 1
Figure imgf000017_0001
Table 1
Figure imgf000017_0001
Tableau 2 Table 2
Figure imgf000018_0001
Figure imgf000018_0001
Tableau 3 Table 3
Figure imgf000019_0001
Figure imgf000019_0001
Tableau 4  Table 4
Les exemples comparatifs Cl à C4 ne permettent pas d'atteindre les performances requises en termes d'adhérence par traction pour les colles à carrelage (minimum de 0,5 N/mm2), contrairement aux exemples selon l'invention. 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.
En l'absence d'argile (exemple Cl) ou d'éther de cellulose (exemple C2), le mortier ne possède aucune propriété adhésive. L'adhérence est presque inexistante dans le cas de l'exemple C3, lequel contient une très grande quantité d'argile crue et pas de filler calcaire. L'absence d'additif ne permet pas à l'exemple C4 d'atteindre de bonnes performances.  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.
Des essais de résistance mécanique après immersion dans l'eau ont également été réalisés. Pour ce faire, des éprouvettes parallélépipédiques de 2*2*10 cm3 ont été réalisées en faisant durcir pendant 14 jours les compositions de mortier dans des moules, puis en immergeant les éprouvettes dans l'eau pendant 3, 7 et 14 jours. La résistance à l'indentation est mesurée au moyen d'un pénétromètre et correspond à la force à exercer pour enfoncer un indenteur conique à travers l'éprouvette. Les compositions testées sont reportées dans le tableau 5 ci- après. La composition de l'exemple 12 correspond à celle de l'exemple comparatif C5 avec ajout, par rapport à cette dernière, de 5% de cire et 5% de ciment alumineux. Mechanical resistance tests after immersion in water were also carried out. To do this, parallelepipedic test pieces of 2 * 2 * 10 cm 3 were produced by curing the mortar compositions for 14 days in molds, then immersing the test pieces in water for 3, 7 and 14 days. The resistance to indentation is measured by means of a penetrometer and corresponds to the force to be exerted to push a conical indenter through the test piece. The compositions tested are reported in Table 5 below. The composition of Example 12 corresponds to that of Comparative Example C5 with the addition, with respect to the latter, of 5% of wax and 5% of aluminous cement.
Figure imgf000020_0001
Figure imgf000020_0001
Tableau 5  Table 5
Dans le cas de l'exemple C5 (comparatif), la résistance à l'indentation est nulle. Pour l'exemple 12 en revanche, la résistance à l'indentation est de 0,3 N/mm2 après 3, 7 et 14 jours d'immersion. La résistance à l'indentation après 3 jours d'immersion est de 0,6 N/mm2 dans le cas de l'exemple 13. L'ajout de liant hydraulique permet donc d'améliorer considérablement les propriétés mécaniques après immersion dans l'eau. Tableau 6 In the case of example C5 (comparative), the resistance to indentation is zero. For example 12, on the other hand, 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
Les exemples du tableau 6 montrent l'effet bénéfique des sables calcaire par rapport aux sables siliceux sur l'adhérence par traction après immersion dans l'eau. L'ajout du latex, de même que l'utilisation d'un sable siliceux plus fin, permet d'améliorer l'adhérence par traction . The examples in Table 6 show the beneficial effect of limestone sands compared to silica sands on traction adhesion after immersion in water. The addition of latex, as well as the use of finer silica sand, improves traction adhesion.
Le tableau 7 compare différentes argiles entre elles.  Table 7 compares different clays to each other.
Figure imgf000022_0001
Figure imgf000022_0001
Tableau 7  Table 7

Claims

REVENDICATIONS
1. Liant comprenant : 1. Binder comprising:
au moins une argile crue comprenant au moins un minéral argileux, la teneur pondérale totale en minéral argileux allant de 1 à 60% par rapport au poids de liant, au moins un filler calcaire ou dolomitique,  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,
au moins un agent rétenteur d'eau,  at least one water retaining agent,
au moins un additif choisi parmi les agents floculants, les agents hydrofuges, les latex, les liants hydrauliques, les agents collants et les tensioactifs cationiques ,  at least one additive chosen from flocculating agents, water-repellent agents, latexes, hydraulic binders, tackifying agents and cationic surfactants,
à condition que, lorsque le liant comprend un liant hydraulique, la teneur pondérale totale en liant hydraulique soit inférieure à la teneur pondérale totale en minéral argileux. provided that, when the binder comprises a hydraulic binder, the total weight content of hydraulic binder is less than the total weight content of clay mineral.
2. Liant selon la revendication 1, dans lequel la teneur pondérale totale en liant hydraulique est d'au plus 25%.  2. Binder according to claim 1, wherein the total weight content of hydraulic binder is at most 25%.
3. Liant selon l'une des revendications précédentes, qui est exempt de ciment Portland ou qui contient du ciment Portland en une teneur pondérale d'au plus 2%.  3. Binder according to one of the preceding claims, which is free of Portland cement or which contains Portland cement in a weight content of at most 2%.
4. Liant selon l'une des revendications précédentes, dans lequel au moins un minéral argileux est choisi parmi la kaolinite, les smectites, l'illite, la sépiolite, l' attapulgite, l'hectorite et la laponite.  4. Binder according to one of the preceding claims, in which at least one clay mineral is chosen from kaolinite, smectites, illite, sepiolite, attapulgite, hectorite and laponite.
5. Liant selon la revendication précédente, dans lequel au-moins une argile crue est choisie parmi les kaolins et les bentonites. 5. Binder according to the preceding claim, in which at least one raw clay is chosen from kaolins and bentonites.
6. Liant selon l'une des revendications précédentes, dans lequel la teneur pondérale totale en minéral argileux est comprise entre 5 et 50%, notamment entre 10 et 30%. 6. Binder according to one of the preceding claims, wherein the total weight content of clay mineral is between 5 and 50%, especially between 10 and 30%.
7. Liant selon l'une des revendications précédentes, tel que l'agent floculant est un polymère polycationique, notamment un polyammonium quaternaire.  7. Binder according to one of the preceding claims, such that the flocculating agent is a polycationic polymer, in particular a quaternary polyammonium.
8. Liant selon l'une des revendications 1 à 6, tel que l'agent floculant est une source de cations polyvalents, notamment une source de calcium ou de magnésium.  8. Binder according to one of claims 1 to 6, such that the flocculating agent is a source of polyvalent cations, in particular a source of calcium or magnesium.
9. Liant selon l'une des revendications précédentes, tel que l'agent hydrofuge est choisi parmi les cires, les silicones, les silanes, et les stéarates et oléates de zinc, de calcium, de magnésium ou de sodium.  9. Binder according to one of the preceding claims, such that the water-repellent agent is chosen from waxes, silicones, silanes, and zinc, calcium, magnesium or sodium stearates and oleates.
10. Liant selon l'une des revendications précédentes, tel que l'agent rétenteur d'eau est un éther de cellulose ou un éther d'amidon.  10. Binder according to one of the preceding claims, such that the water retaining agent is a cellulose ether or a starch ether.
11. Liant selon l'une des revendications précédentes, tel que les tensioactifs cationiques sont des sels d'ammonium quaternaire ou de phosphonium.  11. Binder according to one of the preceding claims, such that the cationic surfactants are quaternary ammonium or phosphonium salts.
12. Liant selon l'une des revendications précédentes, qui est sous forme d'un mélange de poudres sèches.  12. Binder according to one of the preceding claims, which is in the form of a mixture of dry powders.
13. Produit de construction, notamment béton ou mortier, tel que mortier pour enduit de façade, mortier- colle, chape, mortier pour couche de base d'un système d'isolation thermique par l'extérieur, mortier de j ointoiement, comprenant un liant selon l'une des revendications précédentes, et éventuellement des granulats .  13. Construction product, in particular concrete or mortar, such as mortar for facade plaster, adhesive mortar, screed, mortar for base layer of an exterior thermal insulation system, jointing mortar, comprising a binder according to one of the preceding claims, and optionally aggregates.
14. Produit de construction selon la revendication précédente, tel que les granulats comprennent des sables calcaires . 14. Construction product according to the preceding claim, such that the aggregates comprise limestone sands.
15. Produit de construc :ion selon l'une des revendications 13 ou 14, qui est un mortier sec comprenant de 2 à 10% de minéral argileux de 10 à 30% de filler calcaire ou dolomitique et de 50 à 85% de sable, notamment calcaire. 15. Construction product: ion according to one of claims 13 or 14, which is a dry mortar comprising from 2 to 10% of clay mineral from 10 to 30% of calcareous or dolomitic filler and from 50 to 85% of sand, especially limestone.
PCT/EP2019/070277 2018-07-30 2019-07-26 Binder containing a clay WO2020025504A1 (en)

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CN113454043B (en) 2018-12-31 2023-05-23 马特尔阿普 New formulation of low carbon building binder, method for preparing same and building material
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US4370167A (en) * 1982-03-15 1983-01-25 National Gypsum Company Asbestos-free drywall joint compound utilizing sepiolite clay as asbestos substitute
EP1118600A1 (en) * 1999-12-13 2001-07-25 Ziegelei Oberdiessbach AG Building material comprising clay and method of producing the same
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WO2023232775A1 (en) 2022-05-31 2023-12-07 Sika Technology Ag Accelerators for the reaction of high-silica aluminosilicates with water

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