• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    The present invention relates to a hydraulic binder composition comprising at least 50% by weight of granulated blast furnace slag and a system for activating said slag, said system comprising at least calcium sulphate, at least one product chosen from a source Portland clinker and lime, at least one aluminum derivative, and at least one alkali or alkaline earth metal salt. The present invention also relates to a composition of ready-to-mix construction material comprising such a hydraulic binder and granules of inert material capable of being agglomerated in the presence of an aqueous phase. The present invention also relates to a process for implementing the ready-to-mix composition according to the invention, comprising a step of mixing said composition with water, for the preparation of a construction material, such as a concrete or mortar, and in particular a mortar glue, joint mortar, or mortar or smoothing plaster.
    公开号:FR3027897A1
    申请号:FR1460440
    申请日:2014-10-30
    公开日:2016-05-06
    发明作者:Tetyana Kuryatnyk；Jeremy Becquet
    申请人:Bostik SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a hydraulic binder composition comprising at least 50% by weight of ground granulated blast furnace slag (relative to the weight of said binder) and a system of hydraulic binder composition comprising at least 50% by weight of ground granulated blast furnace slag (relative to the weight of said binder) and a system activating said slag, said system comprising at least calcium sulphate, at least one product selected from a source of Portland clinker and lime, at least one aluminum derivative, and at least one alkali metal or alkaline salt earthy. The present invention also relates to a composition of ready-to-mix construction material comprising such a hydraulic binder and granules of inert material capable of being agglomerated in the presence of an aqueous phase. The present invention also relates to a process for implementing the ready-to-mix composition according to the invention, comprising a step of mixing said composition with water, for the preparation of a construction material, such as a concrete or mortar, and in particular a mortar glue, joint mortar, or mortar or smoothing plaster. Hydraulic binders consist essentially of inorganic compounds and are characterized by their ability to set and harden irreversibly when brought into contact with water. The development of the final properties of the binder depends on the reactions that take place in contact with the water and the nature of the reaction products. Unlike the non-hydraulic binder, the hydrates formed during hydration reactions of the hydraulic binder are insoluble in water. After curing, a rigid product is obtained which is stable in contact with water and retains its mechanical properties (resistance) even under water. Among the existing hydraulic binders, Portland cement is undoubtedly one of the most used in the world. Composed of at least 95% by weight of Portland clinker and up to 5% by weight of calcium sulphate, Portland cement mixed with granulates of inert material and tempered with water appropriately, is capable of producing a mortar or concrete which retains its workability for a time long enough for its implementation and achieves sufficiently satisfactory mechanical properties (including mechanical strength) for the intended application, while having a certain dimensional stability. However, in the face of growing environmental challenges, the cement industry is now forced to limit the use and production of Portland cement.
    [0002] The Portland cement manufacturing process is energy intensive and generates significant emissions of carbon dioxide (CO2). Portland clinker is a product based on silicate and calcium aluminate, obtained by calcining at a high temperature (around 1450 ° C) a mixture of limestone and clay in certain proportions (80% / 20 parts respectively). about% by weight), followed by rapid cooling of the mixture. During the limestone calcination stage in quicklime (calcium oxide, CaO), large amounts of CO2 are emitted. In addition, the product obtained after cooling the mixture, is in the form of granules which are crushed before being finely ground with calcium sulfate to form Portland cement, which generates additional energy costs. Another drawback associated with the use of a large quantity of Portland cement is that the Portland clinker is a sensitizing and irritating agent for the body, especially the skin, the eyes and the respiratory tract when it is present at more than 10%. by weight in a product. In fact, in most countries, regulations require special precautions, including the use of safety rules and / or devices, for the handling of products with a high Portland clinker content. Research has therefore turned towards the development of new types of hydraulic binders including industrial waste, ie by-products of the steel industry such as blast furnace slags. However, unlike Portland clinker, these by-products of the iron and steel industry are latent hydraulic compounds, that is to say that an activation is necessary so that they develop rapidly in contact with water mechanical properties interesting. In fact, the addition of water to a sample of non-activated blast furnace slag causes no phenomenon of setting or hardening of the mixture. The activation of blast furnace slag can be achieved by adding one or more chemical compounds of a particular nature. The activation of the blast furnace slag can be obtained by adding either an alkaline agent (for example sodium hydroxide or lime) or a sulphate-based agent (for example gypsum) or a combination of both types. agents: gypsum and soda or gypsum and lime. In the presence of Portland cement, the blast furnace slag can be activated by the lime released by hydrated Portland clinker, and calcium sulphate.
    [0003] However, the use of alkaline activators at high levels in the binder or in the building material poses health problems because they are likely to cause serious skin irritation. Moreover, although the use of calcium sulfate has the advantage of not being irritating or sensitizing to the body, construction materials manufactured with such a binder often have problems of stability over time. They are generally not very resistant to water and the repeated or prolonged contact with water or in humid conditions (inclement weather, wet confined space, immersion under water ...) can lead to a loss of mechanical resistance and durability of building materials.
    [0004] In the application US 6,409,820, it is disclosed a hydraulic binder composition comprising 85% by weight of granulated blast furnace slag having a particle fineness of 5800 cm 2 / g, 13% by weight of a synthetic gypsum corresponding to a content S03 equivalent of 6.1% by weight, 1% by weight of Portland cement and 0.5% by weight of calcium acetate, all of these contents being expressed on the basis of the total weight of the binder composition hydraulic. Although this binder has reduced levels of Portland cement, it remains to be improved, especially in terms of setting speed and hardening. Thus, there is a need to provide a hydraulic binder based on blast furnace slag to remedy all or part of the aforementioned drawbacks of the prior art. In particular, there is a need to develop a blast-furnace slag based hydraulic binder having an improved setting and hardening speed, compared to the hydraulic binder of US 6,409,820, and construction having in particular in the short term improved mechanical properties. As part of the present application, the short-term mechanical properties are generally measured from 24 hours up to 28 days from the preparation of the construction material. The use of a hydraulic binder having such properties can be advantageous for many applications in the field of construction for the manufacture of concretes or mortars for which a rapid return to service of the structure is expected, with a certain level of of mechanical resistance to be achieved at a given time. For example, such a hydraulic binder can be used to make fixing mortars such as adhesive mortars, or jointing mortars, for which adhesion or jointing, fast and efficient is desired.
    [0005] The use of such a hydraulic binder may also be desired for making smoothing mortars including floor coatings, for which it is desired to reduce the opening time to walking. The qualities sought for a smoothing coating are among others defined in the specifications of the Scientific and Technical Center for Building (CSTB) relating to soil coatings. The use of such a hydraulic binder may also be desired to manufacture repair or patching mortars, capable of filling quickly and effectively defects (cracks, holes) on the surface of a building material such as concrete, brick, or plaster.
    [0006] There is also a need for a hydraulic binder also having a reduced environmental and health impact compared to Portland cement, thus obtaining a building material more respectful of people and the environment. In particular, it is desired to be able to formulate from such a binder a construction material which can be handled, transported or manufactured without setting up particular safety devices. There is also a need to provide a hydraulic binder that is insensitive or insensitive to external agents, such as water and moisture, making it possible to produce a durable building material, particularly resistant to repeated and / or prolonged exposures to such agents. .
    [0007] Finally, there is a need to obtain a construction material, such as a concrete or mortar, having one or more of the abovementioned advantages, and moreover satisfying the criteria of mechanical performance, particularly in the short term, of adhesion and / or suitability for use (homogeneity of mixing, fluidity for spreading or self-spreading) desired with respect to the intended use.
    [0008] Surprisingly, it has been discovered that a hydraulic binder according to the invention as defined below, made it possible to meet all or part of the aforementioned needs. In particular, it has been found that the combination of at least one calcium sulphate, at least one product selected from a source of Portland clinker and lime, at least one particular aluminum derivative and at least one particular alkali or alkaline earth metal salt, as further defined hereinafter, provided for better activation of a granulated blast furnace slag, resulting in a hydraulic binder having a taking and curing in water improved compared to the prior art.
    [0009] The hydraulic binder according to the invention is also respectful of man and the environment, particularly with regard to Portland cement. In fact, the hydraulic binder according to the invention makes it possible to obtain a construction material having these same advantages. In addition, thanks to its hydraulic power, the hydraulic binder according to the invention makes it possible to obtain a building material capable of rapidly developing satisfactory mechanical properties (hardness, flexural strength, compressive strength, and / or adhesion). ). In particular, it has been found that it is possible to obtain from a hydraulic binder according to the invention a material of construction having a good aptitude for use (homogeneity of mixing and / or ease of use), after mixing its ingredients with water. It has also been found that it was possible to obtain from a hydraulic binder according to the invention a durable or stable construction material over time. In particular, the mechanical properties of the building material according to the invention are little or not degraded over time, even after prolonged contact with water. The building material is therefore particularly suitable for use in applications in which the material is likely to be subjected to prolonged or repeated contact with water (rain) or high humidity (greater than or equal to 50% relative humidity).
    [0010] In particular, the building material according to the invention has a good flexural strength. In particular, the building material according to the invention has good dimensional stability over time. In particular, it has been found that it is possible to obtain a mortar or smoothing coating, especially for the floor, which has excellent short-term mechanical properties (flexural strength, compressive strength) while having good properties. self-spreading and dimensional stability, over time. The present invention therefore relates firstly to a hydraulic binder composition comprising: a) at least 50% by weight relative to the weight of the hydraulic binder composition, a ground granulated blast furnace slag, b) at least calcium sulphate, c) at least one product selected from a source of Portland clinker and lime, d) at least one aluminum derivative selected from an alumina having a BET surface area ranging from 100 to 400 m2 / g, a monocalcium aluminate and a calcium sulfoaluminate, and e) at least one alkali or alkaline earth metal salt selected from chloride salts, bromide salts, silicate salts, nitrate salts, acid salts, carboxylic acid such as the salts of monocarboxylic acid C1-C4, the total calcium sulphate content expressed as an equivalent content of SO 3 being at least 5% by weight relative to the weight of the hydraulic binder composition; sum of the contents of the products mentioned in points c) and e) being less than 10% by weight based on the weight of the hydraulic binder composition. Other objects, features and advantages of the present invention will become more apparent upon reading the description and examples. In the present application, in the absence of any indication to the contrary: - the quantities expressed as a percentage correspond to weight / weight percentages, - the indefinite article "un (e)" used to designate an ingredient of a composition according to the invention (binder, building material), must be understood as "one or more" thus including the mixture of these ingredients. It is the same for the use of the corresponding definite article "", "the", "la" which must be understood as including the mixture of several of these ingredients. For example, "a" ground granulated blast furnace slag, a granulated blast furnace slag, or a ground granulated blast furnace slag. the term "Blaine finesse" or "Blaine specific surface area" is used to denote the specific surface area of a solid powdery compound, expressed in cm 2 per gram of solid, measured by the air permeabilimetry method (or Blaine method). This method is described by standard NF EN 196-6. the terms "hydraulic binder" and "hydraulic binder composition" are used interchangeably in this application. Similarly, the terms "building material" and "building material composition" are referred to interchangeably.
    [0011] The hydraulic binder composition according to the invention comprises at least 50% by weight of ground granulated blast furnace slag with respect to the weight of said composition. The ground granulated blast furnace slag that can be used according to the invention is in the form of particles.
    [0012] The maximum particle size of the ground granulated blast furnace slag that can be used according to the invention is preferably less than 45 lm. This maximum particle size of the granulated ground blast furnace slag that can be used according to the invention is determined in a manner well known to those skilled in the art by laser granulometric analysis. In particular, at least 99% by volume of the particles of the ground granulated blast furnace slag that can be used according to the invention are preferably less than 32 μm. More particularly, at least 50% by volume of said particles are preferably less than 10 μm and more preferably less than 5.5 μm. These particles 10 therefore have a mean diameter D 50, preferably less than 10 μm and more preferably less than 5.51 μm. The particle size analysis of the average particle size of the granulated ground blast furnace slag used according to the invention can be carried out in a manner well known to those skilled in the art by laser granulometric analysis. The Blaine specific surface area of the ground granulated blast furnace slag that can be used according to the invention is preferably greater than or equal to 5000 cm 2 / g, and more preferably greater than or equal to 6000 cm 2 / g. Even more preferably, the Blaine specific surface area of the ground granulated blast furnace slag that can be used according to the invention ranges from 6500 to 9000 cm 2 / g, and more preferably from 7000 to 8000 cm 2 / g. The chemical composition of the ground granulated blast furnace slag that can be used according to the invention comprises calcium oxide (CaO), magnesium oxide (MgO), silicon dioxide or silica (SiO 2), and magnesium oxide. aluminum oxide (Al 2 O 3), in contents such that the sum of the contents of calcium oxide, magnesium oxide and silicon dioxide represents at least two thirds by weight (66.7% by weight) of the weight of the granulated slag The weight ratio of the sum of the calcium oxide and magnesium oxide contents to the silicon dioxide content (denoted by Ca0 + Mg0) / SiO2) is greater than 1.0. Preferably, the granulated blast furnace slag that can be used according to the invention also comprises a vitreous phase representing at least two thirds by weight of the granulated blast furnace slag that can be used according to the invention and is composed of a vitreous phase. More preferably, the ground granulated blast furnace slag that can be used according to the invention comprises at least 90% by weight, and more preferably at least 95% by weight of vitreous phase, relative to the weight of ground granulated blast furnace slag.
    [0013] Preferably, the chemical composition of the ground granulated blast furnace slag that can be used according to the invention is such that the sum of the weight contents of calcium oxide (CaO), magnesium oxide (MgO), silica (SiO 2) and aluminum oxide (A1203) is greater than or equal to 80% by weight, more preferably greater than or equal to 90% by weight, and more preferably greater than or equal to 95% by weight, relative to the weight of ground granulated blast furnace slag. Preferably, the chemical composition of the ground granulated blast furnace slag that can be used according to the invention comprises less than 39% by weight of silica, less than 15% by weight of aluminum oxide (Al 2 O 3), more than 37% by weight. of calcium oxide (CaO), and less than 13% by weight of magnesium oxide (MgO), based on the weight of ground granulated blast furnace slag. More preferably, the chemical composition of the ground granulated blast furnace slag that can be used according to the invention comprises from 33 to 37% by weight of silica (SiO 2), from 9 to 14% by weight of aluminum oxide (Al 2 O 3), from 38 to 42% by weight of calcium oxide (CaO), and 1 to 12% by weight of magnesia (MgO), based on the weight of ground granulated blast furnace slag. More preferably, the chemical composition of the ground granulated blast furnace slag according to the invention further comprises less than 1% by weight of Fe 2 O 3, less than 2% by weight of TiO 2, up to 2.5% by weight of SO 3 and up to 2% by weight of sulfide ions (S2-), based on the total weight of granulated blast furnace slag. The amounts of calcium oxide, magnesia, alumina and silica present in the ground granulated blast furnace slag that can be used according to the invention preferably satisfy at least one of the following three relationships: (Ca0 + Mg0 ) - - (A1203 + SiO2)> 1.03 (Ca0 + Mg0 +0.3 * Al2O3) -r2 (F11) -> 1.20 (SiO2 + 0.7 * Al2O3) -r3 (F3) - (Ca0 + MgO + , 11203)> 1.6, and the aluminum oxide content (Al 2 O 3) being less than (SiO 2) 13% by weight of the weight of ground granulated blast furnace slag, r 1, r 2 and r 3 corresponding to the weight ratios relative to quantities of calcium oxide, magnesia, alumina and silica present in ground granulated blast furnace slag.
    [0014] More preferably, the amounts of calcium oxide, magnesia, alumina and silica present in the granulated blast furnace slag satisfy the three relations ri, r2 and r3 defined above. The ground granulated blast furnace slag that can be used according to the invention can be obtained in a manner well known to those skilled in the art. Blast furnace slag is a by-product of iron production that is obtained by melting iron ore in a blast furnace at a temperature above the melting temperature of the iron and slag, for example, greater than 1500-1600 ° C. Blast furnace slag and cast iron are separated by density difference in the liquid state. Then the blast furnace slag will undergo rapid cooling which will vitrify the blast furnace slag. The vitrified blast furnace slag thus obtained is commonly referred to as "granulated blast furnace slag". This is then dried and milled to obtain a ground granulated blast furnace slag having the desired fineness and / or granulometry (s). The ground granulated blast furnace slag that can be used according to the invention can be derived directly or indirectly from the above-described preparation process. In particular, the ground granulated blast furnace slag that can be used according to the invention can result from a co-grinding of two or more granulated blast furnace slags, from the mixture of two or more ground granulated blast furnace slags, or be subjected to composition adjustment by additions of metal oxide, annealing in the blast furnace and quenching, as taught in the application CA 1,131,664. The hydraulic binder composition according to the invention preferably comprises a total content of ground granulated (s) granulated slag (s) ranging from 50 to 90% by weight, and more preferably from 60 to 70% by weight. , based on the weight of the hydraulic binder composition.
    [0015] The hydraulic binder composition according to the invention comprises at least calcium sulfate in a particular content. In general, the term calcium sulphate (generally denoted CaSO4) covers calcium sulphate in any of its hydrated or non-hydrated forms, and the various mixtures of said hydrated or non-hydrated forms.
    [0016] Thus, the calcium sulphate that can be used according to the invention can be chosen from anhydrous calcium sulphate (or anhydrite) (generally denoted anhydrous CaSO4), calcium sulphate hemihydrate (hemihydrate or bassanite) (generally denoted CaSO4 × 0, 5H20), calcium sulfate dihydrate (or gypsum) (CaSO4.2H2O), and mixtures of these compounds.
    [0017] Preferably, the calcium sulfate that can be used according to the invention comprises at least 90% by weight and more preferably at least 95% by weight of anhydrous calcium sulphate with respect to the weight of calcium sulphate. More preferably, the calcium sulfate used according to the invention is anhydrous calcium sulfate.
    [0018] The calcium sulphate which can be used according to the invention preferably has a pH greater than or equal to 7, more preferably greater than or equal to 8, and more preferably greater than or equal to 11. The calcium sulphate which can be used according to the invention can be of natural or synthetic origin.
    [0019] In particular, the calcium sulphate which can be used according to the invention can be obtained by synthesis as a by-product of the manufacture of a mineral acid (boric acid, hydrofluoric acid, phosphoric acid), of an organic acid (citric acid). tartaric acid) or titanium oxide. It can also be obtained by desulfurization of gases and fumes.
    [0020] The total weight content of calcium sulphate present in the hydraulic binder composition according to the invention is expressed in equivalent weight content of SO 3. The calcium sulphate present in the hydraulic binder composition of the invention may possibly be brought in part by other ingredients of the hydraulic binder, particularly when the source of Portland clinker is a cement (Portland, compound or pozzolanic) such as described later. However, the total content of calcium sulphate present in the hydraulic binder composition according to the invention, expressed as SO.sub.3 content, must be greater than 5% by weight relative to the weight of the hydraulic binder, in order to achieve satisfactory mechanical properties rapidly. on the hardened product. Preferably, the hydraulic binder composition according to the invention comprises a total weight content of calcium sulphate expressed in equivalent weight content of SO 3 ranging from 5 to 25% by weight, and more preferably from 13 to 20% by weight, relative to the weight of the hydraulic binder composition. The hydraulic binder composition according to the invention comprises at least one product chosen from a source of Portland clinker, lime, and their mixture.
    [0021] The Portland clinker source that may be used according to the invention may be chosen from a Portland clinker, a Portland cement, a Portland cement compound, a pozzolanic cement, and mixtures thereof. In particular, it is possible to use, as a Portland clinker source, a Portland clinker comprising: at least the following crystalline mineralogical phases: tricalcium silicates and dicalcium silicate (3CaO.SiO 2 and 2CaO.SiO 2 respectively denoted C3S and C2S) , - tetracalcium ferroaluminate (A1203.Fe203.4CaO - noted C4AF), and optionally tricalcium aluminate (Al 2 O 3 .3CaO - noted C3A), in contents such that: the crystallized C3S and C2S mineralogical phases represent at least two one third of the weight of the Portland clinker, the total contents of calcium oxide and silica are such that the weight ratio (Ca0) / (SiO2) is greater than or equal to 2, - and possibly magnesium oxide ( MgO) in a content of less than or equal to 5% by weight of the weight of the Portland clinker. Preferably, the weight ratio (Ca0) / (SiO2) is greater than or equal to 3. Preferably, the content of magnesium oxide is less than or equal to 1% by weight of the weight of the Portland clinker. The Portland clinker may further comprise one or more of the following chemical elements: phosphorus fluoride (PF), titanium dioxide (TiO 2), manganese oxide (MnO), sodium oxide (Na 2 O), phosphorus pentoxide (P 2 O 5), strontium oxide (Sr0).
    [0022] In particular, it is possible to use, as Portland cement clinker source, a CEM I type Portland cement as defined by standard NF EN 197-1. Such a cement comprises at least 95% by weight of Portland clinker, relative to the weight of said cement. The Portland clinker is preferably as defined in any one of the paragraphs of this application. More preferably, a CEM I 52.5 R type Portland cement is used as defined by standard NF EN 197-1. In particular, it is possible to use, as Portland cement clinker source, a Portland cement compound of the CEM II type as defined by the NF EN 197-1 standard. Such a cement comprises from 65 to 94% by weight of Portland clinker, relative to the weight of said cement. The Portland clinker is preferably as defined in any one of the paragraphs of this application. In particular, it is possible to use, as a source of Portland clinker, a pozzolanic cement of the CEM IV type as defined by the NF EN 197-1 standard. Such a cement comprises from 45 to 89% by weight of Portland clinker, relative to the weight of said cement. The Portland clinker is preferably as defined in any one of the paragraphs of this application. In particular, it is possible to use, as Portland cement clinker source, a composite cement of the CEM V type as defined by the NF EN 197-1 standard. Such a cement comprises from 20 to 64% by weight of Portland clinker, relative to the weight of said cement. The Portland clinker is preferably as defined in any one of the paragraphs of this application. The cements described above comprise in principle calcium sulphate in a content expressed in equivalent content of SO 3 less than or equal to 4% by weight of the weight of said cement. According to a more preferred embodiment, the Portland clinker, which can be used according to the invention or contained in the cements that can be used according to the invention, comprises, in addition to the crystalline mineralogical phases mentioned above, at least the following crystallized mineral phases C35, C25, C4AF, C3A and K2504 (Arcanite).
    [0023] More preferably, the weight content in the C35, C25, C4AF, C3A, K2504 mineral phases present in the Portland clinker is such that the source of Portland clinker comprises: from 60 to 70% by weight of C35, from 5 to 15 % by weight of C25, 2 to 6% by weight of C4AF, 5 to 15% by weight of C3A, 0.1 to 2% of K2504 (Arcanite), based on the weight of the source of Portland clinker. Among the sources of Portland clinker that can be used according to the invention, it is preferred to use Portland cement CEM I 52.5 R. By way of example, such a cement may comprise: from 3 to 4% of calcium sulphate expressed as a% of weight of SO 3 in cement, and 60 to 70% by weight of C 35, 5 to 15% by weight of C 25, 2 to 6% by weight of C 4AF, 5 to 15% by weight of C3A, from 0.1 to 2% by weight of K2504 (Arcanite), relative to the weight of said cement. The calcium sulphate present in Portland cement CEM I 52.5R can be chosen from gypsum, hemihydrate, anhydrite and their mixture.
    [0024] Preferably, the content of calcium sulphate present in Portland cement CEM I 52.5R expressed in SO 3 content ranges from 3.5 to 4% by weight of the weight of said cement. The lime that can be used according to the invention can be chosen from quicklime (CaO) and slaked lime (Ca (OH) 2).
    [0025] Preferably, the hydraulic binder composition according to the invention comprises at least one source of Portland clinker. The hydraulic binder composition according to the invention preferably comprises a total content of product (s) chosen (s) from a source of Portland clinker, lime, and their mixture, less than 5% by weight, more preferably, ranging from 0.2 to 4% by weight, and more preferably from 0.4 to 1.8% by weight, based on the total weight of the hydraulic binder composition. The hydraulic binder composition according to the invention comprises at least one aluminum derivative chosen from an alumina having a BET specific surface area ranging from 100 to 400 square meters per gram (m 2 / g), a monocalcium aluminate and a calcium sulfoaluminate.
    [0026] The aluminum derivative which can be used according to the invention is in the form of particles. The alumina that can be used as the aluminum derivative preferably has a BET specific surface area ranging from 250 to 350 m 2 / g. In particular, it is possible to use a transition alumina (flash alumina) having such a specific surface area.
    [0027] The BET surface area is determined by nitrogen adsorption, in accordance with ISO 9277: 2010. The monocalcium aluminate that can be used as aluminum derivative can be added to the hydraulic binder composition according to the invention by a calcium aluminate cement (CAC) comprising monocalcium aluminate. In this case, it is preferable to use a calcium aluminate cement whose alumina content (expressed as Al 2 O 3) is at least 35% by weight, more preferably at least 45% by weight, more preferably at least 55% by weight, based on the weight of the calcium aluminate cement. Better still, using a calcium aluminate cement whose alumina content is 65 to 75% by weight of said cement.
    [0028] The calcium sulfoaluminate which can be used as the aluminum derivative is preferably yeelemite (4CaO, 3A1203, SO3). Yeelimite can be provided in the hydraulic binder composition according to the invention by a calcium sulfoaluminate cement ("CSA") comprising yeelemite. In this case, a calcium sulphoaluminate cement is preferably used, the yeelimite content of which is at least 10% by weight, more preferably at least 50% by weight, and more preferably at least 60% by weight. weight, relative to the weight of the calcium sulfoaluminate cement. More preferably, a calcium sulfoaluminate cement is used, the yelemite content of which is at least 65% by weight of the weight of said cement.
    [0029] The hydraulic binder composition according to the invention preferably comprises from 0.2 to 2.1% by weight, and more preferably from 0.3 to 0.8% by weight, of at least one aluminum derivative such as defined above, relative to the weight of the hydraulic binder composition. The hydraulic binder composition according to the invention comprises at least one inorganic or alkaline earth metal salt (Na, Ca, K, Li), mineral or organic, chosen from chloride salts, bromide salts, silicate, nitrate salts, carboxylic acid salts such as C1-C4 monocarboxylic acid salts. Preferably, among the alkali metal or alkaline earth metal salts as defined above, calcium chloride (CaCl 2), calcium formate and / or calcium acetate are used. The hydraulic binder composition according to the invention preferably comprises a total content of alkali metal or alkaline earth metal salt (s), as defined above, of less than 5% by weight, more preferably ranging from 1 to 4% by weight, and more preferably ranging from 1.1 to 3.2% by weight, based on the total weight of the hydraulic binder composition. The hydraulic binder composition according to the invention is in the form of a powder and is obtained by simply mixing its ingredients which are themselves in the form of solids in the powdery state. The subject of the present invention is also a second composition of a ready-to-mix construction material comprising: a hydraulic binder according to the invention and aggregates of inert materials capable of being agglomerated in aqueous phase by means of said binder to form an aggregate. By "ready-to-spoil" it is meant that the composition according to the invention is intended to be mixed with water just before or at the time of its use, with a view to the preparation of a construction material such as a mortar or concrete, and in particular a mortar glue, joint mortar, mortar or smoothing plaster. Preferably, the mixing ratio used is as defined below.
    [0030] The composition of ready-to-mix construction material according to the invention preferably comprises a content of hydraulic binder ranging from 15 to 75% by weight, and more preferably from 20 to 50% by weight, relative to the weight of said composition Agacher nominee.
    [0031] Preferably, the total content of products mentioned in c) and e) above is less than or equal to 1% by weight relative to the weight of the ready-to-mix construction material composition. The aggregates of inert materials that may be used according to the invention may be fillers, sand or gravel as defined by standard NF-EN 12-620 (2008) or NF-EN 13-139 (2003). Preferably, the size of said granules varies from 1 μm to 8 mm. As aggregates of inert materials that can be used according to the invention, it is possible to use, for example, calcareous or siliceous aggregates or silico-calcareous aggregates. Preferably, calcareous fillers and / or siliceous sands are used.
    [0032] The composition of ready-to-mix construction material according to the invention preferably comprises a content of granules of inert materials ranging from 25 to 85% by weight, and more preferably from 50 to 80% by weight, relative to the weight of said composition ready to spoil. The ready-to-mix construction material composition according to the invention preferably further comprises at least one polymer. The polymer which can be used according to the invention can be in the form of a powder which can be dispersed in water or of solid-liquid dispersion in water (that is to say in the form of an aqueous polymer dispersion). When the polymer is in the form of water-dispersible powder, it is preferably selected from vinyl acetate, vinyl versatate and ethylene copolymers. Such polymers are commercially available from Wacker, Hexion and Elotex. By way of example, mention may be made in particular of: polymers of vinyl acetate, vinyl versatate and maleic ester, available in powder form from the company Hexion under the name Axilate UP 620E; polymers of vinyl acetate, vinyl versatate and ethylene, available in powder form from Elotex under the name Elotexe FL3200 or FX3300, - copolymers of vinyl acetate and ethylene, available in the form of powder from Wacker under the name Vinnapase 5011L or Vinnapase 4023N. The content of polymer in the form of water-dispersible powder that may be used in the composition of the ready-to-mix construction material according to the invention is preferably less than or equal to 10% by weight relative to the weight of said ready-to-use composition. to-spoil according to the invention. When the polymer is in the form of a solid-liquid dispersion in water, it is preferably chosen from aqueous styrene-butadiene, styrene-acrylic, styrene-acrylate, acrylic, vinyl acetate, vinyl acetate and ethylene dispersions. , and versatate vinyl and ethylene. Such polymer dispersions in water are commercially available from Rohm & Haas, BASF and Synthomer. By way of example, mention may be made in particular of: acrylic acid ester and styrene ester copolymers, in the form of an aqueous dispersion, available from the company BASF under the name Acronale DS 5018 (at 50% by weight of solid in water), - styrene-butadiene carboxyl copolymers, available in the form of an aqueous dispersion from Synthomer, under the names Lipatone SB 29Y141 (at 47% by weight of solid in water) and Lipatone SB 29Y146 (at 47% by weight of solid in water). The content of aqueous dispersion of polymer that can be used in the ready-to-mix construction material composition according to the invention can represent up to 20% by weight of the total weight of said ready-to-mix composition according to the invention. The polymer content in the aqueous dispersion may represent 30 to 60% by dry weight, and preferably 40 to 55% by dry weight, of the total weight of said aqueous dispersion. The composition of ready-to-mix building material according to the invention may also comprise at least one adjuvant chosen from plasticizers or superplasticizers, antifoaming agents, air-entraining agents, water-repellent agents, retention agents and water or rheology agent, set retarders or curing agents, dyes, and mixtures of these compounds. These adjuvants may be in the solid or liquid state, for example in the form of a powder or an aqueous dispersion. Preferably, these adjuvants are in the form of powder.
    [0033] The composition of ready-to-mix construction material according to the invention may be a monocomponent product when it does not comprise a liquid ingredient composed in particular of water. In this case, the ingredients of the ready-to-mix composition according to the invention can be stored in the same container, for example in the form of a bag of powder, before being mixed with water to form the building material. The ready-to-mix construction material composition according to the invention is generally a two-component product when it comprises at least one liquid ingredient. In this case, the liquid ingredients are stored separately from the other ingredients (powdery solids) of the ready-to-mix composition according to the invention, and are mixed only at the moment of use during the mixing step. with water. The process for carrying out the ready-to-mix composition according to the invention is described further below. According to a preferred embodiment of the invention, the ready-to-mix construction material composition according to the invention is a one-component product consisting of a pulverulent composition (denoted A ')) comprising: - a hydraulic binder according to the invention; invention, aggregates of inert materials, capable of being agglomerated in the aqueous phase by means of said binder to form an aggregate, at least one polymer in the form of water-dispersible powder as described above, and optionally in less an adjuvant in the form of powder as described above. The weight contents of ingredients described above remain applicable to this preferred embodiment of the composition of ready-to-break construction material according to the invention.
    [0034] According to another variant embodiment of the invention, the construction material composition is a two-component product consisting of: a pulverulent composition (denoted A) comprising: a hydraulic binder according to the invention, granules of materials inert, capable of being agglomerated in aqueous phase by means of said binder to form an aggregate, of a liquid composition (denoted by B) comprising: at least one aqueous polymer dispersion, as described above, and optionally at least one liquid adjuvant as described above.
    [0035] The pulverulent composition A) of the two-component product according to the invention may also comprise at least one polymer in the form of a powder that is dispersible in water as described above, and / or at least one adjuvant in powder form as described above.
    [0036] The weight contents of ingredients described above remain applicable to this preferred embodiment of the composition of ready-to-break construction material according to the invention. In each of the two embodiments described above, the powder composition of the mono or two-component product can be obtained by simultaneous mixing of the ingredients of the hydraulic binder with the granules of inert materials and the other powdery ingredients present or possibly present in said composition. Thirdly, the subject of the present invention is a process for implementing a composition of ready-to-mix construction material according to the invention, comprising a step of mixing (or mixing) said composition with water. , for the preparation of a building material, such as a concrete or mortar, and in particular a mortar glue, joint mortar, or mortar or smoothing plaster. In particular, the construction material can be prepared from a one-component or two-component product as previously described. When the building material is prepared from a monocomponent product, said product is mixed with water. When the building material is prepared from a two-component product, the liquid ingredients of said product (liquid composition B) are mixed with water before the assembly is mixed with the non-liquid ingredients of said product (pulverulent composition A ).
    [0037] At the end of these mixing steps, a homogeneous paste is obtained which will progressively become stiffer on contact with the water. After 24 hours, a sufficiently hard product is obtained to evaluate the mechanical properties of the building material. The above-described steps of the preparation process according to the invention are generally carried out at room temperature (about 23 ° C.).
    [0038] Preferably, the mixing rate is adjusted so as to obtain at the end of the preparation process, a product of desired consistency, easy to implement for the intended purpose.
    [0039] The mixing rate corresponds to the weight ratio of the amount of water used to prepare the construction material according to the invention on the sum of the amounts of the solids used to prepare the construction material according to the invention. The water used to prepare the construction material according to the invention corresponds to the water added to the composition of the ready-to-mix building material according to the invention, and, if appropriate, to the water of the liquid ingredients of said composition. The dry materials used to prepare the construction material according to the invention correspond to the non-liquid ingredients of the ready-to-mix construction material composition according to the invention, and where appropriate to the dry extract of the liquid ingredients of the invention. said composition. It is possible to use a mixing ratio ranging from 0.1 to 0.4. Preferably, the mixing ratio is from 0.1 to 0.3, corresponding to the mixture of 10 to 30 grams of water with 100 grams of solid powdery ingredients. The construction material thus obtained is easy to implement.
    [0040] It can be used in particular as: - fixing mortar, in particular, an adhesive mortar, intended for the installation of tiles such as ceramic or glass tiles; jointing mortar, intended to fill interstices between different elements of masonry or tiling, mortar or smoothing compound for the floor, wall or ceiling, such as a self-leveling or self-leveling coating for flooring. mortar repair or patching, intended for filling cracks or cavities on the surface of a construction material of identical or different composition, essentially mineral, such as concrete, brick, or plaster.
    [0041] The following examples are given purely by way of illustration of the invention and can not be interpreted to limit its scope. Examples: Soil smoothing coatings: Five ready-to-mix pulverulent compositions are prepared from five different hydraulic binders, by mixing the various ingredients of Table 1 below.
    [0042] The hydraulic binder 1 (according to the invention) is prepared by mixing: a) 20 g of ground granulated blast furnace slag used according to the invention (representing 64.3% by weight of the weight of the binder), b) 10 g of sodium sulfate. synthetic calcium containing at least 90% by weight of anhydrous calcium sulphate according to the invention (representing 32.2% by weight of the weight of the binder, and corresponding to 18.9% by weight of SO 3 based on the weight of the binder) (c) 0.20 g of Portland cement CEM I 52.5 R (representing 0.6% by weight of the weight of the binder), d) 0.1 g of flash alumina with BET specific surface area ranging from 100 to 400 m 2 / g (representing 0.3% by weight of the weight of the binder), e) 0.8 g of CaCl 2 .2H 2 O (representing 2.6% by weight of the weight of the binder). The hydraulic binder 2 (comparative) is prepared by mixing: a) 20.56 g of ground granulated blast furnace slag used according to the invention (representing 66.1% by weight of the weight of the binder), b) 10.28 g of sulphate synthetic calcium containing at least 90% by weight of anhydrous calcium sulphate according to the invention (representing 33.1% by weight of the weight of the binder, and corresponding to 19.4% by weight of SO 3 based on the weight of the binder ), c) 0.26 g of Portland cement CEM I 52.5 R (representing 0.8% by weight of the weight of the binder) The hydraulic binder 3 (comparative) is prepared by mixing: a) 20.48 g of granulated blast furnace slag ground material used according to the invention (representing 65.8% by weight of the weight of the binder), b) 10.24 g of synthetic calcium sulphate containing at least 90% by weight of anhydrous calcium sulphate according to the invention (representing 33% by weight of % by weight of the weight of the binder, corresponding to 19.4% by weight of SO 3 based on the weight of the binder), c) 0.26 g of Portland cement CEM I 52.5 R (r representing 0.8% by weight of the weight of the binder), d) 0.13 g of flash alumina with BET specific surface area ranging from 100 to 400 m 2 / g (representing 0.4% by weight of the weight of the binder). The hydraulic binder 4 (comparative) is prepared by mixing: a) 19.9 g of granulated blast furnace slag used according to the invention (representing 64% by weight of the weight of the binder), b) 9.95 g of calcium sulphate at least 90% by weight of anhydrous calcium sulphate according to the invention (representing 32% by weight of the weight of the binder, and corresponding to 18.9% by weight of SO 3 relative to the weight of the binder), c) 0.25 g of Portland CEM I 52.5 R cement (representing 0.8% by weight of the weight of the binder), e) 1 g of CaCl 2 .2H 2 O (representing 3.2% by weight of the weight of the binder). The hydraulic binder 5 is a commercial reference product composed of at least 50% by weight of Portland cement relative to the weight of commercial product. The granulated blast furnace slag used in the examples of the present application has the following characteristics: -Granulometry: D50 = 5 iam, maximum particle size <45 iam, -Finesse: Blaine specific surface = 7000-8000cm2 / g, Percentage of vitreous phase greater than 90% by weight of the weight of the slag, - chemical composition of the slag comprising: - 33 to 37% by weight of silica (5iO 2), - 9 to 13% by weight of alumina (Al 2 O 3), 38 to 42% by weight of calcium oxide (CaO), 1 to 12% by weight of magnesia (MgO), less than 1% by weight of Fe 2 O 3, less than 2% by weight of TiO 2, 2.5% by weight of SO 3, and up to 2% by weight of sulphide ions (52-) and whose weight contents of silica (5iO 2), alumina (Al 2 O 3), calcium oxide (CaO 2) ), and magnesium oxide (MgO) satisfy the following relationships: - (Ca0 + Mg0)> 103 (A1203 + St02) '(Ca0 + Mg0 + 0.3 * A / 203) -r2 (F11) -> 1 , (SiO2 + 0.7 * Al2O3) -r3 (F3) - (CaO + Mg0 + Al2O3)> 1.6 (SiO2) - - the sum of The weight contents of CaO + MgO + Al 2 O 3 + 5IO 2> 80% by weight, all the percentages by weight indicated above being expressed on the basis of the total weight of ground granulated blast furnace slag. The contents of the ingredients of Table 1 below are expressed in grams.
    [0043] Ingredients Exl Ex2 Ex3 Ex4 Ex5 (Invention) (Comparative (Comparative (Comparative (Comparative 1) 2) 3) 4) Binder 31.1 - - - - Hydraulic 1 Binder - 31.1 - - - Hydraulic 2 Binder - - 31, 1 - - hydraulic 3 Binder _ - - 31.1 - hydraulic 4 Binder _ _ _ - 31.1 hydraulic 5 Sand siliceous 34.2 34.2 34.2 34.2 34.2 (0,1 -0,3 mm) Calcium carbonate (D50 = 8 μm) 32.6 32.6 32.6 32.6 32.6 Polymer of vinyl acetate, vinyl versatate and ethylene in powder form 2 2 2 2 2 Cellulose ethers, gums, antifoam and colorants 0.1 0.1 0.1 0.1 0.1 Total weight of the powder composition 100 100 100 100 100 Table 1 Each of these five compositions is then mixed with water to form a soil coating, at the rate of 16g of water per 100g of powder composition. This corresponds to a mixing rate of 16% (ie 0.16).
    [0044] Unless otherwise indicated in the present application, the preparation of soil coatings and the measurement of their properties relating to self-spreading, setting speed, flexural strength (Rf), compressive strength (Rc) ) and the shrinkage were carried out in accordance with the protocol and the operating conditions defined in the CSTB technical document relating to floor coatings, titled test methods and controls carried out by the manufacturer, DT7, Revision 01. I-Series d Tests on the compositions of Examples 1, 2 and 5 I.1-Tests on wet product 1.1.1-Preparation of the tempered product (soil smoothing coating) In a bowl, 2 kilograms of pulverulent composition are kneaded with water at a mixing rate of 16% for 1 minute using a mechanical mixer as described in standard NF EN1937 at slow speed (rotation speed 140 revolutions per minute (rpm) and rotational speed planetary 62 rpm). Then the wall of the container and the kneader of the kneader are scraped with a spatula to detach the possibly agglomerated powder. Again, the whole is kneaded for 1 minute at slow speed (rotation speed 140 revolutions per minute (rpm) and planetary rotation speed 62 rpm). I.1.2-Measurement of the spread diameter and homogeneity of the soil smoothing coating Measurements of the spreading diameter and homogeneity of the soil coating at 5 minutes and then at 20 minutes are carried out from the same tempered product, prepared as described above in 1.1.1. Measurement at 5 minutes (min): After 5 minutes of rest, the tempered product is poured into a ring 30 mm in diameter and 50 mm high placed in the center of a glass plate. Once filled, the ring is raised and releases the product that spreads on the glass plate. After waiting for 5 minutes, the spreading diameter of the product, expressed in millimeters and measured along two perpendicular axes, is measured and the homogeneity of the spread product is evaluated visually by noting the presence or absence of sedimentation at the periphery of the product. dough. The results are listed in Table 2 below and correspond to the average value calculated over three trials. Measurement at 20 minutes (min): After 20 minutes at rest, it is evaluated visually on the tempered product that it remained homogeneous, that is to say that there was no sedimentation of its ingredients at the bottom of the bowl. The product is then mixed manually with 3 turns of blade before being poured into a ring of the same size as previously described. Measurement of the spread diameter of the product is made as before, 5 minutes after lifting the ring. The results are listed in Table 2 below and correspond to the average value calculated over three trials.
    [0045] I.1.3-Measurement of the setting time (Vicat) The measurements of the starting time of setting and the end of setting of the soil coating are carried out starting from the same tempered product, prepared as described in 1.1 above. .1. The measurements of the start time of setting and the end of setting of the floor coating are carried out with a Vicat apparatus as described in the standard EN 13454-2.
    [0046] The tempered product is poured into a standard mold which is filled to make the measurements. The mold used is a frustoconical rubber mold having upper and lower inner diameters of 7cm and 8cm, respectively, and provided at its base with a removable glass plate wider than the rubber mold and having a thickness of less than 2.5 mm.
    [0047] The setting time is determined by observing the penetration of a 1.13 mm diameter needle into the tempered product, under a load of 300 grams, corresponding to the self weight of the Vicat apparatus. The start of setting corresponds to the time at which the needle stops sinking under the effect of the applied load and stops at a distance of 4 mm ± 1 mm from the bottom of the mold, from the beginning of mixing of pulverulent composition with water. To determine the end of setting, the mold is returned after determining the start of setting of the product and the glass plate is removed in order to carry out the measurements of insertion of the needle on the face of the product which has been in contact with the glass plate. Measurements of depression of the needle are made at different places on the surface of the product. The end of setting corresponds to the time after which the needle penetrates for the first time only to 0.5 mm in the product, starting from the beginning of kneading of the pulverulent composition with water. The results, expressed in minutes, are listed in Table 2 below and correspond to the average value calculated over three tests. 1.2-Tests on hardened product I.2.1-Preparation of test pieces The tempered product prepared previously in 1.1.1 from 2 kg of powder composition and water at a mixing rate of 16% is used to produce the test pieces which will be used for the following tests on the hardened floor rendering.
    [0048] The tempered product is poured into each of the three rectangular compartments of a mold allowing the simultaneous preparation of three parallelepiped-shaped test pieces of 16cm height and having as a basis a square of 4 cm side. Before demolding, the test pieces are stored covered with a glass plate at 23 ° C. and 50% relative humidity. 24 hours after the beginning of mixing with water, the test pieces are demolded. Once demolded, and between two measurements, the test pieces are stored at 23 ° C and 50% relative humidity. I.2.2-Measurement of the flexural strength (Rf) The flexural strength tests were carried out at 24 hours, 7 days and 28 days after casting the specimens, using a resistance test machine. bending and compression as described in standard NF EN 196-1. The device for the bending strength test comprises two support rollers placed in parallel on the same horizontal plane at a distance of 100 mm from each other, and a third parallel roll (called a loading roller ), overcoming the other two and placed equidistant from the other two rollers. The three rollers are made of steel, each having a diameter of 10 mm and a length of 48 mm. The test specimen is placed in the apparatus, so as to be clamped by the three rollers, the axes of the three rollers being perpendicular to the length of the specimen and the axis of the loading roller coinciding with the medium of the length of the test piece. A load is applied to the upper side face of the prism by causing the loading roll to fall vertically and then the roll returns to its initial position. . As long as the specimen does not break, this step is repeated by applying a higher load. The applied load is gradually increased at a loading speed of 50 Newton per second (N / s) (50 N / s ± 10 N / s) until the test piece breaks. Flexural strength is the force required to break the specimen and is expressed in megapascal (MPa). The results are listed in Table 2 below and correspond to the average value calculated over three trials.
    [0049] I.2.3-Measurement of the compressive strength (Rc) The compressive strength tests were carried out on the two halves of each of the broken specimens according to the protocol of the flexural strength tests described above. A total of six tests are therefore carried out for each age of the building material (24 hours, 7 days, 28 days).
    [0050] One half of the test specimen is sandwiched between the two parallel moving plates of the measuring apparatus, so that the lateral faces of the half-test piece are centered and in contact with the movable plates. Each plate is 40 mm long and 40 mm wide.
    [0051] A load is applied to the half-specimen by exerting a compressive force with the aid of the two movable plates and the compressive strength of the half-specimen is simultaneously measured. The applied load is progressively increased at a loading speed of 2400 N / s ± 200 N / s and the value of the compressive strength (expressed in MPa) is recorded continuously, until rupture, ie that is to say until the resistance opposed by the half-test is zero. The results are listed in Table 2 below and correspond to the average value calculated over six trials for each age (24h, 7d, 28j). I.2.4-Removal measurement The withdrawal measurements were performed on a series of 3 test pieces prepared as previously described in 1.2.1. The withdrawal measurements were carried out using a deformeter as described in standard NF P15-433 and a rod 16 cm long ingvar serving as reference. As soon as the prisms are demolded, ie 24 hours after the beginning of kneading of the powdery composition with water, the initial length of each of the 20 test pieces is measured. After the measurement, the test pieces are restocked under the same conditions as previously described in 1.2.1. The final length of the test pieces is then measured at 28 days, that is to say 28 days after the start of kneading of the pulverulent composition with water. Then, for each specimen, the shrinkage is calculated as the difference between the final length and the initial length of the specimen, all divided by the length of the reference (16 cm). The results, expressed in micrometre per meter (p.m / m), are listed in the following Table 2 and correspond to the average retreat value calculated on the three specimens.
    [0052] Results of the test series Nol on the compositions of Examples 1, 2 and 5 Properties of the Ex! Ex2 Ex5 (Invention) (Comparative!) (Comparative 4) Spreading diameter after 5 min of rest (mm) 150 150 150 Sedimentation after 5 min of rest (mm) no no no Spreading diameter after 20 min of rest ( mm) 150 150 135 Sedimentation after 20 min of rest (mm) no no no Beginning of catch Vicat (min) 230 300 230 End of setting Vicat (min) 270 330 270 Rc 24h (Mpa) 8 6 2 Rf 24h (Mpa) 2 2 0.5 Rc 7j (Mpa) 35 Rf 7j (Mpa) 5 5 2 Rc 28j (Mpa) 40 35 Rf 28j (Mpa) 6 6 5 Retraction at 28 days (um / m) <1500 <2000 <2000 Table 2 These test results show that: the floor coating according to the invention (ex.1) does not sediment and has a good property of self-spreading over time, the floor coating according to the invention. The invention (ex.1) has very good mechanical strengths in short-term compression while having a desired fitness for use in its implementation. The comparative soil coatings (ex.2 and 5) do not allow for equivalent setting times, to obtain satisfactory compressive strength in the short term, - the kinetics of the mechanical strengths of the floor coating according to the invention. invention is also better compared to the reference floor coating, - the floor coating according to the invention has flexural strength values higher than the reference floor coating. The flexibility of the hardened floor coating according to the invention allows it to gain in particular durability when the soil is subjected to deformation or vibration, - the floor coating according to the invention has a lower shrinkage and therefore dimensional stability improved compared to comparative soil coatings. In particular, no cracking is observed on the cured product of the invention.
    [0053] II-Series of Tests No. 2 on the Compositions of Examples 1 to 4 Measurement of Setting Time and Total Heat of Hydration (by Isothermal Calorimetry) Measurements of setting time and total heat of hydration are carried out on a sample of 7.5 grams of tempered product, prepared as previously described in 1.1.1.
    [0054] The sample is introduced into a thermally sealed ampoule. The ampoule is introduced into a TAM Air insulated calorimeter, regulated at 23 ° C, with a thermally sealed reference ampoule containing water. The amount of water contained in the reference bulb is calculated in a manner well known to those skilled in the art so that the heat capacity of the measuring bulb containing the tempered product is equal to the heat capacity of the heat sink. reference bulb. Isothermal calorimetry is used to measure heat differences between the sample and the reference. Since the hydration reaction of the hydraulic binder responsible for the setting and hardening of the binder is exothermic, the heat differences caused by this reaction as a function of time are followed, by isothermal calorimetry, in order to evaluate the reactivity of the binder on contact. some water. The heat flux curve generated by the tempered product (in Watt per gram of product) is plotted and the heat curve evolved by the tempered product (in Joule per gram of product), as a function of the time elapsed from the preparation tempered product (up to about 72 hours) for each soil test tested.
    [0055] The heat flux curve generated by the tempered product as a function of time represented in FIG. 1 illustrates the hydration kinetics of the various soil coatings tested (FIG. 1). The heat curve generated by the tempered product as a function of time, represented by FIG. 2, makes it possible to determine the value of the start of setting and the end of setting of the product by searching for the points of inflection. However, in practice it is difficult. Also, the first derivative d (q) / d (t) of the heat flux curve generated by the tempered product as a function of time is plotted in FIG. 3 for each of the soil coatings tested, in order to identify more precise the values of start of setting and end of setting of each of these products.
    [0056] The beginning of setting (DP) and end of setting (FP) are identified with the aid of FIG. 3, as well as the total heat released by the product 72 hours after its hydration. The tap start value is the elapsed time from the preparation of the tempered product, for which the maximum of the derivative d (q) / d (t) is reached. The end of set value corresponds to the elapsed time from the preparation of the tempered product, for which the value of the derivative d (q) / d (t) is zero of the derivative. The beginning and end of setting of the binder make it possible to characterize the setting speed of the binder and therefore the reactivity of the latter in contact with water. In particular, the beginning of binder setting corresponds to the moment, from the beginning of the mixing with the water, where the product suddenly thickens and begins to heat up. Whereas, the end of setting of the binder which coincides with the beginning of the hardening of the binder, corresponds to the moment, from the beginning of the mixing with the water, where the product becomes rigid and ceases to be deformable. The release of heat begins to slow down from that moment. The total heat released by the product during its hydration is correlated with the mechanical properties developed by the product during its hydration.
    [0057] The total heat released by the product measured after 72 hours of hydration thus makes it possible to characterize the degree of rigidity achieved by the product. In fact, the greater the kinetics of the hydration reaction and the total heat of hydration of the product, the more the binder is activated. The results are summarized in the following Table 3 and illustrated by the calorimetry curves shown in FIGS. 1 to 3. Results of Test Series No. 2 on the Compositions of Examples 1 to 4 Ex1 Ex2 Ex3 Ex4 (Invention) (Comparative 1) (Comparative 2) (Comparative 3) DP (hours) 3.2 6.5 4.7 5.1 FP (hours) 5.3 8.9 6.9 7.1 Total heat 45.4 37.3 37, 6 45.3 hydration after 72h (J / g) Table 3 The floor coating according to the invention (ex.1) comprising a 4-component activation system, has a lower setting time and total heat After 72 hours of hydration, the values found for comparative soil coatings (eg 2 to 4) are comparable in content to an activation system with only 2 or 3 components.
    [0058] These test results therefore show that the soil coating according to the invention (ex.1) has an improved setting speed and makes it possible to achieve (beyond 72h of hydration) an improved mechanical strength, compared to comparative soil coatings (eg 2-4) with different activation systems.
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. A hydraulic binder composition comprising: a) at least 50% by weight based on the weight of the hydraulic binder composition, a ground granulated blast furnace slag, b) at least calcium sulfate, c) at least one product selected from a source of Portland clinker and lime, d) at least one aluminum derivative selected from an alumina having a BET surface area ranging from 100 to 400 m 2 / g, a monocalcium aluminate and a calcium sulfoaluminate, and ) at least one alkali metal or alkaline earth metal salt selected from chloride salts, bromide salts, silicate salts, nitrate salts, carboxylic acid salts such as C1 monocarboxylic acid salts; -C4, -the total calcium sulphate content expressed as an equivalent content of SO 3 being at least 5% by weight relative to the weight of the hydraulic binder composition, - the sum of the contents of the products mentioned in points c) and e) being less than 10% by weight by rap weight bearing of the hydraulic binder composition.
    [0002]
    Hydraulic binder composition according to claim 1, characterized in that the ground granulated blast furnace slag comprises amounts of calcium oxide, magnesia, alumina and silica satisfying at least one of the three relationships. following: -ri - (Ca0 + Mg0)> 103 (A1203 + SiO2) '(Ca0 + Mg0 +0.3 * Al2O3) -r2 (F11) -> 1.20 (SiO2 + 0.7 * Al2O3) -r3 ( F3) - (Ca0 + Mg0 + Al2O3)> 1.6, and the content of aluminum oxide (Al2O3) being less than (SiO2) 13% by weight of the weight of granulated blast furnace slag, r1, r2 and r3 corresponding to the weight ratios relative to the quantities of calcium oxide, magnesia, alumina and silica, present in ground granulated blast furnace slag.
    [0003]
    3. A hydraulic binder composition according to claim 1 or 2, characterized in that the Blaine specific surface area of ground granulated blast furnace slag is from 7000 to 8000 cm2 / g.
    [0004]
    4. A hydraulic binder composition according to any one of claims 1 to 3, characterized in that the maximum particle size of ground granulated blast furnace slag is less than 45pm.
    [0005]
    5. A hydraulic binder composition according to any one of claims 1 to 4, characterized in that it comprises a total content of slag (s) granulated (s) blast furnace (s) ranging from 60 to 70% in weight relative to the weight of the hydraulic binder composition.
    [0006]
    6. A hydraulic binder composition according to any one of claims 1 to 5, characterized in that the calcium sulfate comprises at least 90% by weight of anhydrous calcium sulfate relative to the weight of calcium sulfate.
    [0007]
    7. A hydraulic binder composition according to any one of claims 1 to 6, characterized in that it comprises a total content of product (s) selected (s) from a source of Portland clinker, lime, and their mixture , ranging from 0.2 to 4% by weight relative to the total weight of the hydraulic binder composition.
    [0008]
    8. A hydraulic binder composition according to any one of claims 1 to 7, characterized in that it comprises a total content of aluminum derivative (s) as defined in claim 1 ranging from 0.2 to 2.1% by weight relative to the total weight of the hydraulic binder composition.
    [0009]
    9. A hydraulic binder composition according to any one of claims 1 to 8, characterized in that it comprises a total content of salt (s) of alkali or alkaline earth metaltel (s) as defined in the claim 1 less than 5% by weight relative to the total weight of the hydraulic binder composition, the said salt (s) being chosen from calcium chloride (CaCl 2), calcium formate and / or calcium acetate.
    [0010]
    10. Composition of ready-to-mix construction material comprising: a hydraulic binder as defined in claim 1, and aggregates of inert materials capable of being agglomerated in aqueous phase by means of said binder to form an aggregate.
    [0011]
    11. ready-to-mix composition according to claim 10, characterized in that it comprises at least one polymer in powder form dispersible in water or in the form of aqueous polymer dispersion.
    [0012]
    12. A method of implementing a ready-to-mix composition as defined in claim 10 or 11, comprising a step of mixing said composition with water, for the preparation of a material of construction.
    [0013]
    13. The method of claim 12, for the preparation of a mortar glue, joint mortar, or mortar or smoothing compound.
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    同族专利:
    公开号 | 公开日
    BR102015027886A2|2016-10-04|
    US20160122246A1|2016-05-05|
    EP3015438B1|2020-01-01|
    FR3027897B1|2019-06-07|
    EP3015438A1|2016-05-04|
    US9656918B2|2017-05-23|
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    法律状态:
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    2016-05-06| PLSC| Search report ready|Effective date: 20160506 |
    2016-09-19| PLFP| Fee payment|Year of fee payment: 3 |
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    2020-02-28| CA| Change of address|Effective date: 20200122 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1460440|2014-10-30|
    FR1460440A|FR3027897B1|2014-10-30|2014-10-30|WATER-BASED HYDRAULIC BINDER GRANULATED HIGH GROCERY MILL WITH IMPROVED TAKING AND CURING|FR1460440A| FR3027897B1|2014-10-30|2014-10-30|WATER-BASED HYDRAULIC BINDER GRANULATED HIGH GROCERY MILL WITH IMPROVED TAKING AND CURING|
    EP15191939.6A| EP3015438B1|2014-10-30|2015-10-28|Hydraulic binder made of cast blast-furnace granulated slag with improved curing and hardening|
    BR102015027886A| BR102015027886A2|2014-10-30|2015-10-30|ground granular blast furnace slag-based hydraulic binder having improved hardening and improved cure|
    US14/928,480| US9656918B2|2014-10-30|2015-10-30|Hydraulic binder based on ground granulated blast furnace slag having improved setting improved curing|
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