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    • 专利摘要:
    The present invention relates to a method of manufacturing a low density mineral foam. The invention also relates to the use of this mineral foam as an insulating material.
    公开号:FR3030504A1
    申请号:FR1463226
    申请日:2014-12-23
    公开日:2016-06-24
    发明作者:Freddy Bernard；Pierre Henri Jezequel；Sandrine Reboussin
    申请人:Lafarge SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a process for the continuous manufacture of a low-density mineral foam based on cements, and to the use of this foam as a process for the production of low-density mineral foam. insulating material. In general, the mineral foam is very advantageous for many applications because of its thermal insulation properties. The mineral foam refers to a material in the form of a foam. This material is lighter than traditional concrete because of the pores or voids it includes, it is also called cement foam. These pores or voids are due to the presence of a gas in the mineral foam and may be in the form of bubbles. Indeed with 1 m3 of raw material, it is possible to manufacture about 5 m3 of finished product, ie a material composed of 20% of material and 80% of gas (valid for a density element of 400 kg / m3). Thus, the mineral foam comprises a network of bubbles more or less distant from each other, that is to say pockets of gas contained in a solid envelope of mineral binder. The manufacture of mineral foams is delicate because it results from the solidification of a liquid foam into a solid foam. This solid foam is firstly a liquid foam that is to say a network of air bubbles or gas surrounded by a hydraulic binder slurry that evolves over time into a solid mineral foam. Also the manufacture of mineral foams involves the passage through a manufacturing step of a liquid foam which must be stable. The stability of the liquid foam is therefore important, and the manufacturing process should be able to control the phenomena of destabilization of the foams during setting, such as, for example, coalescence, Ostwald ripening or drainage. These difficulties are exacerbated when the manufacturing process is a continuous process, that is to say that the finished product is developed in an uninterrupted manner. Continuous manufacturing processes are well suited to an industrial environment and are recommended in the factory or on site.
    [0002] The difficulty in producing inorganic foams continuously in an industrial context is therefore to manufacture a stable foam that overcomes these destabilizing phenomena. However, the known processes for producing foams do not make it possible to obtain sufficiently stable foams. Moreover, when this mineral foam is used as insulation material, it is advantageous that it can be projected onto a support, which can also be horizontal, inclined or vertical. It then becomes interesting that the foam clings to this support and that it remains attached to this support until it solidifies. Indeed, when the foam is in the liquid state, it can flow under the effect of gravity and it is important that once on its support, this foam does not run or fall under the effect of gravity. In order to meet the requirements of users, it has become necessary to find a method for producing a continuous mineral foam in an industrial context or on site, with a facilitated implementation of this foam. Also the problem to be solved by the invention is to find a continuous process of producing a mineral foam, it may remain in place when applied to a support regardless of the shape and inclination of the support. The invention also relates to a mineral foam that can be obtained according to the method of the invention.
    [0003] According to another object of the invention, the mineral foam according to the invention can be used as a construction material. For example, the mineral foam may be used as projected or non-projected insulation, or as a structural filler. The present invention seeks to provide new mineral foams which have one or more of the following characteristics: the mineral foam according to the invention has excellent stability properties. In particular, it is possible to obtain a foam that can be projected onto and hung on a support, regardless of the position of this support and independently of the forces of gravity; the mineral foam according to the invention has excellent thermal properties, and in particular a very low thermal conductivity. Decreasing the thermal conductivity of building materials is highly desirable as it provides heating energy savings in apartment buildings and workplaces. In addition, this reduction makes it possible to reduce the thermal bridges, particularly in multi-storey building constructions with thermal insulation from the inside, in particular the thermal bridges of the intermediate floors. The present invention relates to a process for the continuous production of a mineral foam whose density in the dry state (d) is from 40 to 600 kg / m 3, comprising the following steps: (i) mixing PA14021 FR n cement; n a water reducing agent; n 0.5 to 10%,% by weight, based on the total mass of cement, of ultrafine particles having a liquid-solid contact angle of from 30 ° to 140 ° and having a D50 of 600 nm; n water, with a water / cement mass ratio of 0.3 to 2.5; (ii) adding to the mixture from 0.5 to 10% of a blowing agent,% by weight relative to the mass of cement; (iii) placing the mixture obtained in step (ii) on a support; (iv) allow the mixture to expand on the support. The cement suitable for producing the mineral foam according to the method of the invention is preferably the cement described in accordance with European Standard NF EN 197-1 of April 2012 or their mixtures. The preferred cement that is suitable according to the invention is Portland cement CEM I, alone or mixed with other cements such as those described in accordance with the European Standard NF EN 197-1 of April 2012. Preferably, the mixture of step (i) of the process according to the invention comprises from 60 to 95% of cement, preferably from 65 to 90%, percentage by weight relative to the total mass of the mixture of step (i) without water.
    [0004] A calcium aluminate cement could also be suitable for producing the mineral foam according to the invention. It could be a cement comprising a mineralogical phase C4A3 $, CA, C12A7, C3A or Ci 1A7CaF2 or their mixtures, such as for example Ciments Fondu®, sulphoaluminous cements, calcium aluminate cements conforming to to the European standard NF EN 14647 of December 2006, the cement obtained from the clinker described in the patent application VVO 2006/018569 or their mixtures. The calcium aluminate cement suitable for producing the mineral foam according to the invention could be either in crystallized form or in amorphous form. The preferred calcium aluminate cement according to the invention is Ciment Fondu®.
    [0005] Preferably, the cement of the mixture of step (i) of the process according to the invention has a Blaine specific surface greater than or equal to 5000 cm 2 / g, more preferably greater than or equal to 6500 cm 2 / g. Preferably, the cement of the mixture of step (i) of the process according to the invention is a cement whose Blaine specific surface is between 5000 and 9000 cm 2 / g. PA14021 EN It may be envisaged to use several cements in the mixture of step (i) of the method according to the invention of different Blaine specific surface area. For example, it is possible to use a Blaine specific surface cement greater than or equal to 5000 cm 2 / g, mixed with a Blaine specific surface cement less than or equal to 5000 cm 2 / g, for example a Portland cement. The cement that can be used according to the present invention can be milled and / or separated (by a dynamic separator) to obtain a cement having a Blaine specific surface greater than or equal to 5000 cm 2 / g. This cement can be called ultrafine. The cement may for example be ground according to two methods.
    [0006] According to a first method, the cement or clinker can be ground up to a Blaine specific surface area of 5000 to 9000 cm 2 / g. A high efficiency separator, second generation or third generation, or a very high efficiency separator, can be used in this first step to separate the cement having the desired fineness and remove the cement not having the desired fineness. This cement is then returned to the mill. According to a second method, a cement can pass into a very high efficiency separator, called THF (very high fineness), in order to separate the cement particles having a Blaine surface area greater than or equal to the target fineness (the target fineness being greater at 5000 cm 2 / g) and the cement particles having a Blaine specific surface area less than the target fineness. The cement particles having a Blaine specific surface greater than or equal to the target fineness can be used as they are. The cement particles having a Blaine specific surface area less than the target fineness can be separated or ground separately until the desired Blaine surface area is obtained. The grinders that can be used in both methods are for example a ball mill, a vertical mill, a roller press, a horizontal mill (for example of the Horomill © type) or a vertical agitated mill (for example Tower Mill type). ). The mixture of step (i) of the process according to the invention could also contain calcium sulphate, which may be gypsum, anhydrous calcium sulphate or calcium sulphate hemihydrate. The mixture of step (i) of the process according to the invention comprises a water-reducing agent, a plasticizer or a superplasticizer. A water reducing agent can reduce by about 10 to 15% by mass the amount of mixing water for a given workability time. Examples of water-reducing agents that may be mentioned are lignosulphonates, hydroxycarboxylic acids, carbohydrates and other specific organic compounds, for example glycerol, polyvinyl alcohol or alumino-methyl. sodium siliconate, sulfanilic acid and casein (see Concrete Admixtures Handbook, Properties Science and Technology, VS Ramachandran, Noyes Publications, 1984) Superplasticizers belong to the new generation of water-reducing agents and can reduce 30% by mass the amount of mixing water for a given workability time. As an example of a superplasticizer, there may be mentioned superplasticizers of the POP type without antifoam agent. The term "POP" or "polycarboxylate polyoxide" according to the present invention is understood to mean, inter alia, a copolymer of acrylic acids or methacrylic acids and of their poly (ethylene oxide) (POE) esters. Preferably, the mixture of step (i) of the process according to the invention comprises from 0.01 to 1%, more preferably from 0.05 to 0.5% of a water-reducing agent, from plasticizer or superplasticizer, percentage expressed by weight relative to the mass of the mixture of step (i). When the water reducing agent, the plasticizer or the superplasticizer is used in solution, the amount is expressed as active ingredient in the solution. According to one variant of the invention, the mixture of step (i) or of step (ii) of the process according to the invention does not comprise an antifoaming agent, or any agent having the property of destabilizing a air emulsion in a liquid. Some commercial superplasticizers may contain anti-foaming agents and therefore these superplasticizers may not be suitable according to the invention. The mixture of step (i) or step (ii) of the process according to the invention could comprise a retarding agent. The retarding agent corresponds to the definition of the retarding agent mentioned in European Standard NF EN 934-2 of September 2002. According to a variant of the invention, the mixture of step (i) or of step (ii) ) of the process according to the invention does not comprise foaming agent. Preferably, the mixture of step (i) or step (ii) of the process according to the invention further comprises a transition metal salt, for example a manganese salt or an iron salt. It can be envisaged that the transition metal salt could be a catalyst precursor facilitating the decomposition of the porogen into oxygen. By way of example of a catalyst precursor, mention may be made of manganese salts and oxides, such as, for example, permanganates and manganates, salts and oxides of iron, cobalt, copper, molybdenum and tungsten. of chromium, PA14021 silver and enzymes preferably catalases. In some cases, the transition metal salt may be provided by the cement itself, especially in the case of cement containing a large amount of iron, whether in oxide form or not. The catalyst precursor may in particular be chosen from water-soluble manganese (II) salts, such as manganese acetate (II), manganese sulphate (II), manganese chloride (II) and manganese nitride (II). These salts can decompose, in a basic medium, into insoluble compounds comprising manganese with a +4 oxidation state, such as MnO 2, which is a known catalyst for the decomposition of peroxides.
    [0007] The mixture of step (i) of the process according to the invention comprises from 0.5 to 10%,% by weight relative to the total mass of cement, of ultrafine particles having a liquid-solid contact angle of 30 ° at 140 °, and whose D50 is 10 to 600 nm. Preferably, the mixture of step (i) of the process according to the invention comprises from 1 to 9%,% by weight relative to the total mass of cement, of ultrafine particles having a liquid-solid contact angle comprised of 30 ° to 140 °, and whose D50 is 10 to 600 nm. Preferably, the mixture of step (i) of the process according to the invention comprises from 2 to 8%,% by weight relative to the total mass of cement, of ultrafine particles having a liquid-solid contact angle of 30 ° to 140 °, and whose D50 is 10 to 600 nm. Preferably, the ultrafine particles of the mixture of step (i) of the process according to the invention are partially hydrophobed, for example by a stearic acid. It is also possible to talk about functionalization.
    [0008] The ultrafine particles of the mixture of step (i) of the process according to the invention have a liquid-solid contact angle of between 30 ° and 140 °, preferably between 40 ° and 130 ° and even more preferentially with 70 °. at 130 °. This contact angle is also called the wetting angle. By the term "contact angle" or "wetting angle" is meant the angle formed between a liquid / vapor interface and a solid surface. This is the angle formed between the interface of a liquid and the solid surface on which the liquid is placed. It is generally considered that a wall is hydrophilic when the static contact angle of a drop of water disposed on the wall is less than about 30 degrees and that the wall is hydrophobic at varying levels of hydrophobicity when the static contact angle of a drop of distilled water disposed on the wall is greater than about 30 degrees and less than about 140 °. The wall is said to be superhydrophobic when the static contact angle of a drop of distilled water disposed on the wall is greater than about 140 degrees. To make a foam from the process according to the invention, it would be desirable for the ultrafine particles of the mixture of step (i) not to be superhydrophobic, that is to say not having a strictly greater contact angle. at 140 °. Preferably, the ultrafine particles of the mixture of step (i) of the process according to the invention are not hydrophilic. The ultrafine particles that are suitable according to the process of the invention have a D50 of from 600 to 500 nm, preferably from 20 to 500 nm, more preferably from 30 to 200 nm. The D50, also denoted Dv50, corresponds to the 50th percentile of the particle size distribution, ie 50% of the volume consists of particles smaller than D50 and 50% larger. to the D50.
    [0009] It should be noted that the ultrafine particles generally comprise elementary particles having a diameter of 10 to 50 nm. These elementary particles can agglomerate to form agglomerated particles having a diameter of 40 nm to 150 nm. These agglomerated particles can agglomerate to form aggregates having a diameter of 100 nm to 600 nm.
    [0010] The ultrafine particles that are suitable according to the method of the invention can come from one or more materials chosen from limestone powders, precipitated calcium carbonates, natural and artificial pozzolans, pumice stones, crushed fly ash, hydrated silica. , in particular the products described in document FR 2708592, and mixtures thereof.
    [0011] According to one variant, the mixture of step (i) of the process according to the invention additionally comprises a mineral addition such as pozzolan, a slag, calcium carbonate, a fly ash, a sand or their mixtures, and whose particles have a D50 of 0.1 to 4 mm. Preferably, the mixture of step (i) of the process according to the invention may comprise from 15 to 50% of mineral additions, preferably from 15 to 40%, still more than from 20 to 35%, the percentages being expressed in mass relative to the mass of the mixture of step (i). Preferably the D50 of the mineral additive particles suitable for the mixing of step (i) of the process according to the invention is from 0.2 to 500 μm, for example from 0.25 to 250 μm. The D50 of the mineral particles is preferably from 0.1 to 150 μm, more preferably from 0.1 to 100 μm. PA14021 EN The mineral additives suitable for the mixing of step (i) of the process according to the invention are chosen from calcium carbonate, silica, crushed glass, solid or hollow glass beads, glass granules, expanded glass powders, silica aerogels, silica fumes, slags, milled sedimentary siliceous sands, fly ash or pozzolanic materials or mixtures thereof. The mineral additions suitable for the mixing of step (i) of the process according to the invention may be pozzolanic materials (for example as defined in European Standard NF EN 197-1 of February 2001, paragraph 5.2.3), fumes silica (for example as defined in the European standard NF EN 197-1 of February 2001 paragraph 5.2.7), slags (for example as defined in the European standard NF EN 197-1 of February 2001 paragraph 5.2.2 ), materials containing calcium carbonate, for example limestone (for example as defined in European Standard NF EN 197-1 paragraph 5.2.6) of the siliceous additions (for example as defined in the "Concrete" NF standard). P 18-509 "fly ash (for example those as described in the European standard NF EN 197-1 of February 2001 paragraph 5.2.4) or mixtures thereof.A fly ash is generally a powder particle included in the fumes coal-fired power stations. It is usually recovered by electrostatic or mechanical precipitation. The chemical composition of a fly ash depends mainly on the chemical composition of the burned coal and the process used in the thermal power plant from which it originated. It is the same for its mineralogical composition. The fly ash used according to the invention may be of siliceous or calcic nature. Slags are generally obtained by rapidly cooling the molten slag from the smelting of iron ore in a blast furnace. The slags that are suitable for the mixing of step (i) of the process according to the invention may be chosen from granulated blast furnace slags according to the European standard NF EN 197-1 of February 2001, paragraph 5.2.2. The silica fumes suitable for the mixture of step (i) of the process according to the invention may be a material obtained by reduction of high-purity quartz by charcoal in electric arc furnaces used for the production of silicon and silica. ferrosilicon alloys. The silica fumes are generally formed of spherical particles comprising at least 85% by mass of amorphous silica. Preferably, the silica fumes suitable for the mixture of step (i) of the process according to the invention may be chosen from silica fumes according to European Standard NF EN 197-1 of February 2001, section 5.2.7. PA14021 EN The pozzolanic materials suitable for the mixing of step (i) of the process according to the invention may be natural siliceous or silicoaluminous substances, or a combination thereof. Pozzolanic materials include natural pozzolans, which are generally materials of volcanic origin or sedimentary rocks, and calcined natural pozzolans, which are materials of volcanic origin, clays, shales or rocks. sedimentary, thermally activated. Preferably, the pozzolanic materials suitable for mixing step (i) of the process according to the invention may be chosen from pozzolanic materials according to European Standard NF EN 197-1 of February 2001, paragraph 5.2.3. Preferably, the mineral additions suitable for mixing of step (i) of the process according to the invention may be limestone powders and / or slags and / or fly ash and / or silica fumes. Preferably, the mineral additions suitable for the mixing of step (i) of the process according to the invention are calcareous powders and / or slags. Other mineral additions suitable for mixing in step (i) of the process according to the invention are limestone, siliceous or silico-calcareous powders, or mixtures thereof. The mineral additions suitable for the mixture of step (i) of the process according to the invention may come partly or completely from the cement when it is a composite cement. The mixture of step (i) of the process according to the invention comprises water. The water / cement mass ratio is from 0.45 to 1.3, preferably from 0.5 to 1.2, more preferably from 0.6 to 0.8. This total water / cement ratio may vary for example because of the water demand of ultrafine particles or mineral additions when they are used. This total water / cement ratio is defined as the ratio by mass of the quantity of water (E) to the mass of all the cements (C). According to one variant, the mixing of step (i) of the process according to the invention may comprise hydraulic lime.
    [0012] Preferably, the mixture of step (i) of the process according to the invention does not comprise light aggregates as described in accordance with European Standard NF EN 206-1 of April 2004, for example perlite. According to another variant of the invention, the mixture of step (i) of the process according to the invention does not comprise light fillers, for example polystyrene beads. Step (ii) of the process according to the invention comprises the addition to the mixture of step (i) of 0.5 to 10% of a blowing agent,% by weight relative to the mass of cement. PA14021 EN Preferably, step (ii) of the process according to the invention comprises the addition of 2 to 8% of a pore-forming agent. The blowing agent added in step (ii) of the process according to the invention may be a solution of hydrogen peroxide, a solution of peroxomonosulphuric acid, a solution of persoxodisulfuric acid, a solution of alkaline peroxides, a solution of alkaline earth peroxides or an organic peroxide solution such as peroxoacetic acid or peroxobenzoic acid, or a suspension of aluminum particles or mixtures thereof. Preferably, the blowing agent is hydrogen peroxide. Preferably, it is hydrogen peroxide whose concentration is between 8% and 35%. At the end of step (ii) of the process according to the invention a mixture is obtained. This mixture can be produced according to the method of the invention using a device comprising pipes, possibly of different sizes, all forming a pipe. This pipe may or may not include a mechanical mixing aid such as a static mixer. The reaction between the blowing agent and the transition metal salt (catalyst precursors) and / or the cement starts immediately, and a fraction of the total oxygen is immediately released, so that the pipe contains bubbles. At the exit of the pipe, the mixture which contains a fraction of bubbles is intended to be immediately cast in a mold or projected on a support. During this operation of output of the mixture of the pipe, this mixture is not fractionated. Preferably, the mixture obtained in step (ii) of the process according to the invention is not fractionated. By the expression "is not fractionated", it is generally understood that the mixture leaves the pipe in the form of a jet and keeps its integrity, and in particular it is not sprayed in the mold or on the support, even if a few occasional drops can be formed during contact with the support. Step (iii) of the process according to the invention comprises placing the mixture obtained in step (ii) on a support. This step of setting up can be done without using spray nozzles or an equivalent. In addition, this setting up can be done without using elements at the output of the device. In fact the spraying will generally result in the fractionation of the mixture or the formation of drops. The setting up can be done by allowing the mixture obtained in step (ii) to flow naturally on the support. Thus the mixture by flowing naturally is not propelled or accelerate which could destabilize the mixture and form drops. PA14021 EN Preferably, in step (iii) the mixture is put in place without using a spray nozzle. Preferably, step (iii) of the process according to the invention is carried out without spraying.
    [0013] According to a variant of the invention, step (iii) can be repeated in order to obtain successive or superposed layers. Preferably, the most recently deposited layer is deposited on a layer having already acquired a mechanical strength by hydration of the cement. The support used in step (iii) of the process according to the invention can be vertical, horizontal, inclined or in any position. It may also be a receptacle, a mold, a hollow or solid building block, a hollow or solid wall, a ceiling, a floor (screed or insulation) . The support used in step (iii) of the process according to the invention may be treated prior to the introduction of the mixture obtained in step (ii).
    [0014] According to one variant, the process according to the invention furthermore uses an accelerator for the hydration of the cement, which is present either in the mixture of step (i) or (ii), or on the surface of the support of the step (iii). Preferably, the mixture of step (i) of the process according to the invention further comprises an accelerator of the hydration of the cement, for example calcium chloride. When a cement hydration accelerator is present in the mixture of step (i) or (ii), it is preferably a calcium salt, such as for example calcium chloride. The accelerator of cement hydration can be integrated continuously before step (iii) of the process according to the invention. When an accelerator of cement hydration is present on the surface of the support of step (iii), it is preferably aluminum sulphate. The cement hydration accelerator may be introduced in step (i) before or after the addition of water, or sprayed onto the support of step (iii). Water may be applied to the support used in step (iii) of the process according to the invention before step (iii). Other additives can also be used in the process according to the invention such as, for example, colored pigments, hydrophobic agents, depolluting agents (for example zeolites or titanium dioxide). In step (iv) of the process according to the invention, the mixture expands. This expansion started as soon as the pore-forming agent reacts chemically, i.e., in step (ii), and ends in step (iv). The aerated mineral foam thus obtained can be smoothed and have a thickness greater than 1 cm. Then the setting is carried out until obtaining a solid mineral foam. This expansion corresponds to the evolution of gas following the chemical reaction of the blowing agent, optionally in the presence of a catalyst. When the blowing agent is based on peroxide, the decomposition reaction of the blowing agent carried out in the presence of a catalyst is an exothermic reaction generating oxygen and water. It is known that the decomposition of peroxides is accelerated in the presence of a metal. The mixture of step (i) can be prepared using kneaders conventionally used to make cement grouts. It can be a grouting machine, a concrete mixer, a mixer described in the European standard NF EN 196-1 of April 2006 - Section 4.4, or a mixer-beater with planetary motion. The mixture of step (i) can be prepared by introducing into the kneader the various materials in the form of powders. The powders are kneaded to obtain a homogeneous mixture. Then the water is introduced into the mixer. Then the mineral particles, the adjuvants such as, for example, the water-reducing agent, the plasticizer, the superplasticizer, the accelerator, the thixotropic agent, the viscosifying agent, the water-retaining agent or the retarder are introduced when present in the formulation of the mineral foam. The paste obtained is kneaded to obtain a mixture of cement slurry. Preferably, the mixtures of step (i) or (ii) are stirred with the aid of the light deflocculator throughout the process of manufacturing the mineral foam according to the invention.
    [0015] The method according to the invention can be implemented on a building site by installing a foaming system directly on the site, or implemented in a prefabrication plant. The subject of the invention is also a mineral foam capable of being obtained according to the method of the invention. Preferably, the mineral foam produced according to the process of the invention has a density in the dry state of 50 to 600 kg / m 3, more preferably 60 to 500 kg / m 3, even more preferably 70 to 450 kg / m 3. . It should be noted that the density of fresh mineral foam (wet density) differs from the density of the mineral foam in the dry state, i.e. after setting (density of hardened material) . The density of the fresh mineral foam is always higher than the density of the foam in the dry state. The invention has the advantage that the mineral foam according to the invention has a great lightness, and in particular a very low density. The invention offers another advantage that the mineral foam according to the invention has excellent stability properties. In particular the bubbles that make up the mineral foam in the fresh state are slightly degraded after pouring into the mold or deposited on the support. The support can be of different natures and different forms. The medium can be a receptacle to fill. In this case, it is envisaged to fill masonry blocks with the mineral foam according to the invention. For example, it may be masonry blocks, terra cotta blocks, cellular concrete blocks that are filled with the foam according to the invention. The support may be a wall to be covered with mineral foam according to the invention. For example, it can be a concrete veil, a concrete slab, a wall of block masonry, a wall of terracotta blocks, a wall of cellular concrete blocks, a wall covered with mortar or plaster, The support can be of different types such as concrete, terracotta, plaster, raw wood, plasterboard, cardboard or any other material used in construction. The support may be treated, or covered with a first layer of mineral foam according to the invention. The support can be treated before removal of the foam. The treatment may for example consist of one or more water splashes, the projection of setting accelerator solutions such as aluminum sulphate, or the removal of primer primers, or any other solution of a physical nature. or chemical to accelerate the setting of the cement at the interface between the support and the mixture, or to allow better adhesion of the mixture on the support or to increase the roughness of the support. The invention offers another advantage that the mineral foam according to the invention has excellent thermal properties, and in particular a very low thermal conductivity. Decreasing the thermal conductivity of building materials is highly desirable as it provides heating energy savings in apartment buildings and workplaces. In addition, the mineral foam according to the invention makes it possible to obtain good insulating performance over small thicknesses and thus to preserve the habitable surfaces and volumes. Thermal conductivity (also called lambda (X)) is a physical quantity that characterizes the behavior of materials during conductive heat transfer. Thermal conductivity is the amount of heat transferred per unit area and a unit of time under a temperature gradient. In the international unit system, the thermal conductivity is expressed in watts per meter Kelvin (VV.m-1.K-1). Conventional or conventional concretes have a thermal conductivity between 1.3 and 2.1 measured at 23 ° C and 50% relative humidity. The mineral foam according to the invention has a thermal conductivity of 0.03 to 0.5 VV / m.K, preferably 0.04 to 0.15 VV / m.K, more preferably 0.045 to 0.10 VV / m.K. The invention offers another advantage that the mineral foam according to the invention has good mechanical properties, and in particular good compressive strength compared to known mineral foams. The mineral foam according to the invention has a compressive strength of from 0.04 to 5 MPa, preferably from 0.05 to 2 MPa, more preferably from 0.05 to 1 MPa. The invention also relates to the use of the mineral foam according to the invention as a construction material. For example, the mineral foam according to the invention can be used for pouring walls, floors, roofs during a building site. It is also envisaged to produce prefabricated elements in prefabrication plant from the foam according to the invention such as blocks, panels. The mineral foam according to the invention can be cast on walls during a construction site. The invention also relates to the use of the mineral foam according to the invention as an insulation material, in particular as a thermal or acoustic insulation material. Advantageously, the mineral foam according to the invention makes it possible in certain cases to replace glass wool, mineral wool, asbestos or insulators made of polystyrene and polyurethane.
    [0016] Advantageously, the mineral foam according to the invention can be used for filling or filling a hollow or hollow space of a building, a wall, a partition, a masonry block, for example a cinder block, d a brick, a floor or a ceiling. Such materials or elements of composite constructions comprising the mineral foam according to the invention are also objects of the Persian invention.
    [0017] Advantageously, the mineral foam according to the invention can be used as a clogging material. Advantageously, the mineral foam according to the invention can be used as a facade covering, for example to insulate a building from the outside. In this case, the mineral foam according to the invention may be coated with a finishing coating.
    [0018] The invention also relates to a system comprising the mineral foam according to the invention. The foam may be present in the system as an insulating material. It can be cast vertically between two walls, chosen for example from PA14021 FR concrete sails, brick walls, plasterboard, wood plate, for example thin oriented wood panels, or fiber cement panels, all forming the system. The system according to the invention is advantageously able to withstand or reduce the transfer of air and thermohydric, that is to say that this element has a controlled permeability to transfers of air, water in the form of steam or liquid. The system according to the invention preferably comprises at least one framework or a structural element. This frame may be concrete (posts / beams), metal (amount or rail), wood, plastic or composite material or synthetic material. The mineral foam according to the invention can also coat a structure of the type for example lattice (plastic, metal) or a pillar or beam of a building. The system according to the invention can be used to make or manufacture a doubling, an insulation system, or a partition, for example a partition, a distribution partition or a bulkhead. The invention also relates to a construction element comprising the mineral foam according to the invention. When the mineral foam according to the invention is intended to be projected on a vertical wall, this wall may be provided with elements that facilitate the attachment of the foam, for example wire mesh or based on plastic materials, spaced or not the wall, and integral or not of the wall. Vertical reinforcements may be positioned along the wall to serve as anchor points of the trellises. These lattices may be simple horizontal son. Figure 1 is a diagram illustrating the principle of measuring a contact angle between a drop of water and a surface. FIG. 2 is a diagram illustrating an exemplary embodiment of a device for implementing the method according to the invention. In the example shown in FIG. 2, the device comprises a vessel equipped with an agitator (1), a first pump (3), a first pipe (4), a static mixer (5), a second pump (6) ), a container (7), a second hose (8), an output member (9) and a carrier (10). The mixture (2) is the mixture of step (i), and is contained in the tank (1). The blowing agent is contained in the container (7). They are pumped continuously independently by the pumps (3) and (6) and mixed by means of the static mixer (5). The pipe (8) and the outlet element (9) form a pipe which may comprise additional elements of different sections and lengths. The dimensions (L1) and (D1) of the pipe (8) and the dimensions (L2) and (D2) of the outlet element (9) are chosen such that the pressure losses PA14021 FR in the pipe remain compatible with the characteristics of the flows, such as flow rates and velocities at the outlet of the pipe, and with the pumping means. The pipe (8) and the outlet element (9) are also chosen as a function of the rate of evolution of oxygen in the pipe, and in particular of the ratio between the expected clearance in the pipe and that expected after the outlet ( 11) of the pipeline, and the regularity of the flow. Generally, the diameter (D2) of the end portion of the pipe (outlet (11) is selected as a means of controlling the ejection velocity of the foam while maintaining the integrity of the jet. invention, the expansion is not complete at the exit of the pipe (11), and ends on the support (10) Generally, at least 20% of the expansion remains to be made on the support (10) Other embodiments of a device for implementing the method according to the invention can be envisaged: Method for measuring a wetting or contact angle: FIG. wetting angle between a solid surface 10 of a concrete sample 12 and a drop 14 of a liquid deposited on the surface 10. The reference 16 designates the liquid / gas interface between the drop 14 and the ambient air Figure 1 is a section on a plane perpendicular to the surface 10. In the section plane the wetting angle α corresponds to the angle, measured from inside the drop 14 of liquid, between the surface 10 and the tangent T at the interface 16 at the point of intersection between the solid 10 and the interface 16. To measure the wetting angle, the sample 12 is placed in a room at a temperature of 20 ° C and a relative humidity of 50%. A drop of water 14 having a volume of 2.5 μL is placed on the surface 10 of the sample 12. The measurement of the angle is carried out by an optical method, for example using a shape analysis device. (English Drop Shape Analysis), for example the device DSA 100 marketed by Kriss. The measurements are repeated five times and the value of the contact angle measured between the drop of water and the support is equal to the average of these five measurements.
    [0019] Laser particle size distribution method The particle size curves of the various powders are obtained from a Mastersizer 2000 type laser granulometer (year 2008, MALI 020429 series) sold by Malvern. The measurement is carried out in a suitable medium (for example, in an aqueous medium) in order to disperse the particles; the particle size should be from 1 μm to 2 mm. The light source consists of a red He-Ne laser (632 nm) and a blue PA14021 FR (466 nm). The optical model is that of Fraunhofer, the calculation matrix is of polydisperse type. A background measurement is first performed with a pump speed of 2000 rpm, an agitator speed of 800 rpm and a noise measurement over 10 s, in the absence of ultrasound. It is then verified that the laser light intensity is at least 80%, and that a decreasing exponential curve is obtained for the background noise. If this is not the case, the lenses of the cell should be cleaned. A first measurement is then carried out on the sample with the following parameters: pump speed of 2000 rpm, agitator speed of 800 rpm, absence of ultrasound, obscuration limit between 10 and 20%. The sample is introduced to have a darkness slightly above 10%. After darkening stabilization, the measurement is made with a time between immersion and the measurement set at 10 s. The measurement time is 30 s (30,000 diffraction images analyzed). In the granulogram obtained, it must be taken into account that part of the population of the powder can be agglomerated. Then a second measurement (without draining the tank) with ultrasound. The pump speed is raised to 2500 rpm, agitation at 1000 rpm, ultrasound is emitted at 100% (30 watts). This regime is maintained for 3 minutes, then it returns to the initial parameters: pump speed of 2000 rpm, agitator speed of 800 rpm, absence of ultrasound. After 10 s (to evacuate the possible air bubbles), a measurement of 30 s (30,000 images analyzed) is carried out. This second measurement corresponds to a deagglomerate powder by ultrasonic dispersion. Each measurement is repeated at least twice to check the stability of the result. The apparatus is calibrated before each working session by means of a standard sample (silica Sifraco C10) whose grain size curve is known. All the measurements presented in the description and the ranges announced correspond to the values obtained with ultrasound. BLAINE surface area measurement method The specific surface area of the different materials is measured as follows.
    [0020] The Blaine method at 20 ° C with a relative humidity not exceeding 65% using a Blaine Euromatest Sintco apparatus compliant with the European standard EN 196-6; Before measuring the specific surface, the wet samples are dried in an oven until a constant mass is obtained at a temperature of 50 to 150 ° C (the dried product is then ground to obtain a powder with the maximum particle size is less than or equal to 80 μm). EXAMPLES The process according to the invention was practiced to produce inorganic foams of formulas 391, 390-a, 390-b and 400. A comparative example 389 was also carried out in order to highlight the advantageous aspects of the process. according to the invention. Materials: The cement used is Portland cement CEMI 52, R from the Lafarge Saint Pierre la Cour cement plant. The letter "R" corresponds to the definition of the NF EN 197-1 standard, version of April 2012. This cement was crushed to obtain a Blaine specific surface of 8000 cm2 / g. The water-reducing agent is a new generation high-performance water-reducing superplasticizer based on the modified polycarboxylate sold under the name Chryso Fluid Premia 180 and from the company Chryso. The solids content of Premia 180 is 50%, percentage by mass. The water-reducing agent does not contain an antifoaming agent. The ultrafine particles are precipitated calcium carbonate particles sold under the name Socal 312 and from Solvay PCC. These ultrafine particles have a contact angle varying from 90 ° to 130 ° as measured according to the method described above and a D50 of 40 nm particles as measured with the method described in document EP 1 740 649. The salt of transition metal is manganese sulfate monohydrate from Sigma Aldrich.
    [0021] The mineral addition is a calcareous powder sold under the name of BL200 Orgon and coming from the company Omya for the formulas 389, 391, 390-a and 390-b and a Dunkirk slag (Origin Arcelor) for the formula 400. The D50 of the BL200 is 6! Am and the D50 of the slag is 14.2! Am. The cement hydration accelerator is 1 mol / l aluminum sulphate prepared from powdered hydrated aluminum sulphate (14H20) from the company VVVR. The blowing agent is 30% hydrogen peroxide from the company VVVR. Water is tap water.
    [0022] PA14021 FR Materials used: Rayneri mixers: - A model R 602 EV mixer (2003) supplied by the company Rayneri. The mixer consists of a frame on which are positioned tanks ranging from 10 to 60 liters. The 10L tank was used with a paddle type blade adapted to the volume of the tank. This blade exerts a rotational movement on itself accompanied by a planetary movement around the axis of the tank. Pumps: - SeepexTM eccentric screw pump (I) type MD 006-24 Commission no. 244920. - SeepexTM eccentric screw pump (II) type MD 006-24 cat. No. 278702. Static mixer: - A static mixer composed of 32 Kenics type helical elements of 19mm diameter referenced 16La632 at ISOJET I. Realization of mineral foams Preparation of the dough for formulas 389, 391, 390-a and 390-b: The dough is prepared by mixing the compounds of Table I in the respective proportions indicated in this table. The dough is then kneaded with water in a planetary kneader (Rayneri brand) for 5 min. The density of fresh foam after expansion is measured. Table 1 Formulations 389 391 390-a 390-b 400 cement * 71.9 71.9 71.9 71.9 71.46 water reducing agent * 0.2 0.2 0.2 0.2 0.4 ultrafine particles * 4.83 4.83 4.83 4.83 4.8 transition metal salt * 0.72 1.43 0.36 0.36 1.6 mineral addition * 22.35 21.64 22, 71 22.71 21.74 total 100 100 100 100 100 pore-forming agent ** 7.1 4.6 3 5.6 4.5 Water / cement *** 0.76 0.76 0.76 0.76 0, 76 * the values are percentages expressed in mass relative to the mass PA14021 FR ** percentages in mass relative to the mass of cement *** ratio in mass Before application of the foam on a wall in blocks serving as support, the The wall is treated, by means of a spray, by spraying an aluminum sulphate solution of 1 mol / l. Then the pulp is pumped continuously by means of a screw pump (Seepex mark (1)) in a main pipe of 15 mm diameter. Simultaneously, the aqueous solution of hydrogen peroxide is pumped by means of another screw pump (Seepex brand (11)) and injected continuously into the pipe in which the paste flows. The respective pumping rates are shown in Table 2. The mixing between the paste and the solution is accelerated by the presence of a static mixer placed in the main pipe and located immediately downstream of the injection point of the peroxide solution. hydrogen. The pipe downstream of the static mixer is 5.5 m long.
    [0023] Table 2 Formulations 389 391 390-a 390-b flow rate in kg / min 5.5 5.5 5.5 5.5 flow rate in kg / min (H202) 0.590 0.37 0.24 0.52 The pipeline is equipped with an applicator (diameter adapter ) which increases the diameter of the outlet tubing to 20 mm over a length of 20 cm. It is observed that the paste obtained at the outlet of the applicator is only partially aerated (less than 50% of the total oxygen fraction is incorporated into the dough at this stage) and its expansion continues after deposition. The paste is deposited on the wall only by means of the outlet jet, which maintains its integrity to the point of removal. The density of fresh foam after expansion is measured. The wall is covered by gradually varying the position of the point of removal, until the wall is completely covered by the foam after complete expansion. A layer of about 3 cm is thus obtained. The system is left as it is until the setting of the cement is started, about 2h30 at room temperature. The foam removal operation is repeated a second time, exactly under the same conditions as the first time. A second layer of about 3 cm is deposited. The paste is then floated to smooth the inequalities and give it a finished look. PA14021 EN Preparation of the dough for Formula 400: Percentages being expressed by weight, the dough is prepared by mixing the following compounds: 71.46% of ground cement to reach a Blaine specific surface of 8000 cm / g. 22.2% Dunkirk Dairy 4.80% ultrafine particles treated (Solvay PCC Socal 312) 1.6% manganese sulphate monohydrate 0.4% of a Premia 180 superplasticizer 4.5% added, calculated on cement, H202 as a 30% solution. He. Analysis of the mineral foam 11.1 Thermal conductivity of the mineral foams The thermal conductivity (X) was measured using a thermal conductivity meter: CT-meter supplied by Alphis-ERE (Resistance 50, wire 50mm probe). The measurement was performed on samples dried at 45 ° C to constant mass. The sample was then cut into two equal pieces using a saw. The measuring probe was placed between the two flat faces of these two halves of samples (sawed sides). Heat was transmitted from the source to the thermocouple through the material surrounding the probe. The temperature rise of the thermocouple was measured as a function of time and made it possible to calculate the thermal conductivity of the sample. //.2 Density of mineral foams The wet density of foamed cement slurries was measured by weighing the cubes at the moment of casting and after complete expansion. The dry density of the samples was measured on samples dried at 45 ° C to constant mass, always by weighing the cubes.
    [0024] Table 3 Formulations 389 391 390-a 390-b 400 X in VV / mK 0.048 0.072 0.11 0.051 0.070 Fresh Density in kg / m3 80 200 340 98 189 Dry Density in kg / m3 70 160 271 80 130 PA14021 EN
    权利要求:
    Claims (13)
    [0001]
    CLAIMS1- A method of continuously producing a mineral foam whose density in the dry state (d) is from 40 to 600 kg / m3, comprising the following steps: (i) mixing n cement; n a water reducing agent; n 0.5 to 10 (:) / 0,% by weight, based on the total mass of cement, of ultrafine particles having a liquid-solid contact angle of from 30 ° to 140 °, and of which the D50 is comprised at 600 nm; n water, with a water / cement mass ratio of 0.3 to 2.5; (ii) adding to the mixture from 0.5 to 10% of a blowing agent,% by weight relative to the mass of cement; (iii) placing the mixture obtained in step (ii) on a support; (iv) allow the mixture to expand on the support.
    [0002]
    2. The method of claim 1 wherein the cement of the mixture of step (i) is a cement whose Blaine surface area is between 5000 and 9000 cm2 / g.
    [0003]
    3. Process according to any one of the preceding claims wherein there is no foaming agent in the mixture of step (i) or (ii).
    [0004]
    The process according to any one of the preceding claims wherein the mixture of step (i) or step (ii) further comprises a transition metal salt, for example a manganese salt or a salt thereof. iron.
    [0005]
    5. Process according to any one of the preceding claims wherein the mixture of step (i) further comprises a mineral addition such as pozzolan, a slag, calcium carbonate, fly ash, sand or their salts. mixtures, and whose particles have a D50 of 0.1 to 4 mm.
    [0006]
    6. Process according to any one of the preceding claims, in which the blowing agent added in step (ii) is a solution of hydrogen peroxide, a solution of peroxomonosulphuric acid, a solution of PA14021 FR -oxodisulfuric acid, a solution of alkaline peroxides, a solution of alkaline earth peroxides or an organic peroxide solution such as peroxoacetic acid or peroxobenzoic acid, or a suspension of aluminum particles or mixtures thereof.
    [0007]
    7- Process according to any one of the preceding claims wherein the mixture of step (i) further comprises an accelerator of the hydration of cement, for example calcium chloride.
    [0008]
    8- Process according to any one of the preceding claims wherein the mixture obtained in step (ii) is not fractionated.
    [0009]
    9- Process according to any one of the preceding claims wherein in step (iii), the mixture is put in place without using a spray nozzle.
    [0010]
    10- Method according to any one of the preceding claims wherein step (iii) is carried out without spraying.
    [0011]
    11- Method according to any one of the preceding claims wherein the support used in step (iii) is treated prior to the introduction of the mixture obtained in step (ii).
    [0012]
    12- mineral foam obtainable according to the method of claims 1 to 11.
    [0013]
    13- Use of the mineral foam according to claim 12 as an insulation material, in particular as a thermal or acoustic insulation material. PA14021 EN
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    EP3237353A1|2017-11-01|
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    MA41247A|2017-10-31|
    CA2971658A1|2016-06-30|
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    US20170349498A1|2017-12-07|
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    MX2017008515A|2017-09-19|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2007134349A1|2006-05-19|2007-11-29|Manfred Sterrer|Lightweight concrete or mineral foams and method for production thereof|
    JP2008189526A|2007-02-06|2008-08-21|Basf Pozzolith Ltd|Admixture for grout and cement composition for grout|
    FR2986790A1|2012-02-15|2013-08-16|Saint Gobain Weber|CONTINUOUS PROCESS FOR MANUFACTURING A MATERIAL BASED ON EXPANSION-ALIGNED HYDRAULIC BINDER|WO2018184973A1|2017-04-07|2018-10-11|Hilti Aktiengesellschaft|Use of amorphous calcium carbonate in a fire-resistant inorganic mortar system based on aluminous cement to increase load values at elevated temperatures|
    WO2021037989A1|2019-08-30|2021-03-04|Holcim Technology Ltd|Method of production of a mineral foam for filling cavities|
    US11214518B2|2015-10-20|2022-01-04|Hilti Aktiengesellschaft|Fastening system and use thereof|
    US11214519B2|2015-10-20|2022-01-04|Hilti Aktiengesellschaft|Two-component mortar system based on aluminous cement and use thereof|FR2708592B1|1993-07-29|1995-09-29|Lafarge Coppee|Accelerating and hardening agent for silicic hydraulic binders.|
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    FR2873366B1|2004-07-20|2006-11-24|Lafarge Sa|SULFOALUMINOUS CLINKER HAVING A HIGH BELITE CONTENT, PROCESS FOR PRODUCING SUCH A CLINKER AND USE THEREOF FOR PREPARING HYDRAULIC BINDERS.|
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    FR2989083B1|2012-04-06|2014-04-25|Lafarge Sa|INSULATING MINERAL FOAM|EP3483131B1|2017-11-09|2020-12-23|Holcim Technology Ltd|Method of production of a mineral foam obtained from a foaming slurry of high yield stress|
    RU2719895C1|2019-07-03|2020-04-23|Федеральное государственное бюджетное образовательное учреждение высшего образования "Владивостокский государственный университет экономики и сервиса" |Concrete mixture|
    法律状态:
    2015-12-28| PLFP| Fee payment|Year of fee payment: 2 |
    2016-06-24| PLSC| Publication of the preliminary search report|Effective date: 20160624 |
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    2021-11-10| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1463226A|FR3030504B1|2014-12-23|2014-12-23|PROCESS FOR THE CONTINUOUS PRODUCTION OF LOW-DENSITY MINERAL FOAM|FR1463226A| FR3030504B1|2014-12-23|2014-12-23|PROCESS FOR THE CONTINUOUS PRODUCTION OF LOW-DENSITY MINERAL FOAM|
    MA041247A| MA41247A|2014-12-23|2015-12-17|CONTINUOUS MANUFACTURING PROCESS OF LOW DENSITY MINERAL FOAM|
    MX2017008515A| MX2017008515A|2014-12-23|2015-12-18|Method for the continuous production of a low-density mineral foam.|
    CN201580075388.4A| CN107207350A|2014-12-23|2015-12-18|Method for continuously preparing low-density mineral froth|
    RU2017124745A| RU2731119C2|2014-12-23|2015-12-18|Method of continuous production of mineral foam low density|
    EP15823671.1A| EP3237353A1|2014-12-23|2015-12-18|Method for the continuous production of a low-density mineral foam|
    PCT/FR2015/053620| WO2016102838A1|2014-12-23|2015-12-18|Method for the continuous production of a low-density mineral foam|
    US15/538,877| US10538462B2|2014-12-23|2015-12-18|Method for the continuous production of a low-density mineral foam|
    CA2971658A| CA2971658A1|2014-12-23|2015-12-18|Method for the continuous production of a low-density mineral foam|
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