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    • 专利摘要:
    Composition for a construction material comprising a matrix substantially containing an alumino-silicate-based compound, such as a metakaolin, and an alkaline activation solution, characterized in that it contains a mass proportion of cement or clinker less than 10%, and in that the metakaolin is a metakaolin obtained by flash calcination. The reaction between the constituents takes place at a temperature below 30 ° C. The method of manufacturing the building material comprises mixing said composition with various elements such as aggregates, plant fibers, raw clay, expansive agents. Application particularly to the production of floor covering elements, walls or roofs, prefabricated building elements or insulation modules, adhesives or mineral mastics.
    公开号:FR3034094A1
    申请号:FR1552615
    申请日:2015-03-27
    公开日:2016-09-30
    发明作者:David Hoffmann
    申请人:Hoffmann Jb Tech；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of building materials, and more particularly relates to new compositions for building materials, their associated processes and their uses for the realization of particular elements or building modules.
    [0002] Cement, such as Portland cement, is a widely used material in the construction field. However, this cement, although powerful, requires, for its manufacture, on the one hand, the consumption of many resources and, on the other hand, produces a significant amount of pollutants responsible, among others, for global warming and acid rain. . Finally, its lifespan, although long, is limited by multiple degradations, particularly related to air pollution, it can suffer over time. All these features make Portland cement less and less part of a sustainable development approach. There are alternatives to conventional building materials but they only partially meet the necessary performance requirements. In addition, their high economic cost often proves a limit to a wide use. For example geopolymers, invented in the late 70s by Professor Davidovits. Their properties in terms of durability, mechanical performance and sustainable development have recently put these new generation binders on the front of the stage. A geopolymer is formed from a mineral matrix composed of silica and alumina having reaction sites on which crosslinking agents contained in a so-called activation solution, generally alkaline, are reacted. This reaction produces a poly (silico-oxo-aluminate) gel which coats the aggregates and cures as the reaction progresses, until a monolithic block composed of glass' in which aggregates are included. However, the methods for producing these geopolymers are either not adaptable industrially and / or use expensive products. The reactions are generally carried out with heating of the constituents. An example of room temperature manufacture of geopolymeric cement based on silico-aluminous fly ash (so-called class F) is described in the patent EP 2061732 B1 by J. Davidovits. However, the basic material, silico-aluminous fly ash (so-called class F), from coal-fired power plants, is a material that is not widely available in France. In another and more recent patent application FR 2966823 of the same inventor is described a method of manufacturing a binder or geopolymer cement comprising a first stage of treatment of geological elements rich in iron oxides and ferro-kaolinite at a temperature of 600 to 850 ° C for several hours, during which the ferro-kaolinite becomes ferro-metakaolin, then in a second step to react with a Ca-geopolymeric reaction medium at room temperature or below 85 ° C. The examples of this document indicate that the geopolymeric precursor, which is ferro-metakaolin here, is prepared during a long heat treatment (calcination at 750 ° C. for 3 hours, followed by grinding) and therefore very much a consumer of energy. The present invention aims to overcome the disadvantages of the prior art by providing a composition for building material from readily available materials and reagents, and low environmental impact: especially not requiring expensive and long heat treatment.
    [0003] Another object of the invention is to propose a composition for construction material with a reduced amount, or even an absence of cement or clinker, which can be used for making various modules or building elements, by molding or extrusion. Another object of the invention is to provide a composition for construction material that can be used in a method of manufacturing modules or construction elements mixed with raw clay, without the need for firing. For this purpose, the present invention provides a composition for a construction material comprising a matrix substantially containing an alumino-silicate compound, such as a metakaolin, and an alkaline activation solution, characterized in that contains a mass proportion of cement or clinker less than 10%, preferably less than 5%, more preferably less than 1% by weight, and that the metakaolin is a "flash" metakaolin. The flash metakaolin (also called flash metakaolin) is obtained by flash calcining a powdered clay at a temperature between 600 and 900 ° C for a few seconds, followed by a rapid cooling, unlike the "conventional" metakaolin which is obtained by calcination in a rotary kiln for at least 5 hours. Its manufacture requires much less energy, is a low CO2 emission process and is less complex than that of conventional metakaolin since the heating period lasts only a few seconds and no subsequent grinding is necessary. In addition, the preparation of the clay before the heat treatment is minimal. Its environmental impact is therefore lower and its cost is lower. 5 It turns out that this flash metakaolin is very responsive. The inventors have found that the demand for water and activating reagents is much less important when using the flashed metakaolin, of the order of at least 50% activating reagent compared with conventional metakaolin. Flash metakaolin is heretofore used as an additive in cementitious compositions in minority (less than 20%) by weight proportions with Portland cement for example. The inventors have surprisingly discovered that such a flash metakaolin can react at room temperature (below 30 ° C.) with the alkaline activation solution to give materials with interesting properties, as described below. The alkaline activation solution advantageously comprises a source of sodium or potassium silicate (according to the cement nomenclature contains SiO 2 and M 2 O), and an alkaline base, such as NaOH and / or KOH, (according to the C 20 nomenclature of formula M 20). M may represent sodium or potassium). Preferably, the silicate source of the activating solution has a molar SiO 2 / M 2 O ratio greater than 1.5, preferably greater than 3. Preferably, the alkaline activation solution has an overall SiO 2 / molar ratio. M20 between 0.8 and 2.5, preferably between 1.0 and 2.0, more preferably between 1.20 and 1.80, more preferably between 1.25 and 1.65. Activation solutions used in geopolymerization are generally defined by their silica / alkali ratio. When the present invention is carried out with activation solutions with silica / alkali molar ratios (denoted SiO 2 / M 2 O) of between 1.25 and 1.65, a lower propensity to the efflorescence phenomenon is observed than with the formulations. With the molar ratio of less than 1.2 or less than 1 of the geopolymers of the prior art. Which is an important technical advantage. In addition, high-ratio solutions are more stable and easier to use. According to an advantageous variant of the invention, the alkaline base of the alkaline activation solution is an aqueous sodium hydroxide solution NaOH. The examples mentioned later in the description show that it is not necessary to use a highly concentrated sodium hydroxide solution. In the composition according to the invention, the matrix may comprise, mixed with the flashed metakaolin, a non-flashed metakaolin, one or more powdery mineral materials (that is to say with particle size advantageously less than 200 μm) which may be chosen from blast furnace slag, class F fly ash, fireclay and / or nététakaolin scrap, | awm | laatonite, terra cotta powder, issued, in particular scrap manufacturing waste. brickworks, mineral powders with pozzolanic activity, recycled glass powder, cullet, Class C fly ash or slaked lime. With regard to the mass concentrations of the powdery materials containing at least 20% of metakaolin in said matrix, these concentrations are advantageously the following: less than or equal to 80%, preferably less than 60% and more preferably less than 50% for blast furnace slag, Class F fly ash, chamotte and / or metakaolin scrap, | awol | astonite and terra cotta powder, - less than or equal to 40%, preferably less than 25% for mineral powders having pozzolanic activity, recycled glass powder, cullet or fly ash of class C, and less than or equal to 15%, preferably less than 10%, of more preferably less than or equal to 5% for slaked lime.
    [0004] According to an advantageous embodiment of the composition of the invention, the matrix comprises flashed metakaolin and blast furnace slag in a slag mass concentration of less than or equal to 30% of the total weight of the matrix. Preferably, the relative proportions of the activating solution and the matrix are such that the total sum in moles SiO 2 + M 2 O of the activation solution is between 3.5 and 6.5 mol / kg of matrix. preferably between 4.5 and 5.5 mol / kg of matrix. The activation solution may be a ready-to-use activation solution, such as the activation solution of the GEOSIL category (sold by the company 3034094 WOELLNER). The advantage is a simplification of the implementation since the activation solution no longer needs to be prepared on site. The composition according to the invention may furthermore contain one or more adjuvants, such as a superplasticizer (for example of the polyacrylate or lignosulfonate type), a water-repellent agent, a water-retaining agent or an anti-shrinkage agent. Adjuvant is understood to mean an addition, in particular of organic nature, with a view to modifying certain basic properties, in proportions of less than 5% by weight of the composition. The composition may further comprise dyes or pigments. The composition according to the invention may also contain one or more mineral powder additives, chosen from kaolin, powdered raw clay, zinc oxide, plaster, fused aluminous cement, titanium dioxide, ettringitic binder, a fluorosilicate such as sodium hexafluorosilicate, with a view to modifying certain basic properties, in a concentration preferably of less than 20 parts by weight, more preferably between 0.5 and 10 parts by weight, per 100 parts by weight; weight of the matrix. The raw clay powder may comprise mainly kaolinite or montmorillonite. The present invention also relates to various methods of making a building material from the base composition described above. More particularly: - a method of producing a construction material comprising mixing the constituents of said composition with aggregates selected from fillers, powders, sand, gravel, and / or fibers, and optionally pigments; A process for producing a construction material comprising mixing said composition with raw clay, preferably in proportions of up to 70% by weight, more preferably up to 60% by weight material, and cold extrusion or cold molding said mixture; obtaining the material is carried out without cooking, unlike conventional materials based on raw clay which require firing at a temperature of the order of 900 to 1100 ° C. a method of producing a construction material comprising mixing said composition with "aggregates" or fibers of vegetable origin, such as sawdust, chips and wood fibers, straw, hemp, flax , cork or perlite; A process for producing an expanded construction material comprising mixing said composition with an expansive or foaming agent, such as aluminum powder, advantageously in the presence of stabilizing agent. All of these processes can be carried out at temperatures between about 0 ° C and about 30 ° C, without the need for heat treatment. More specifically, the matrix, made from the components presented above, is mixed with the activation solution, itself prepared according to the formula indicated. The combination of the two then constitutes the composition according to the invention, in the form of a thick liquid, which is then mixed with one or more neutral compounds such as aggregates or fibers, of which it will constitute the binder. . The additives or adjuvants, added to the mixture, make it possible to confer certain particular complementary properties. This binder, resembling a resin, allows after reaction, to form with the "aggregates" and "additives" a coherent monolithic assembly having new properties compared to the materials of the prior art, including a short setting time, a very small dimensional shrinkage, a glossy surface appearance. The present invention also relates to the multiple possible uses of said composition according to the invention or methods described above, and in particular: the use of said composition or said process for the production of coating elements, in particular floor coverings, such as tiles, slabs, pavers or curbs, wall coverings, such as interior or exterior facade elements, cladding boards, cladding elements, or tile-like roofing for producing extruded or molded building modules, such as bricks, or for producing various extruded shapes; the use of said composition or said process for producing composite materials, such as prefabricated panel type building panels, prefabricated blocks such as door or window lintels, prefabricated wall elements, or any other prefabricated building elements; the use of said composition with an expansive or foaming agent for the production of insulation modules, such as partition panels, or light insulating building modules (with a density of less than 1.5 kg / L); Preferably less than 1.2 kg / l, more preferably less than 1.0 kg / l, more preferably less than 0.7 kg / l); the use of said composition for production by additive manufacturing, such as by means of a 3D printer, building elements, buildings or houses, or decorative objects; or else - the use of said composition in the form of a two-component system with either the constituents in solid form on the one hand, and the constituents in liquid form on the other hand, or the constituents in the form of two pastes, for making putty, glue or sealing mortar, for example for injection from cartridge gun type apparatus each containing a part of the components of the final composition. These last two uses are very difficult to implement from cementitious compositions because of the hydration reaction of this material as soon as it is mixed with water, requiring the synchronization between the addition of water, the mixing and depositing the dough. The present invention will now be described in more detail and illustrated by the nonlimiting examples hereinafter. In the examples, the abbreviations of Table 1 are used for the composition of the matrix: Abbreviation Component MKF Metakaolin flash LHF Blast furnace blast CVS Class F fly ash CFX Chamotte manufacturing scrap CHX Lime Lime WLS Wollastonite CCL Powder glass Table 1 The metakaolin used is ARGICEM® brand from Argeco Développement.
    [0005] It is a product having a high BET specific surface area (between 5 and 6 m 2 / g (NF ISO 9277).) As regards its particle size, the measurements made according to the standard NF P 18-513 indicate: 0.125 mm: 95%, passing to 0.08 mm: 80% and passing to 0.0063 mm: 79.5% In all the examples below, the alkaline silicate and the alkaline base are in aqueous solution, their Concentrations are expressed in% by mass in this solution Most of the time, no other addition of water than the water of these solutions constituting the activation solution is necessary.The quantity of water is therefore as small as possible. The weight ratio of water E to MSR total dry matter of the binder composition (hereinafter referred to as "resin" or binder) is preferably less than 1, but varies according to the type of matrix, for example E / MSR is advantageously less than 0.6 for a matrix consisting of flashed metakaolin alone, and a ratio E / MSR close to 0.8 for a matrix containing a mixture of flashed metakaolin and non flashed metakaolin. EXAMPLE 1 Table 2 below shows various compositions according to [invention: FR01 to FR11, with indication of the SiO 2 / M 2 O molar ratio of the activating solution and indicating the X / M ratio in mol / kg (total sum of moles SiO2 + M20 of the activation solution per kg of matrix). The mechanical performance, obtained after mixing the binder composition (hereinafter referred to as "resin" or binder) with the aggregates, then molding and curing time at a temperature of 20 ° C are given in terms of compressive strength for a cylinder of 40 mm diameter for 80 mm height. In contrast to the formulas given later in the applications, the aggregates used in these formulas have only a neutral filling role and their stacking was therefore not optimized. Tempo 12 is a water reducer marketed by the company Sika, polyacrylate type. The fine sand is fine Fontainebleau sand of particle size less than or equal to 1 mm, the fine limestone powder has a particle size of less than 200 μm.
    [0006] In this example the plug (setting <24h) has been estimated visually. FR01 FR02 FR03 FR04 FR05 FR06 FPJ37 FR08 FR09 FR10 FR11 Composition Matrix MET (% Mass) 50 49 47 51 50 47 35 40 50 49 30 of LHF Resin (% Mass) 10 CVS (% Mass) 20 CFX (% Mass) 15 CHX (% Mass) 2 3 WLS (Mass%) 6 1 CCL (Mass%) 6 Alkaline silicate solution Molar ratio 3,384 3,384 3,384 3,384 Silica Am 3,384 3,384 3,384 3,384 1,681 3,384 Activation (% SiO2) 26.2 26.2 26.2 26.2 100 26.2 26.2 26.2 26.2 27.5 26.2 (% MS) 34.2 34.2 34.2 3A2 100 34.2 34.2 34.2 34 , 2 44.3 34.2 Qty. (%) 34 33 31 34 9 31 34 34 34 33 34 Alkaline base Type NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH KOH NaOH NaOH (Yo Mass) 32 32 32 50 32 32 32 32 45 32 32 (mol M2Ofkg1 4 4 4 6,25 4 4 4 4 4 4 4 Qty (%) 16 16 16 11 28 16 16 16 16 8 16 Global Ratio Si02 / M20 1,376 1> 352 1,302 1,318 1,339 1,302 1,376 1,376 1,376 1,246 1,376 Complementary Water (% M ass) 3 13 7 Ratio Md mollItg 5,127 4,915 4,516 5,021 5,240 4,516 5,127 5,127 5,127 5,244 5,127 Composition Resin% 49.2 50.0 51.0 49.4 49.7 52.9 49.1 49 , 8 48.9 50.1 49.4 and performance of the Monolith Test. Tempo 12% 0.8 0.8 1.0 0.5 0.8 0.3 0.9 0.2 0.2 1.0 0.6 Sand Fine% 35.0 35.0 34.0 35, 4 35.0 35.2 35.6 35.4 34.6 34.6 35.6 Filler C ale area 15.0 14.2 14.0 14.7 14.5 11.6 14.4 14.6 16.3 14.3 14.4 Seffing <24H OK OK OK OK OK OK OK OK OK OK RC J + 7 Itea 30.2 30 23> 20 33.7 31.5> 25 RCJ + 28 MPa> 38.8 Re J + 56 Iteel 31.4 35 37.3 31 30> 40 28> 40 31.5> 35 3034094 10 Example 2: Table 3 below shows formulations FR-N1 and FR-N2 which have a lower performance than those of Example 1. It has been found that the resin composition FR_N1 is very alkaline and produces efflorescences, and the FRN2 composition with an X / M ratio greater than 2 has a low mechanical strength ( Rc at 28 days <5 MPa). This example shows the importance of the preferred SiO 2 / M 2 O and X / M ratios, to improve the properties of the materials prepared from the composition according to the invention and their performance. FR_N1 FR_N2 of Matrix MKF 50 40 Resin CVS 10 Composition Solution Alkali silicate Molar ratio 3,384 3,384 activation (SiO2) 26,2 26,2 (%) 34,2 34,2 Qty (%) 10 13 Alkaline base Type NaOH (%) 32 32 (mol M20 / kg) 4 4 10 7 Global Si02 / M20 ratio 5 .. 1,268 Complementary water 30 XiM ratio mol / kg 4,331 10 Table 3 The following examples show various (non-limiting) applications that the basic composition according to the present invention. Example 3: Building Blocks In order to produce building elements such as, for example, breeze blocks, curbs or other prefabricated elements, the composition according to the invention is mixed with filler granules, sand, gravel and gravel. optimal by respecting the typical formulation rules to obtain a granular stack with maximum compactness.
    [0007] Table 4 below gives two typical mortar formulations (HP2A-B1 and HP2A-B2 made with standardized sand (ISO 679: 2003, according to EN 196-1) as well as a comparison with a mortar based on Portland cement (column 3034094 11 left) Mechanical performance and environmental impacts are indicated .. cif ...... t 14P2.1% 21:% Der,, ......: e - vs Ci : -, -,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, wink Plazha ta: (l 211 al! uIé 1 Caus' oun 1 HOLINESS ( ) Reio 2.41, -nia +.
    [0008] 3X4 1 ''> e i_ 'irt Coric ....- rg; ,,,,,.......... .,: 1: -:, ..., .. 11..m .., (1, -, nr ... nr., I, ..,.: ....... 11 011 5th Criteria Qi ..... 11-.1 ... t, ...'.-- 1 L i 13511 1x50 Pb: 'ii r- R.11e io- 1-1r2- Rakicti: cl-d _.2..1.:> _ 20, 1-t1s' having I: - m., I ..... F. Ratio: 23M, 3% I.D1.11 :: if Qu.:1]; eif 1.1, A.1.988 51119, F.e.1.1i .. 1 1 builds, F;; e .-., .. tiu, 2.1217.
    [0009] 1I 1,! ..r. ^ F, ... 11 F.t. 1: ... ILL c 3.: a Curlya n, J n r: In 'r 2' C ': =., 4i. : ... f.P.4> 4C: +91 act gl TF 111.13 1 (.167 I Pratt 1 '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' 'Produced Equi -7.81, .. nt Ft 1% .......... _ 0 0) 7,27 ..: cs1113 4 :: 1 ## STR5 ##, R.sub.1, .beta., 0.01, 3: 35.3. ## STR2 ## wherein: ## STR1 ## wherein: ## STR1 ## FC.4 eq - C2E4: eq 13.01 '01 111.0345 1 0.0317 - C.0470 0.041: 3: -11.2 0.0372 a tad '' u - Texicitv kg DCB el 12, 1 , 1.55. -1:, 4 13,50.12 1 Table 4 5 In the environmental impact parameters of this table the meanings are: MP: raw materials; ADP: Abiotic Potential Depletion; Sb: antimony; Human toxicity kg DCB eq: toxicity to humans expressed as dichlorobenzene equivalent. The impact values are computed from the data of the USEPA, US EPA, Supplier Lifecycle Analyzes and the Portland Cement Association. A certain number of points nevertheless penalized the technology of the present invention in the calculations of this table: the impact of water was not counted for the cement-based formula, the calculation method per ton of concrete The product favors the cementitious formula due to the addition of water, and the impact data for the sodium silicate reagent date from before 2000 for a plant with no flue gas treatment. At present, in Western Europe, sodium silicate production plants have been brought up to standard and undoubtedly have much less impact on the environment. Despite these penalties, it is found that the environmental impact of a material produced according to the invention is much lower than a conventional material and in particular at the level of CO2.
    [0010] EXAMPLE 4 In this example, various formulations (HP2A-P01 to HP2A-P08) are presented to produce 1 kg of concrete according to the invention in order to create, in particular, block-type construction elements using a press. or any other application using a concrete type paste. The mechanical performances are also indicated in Table 5 grouping these formulations. HP2A P01 HP2A_PO2 HP2A P03 HP2A PO4 HP2A P05 HP2A JO6 HP2A J07 HP2A J08 Resin Matrix MKF Quantity (g) 133 150 69 84 71 75 99 73 LHF Quantity (g) 30 56 48 40 42 49 59 Solution Silicate Ratio Molar 3,384 3,384 3,384 3,384 3,384 3,384 Geosil SB 3,384 Activation Alkaline% M ass. 34.2 34.2 34.2 342 34.2 342 342 Amount (g) 89 120 83 88 74 79 104 95 Base Type NaOH NaOH NaOH NaOH NaOH NaOH, KOH NaOH Alkaline% M easics 32 32 32 32 32 24 and II 32 Quantity (g) 44 60 42 44 40 40 37 Additive Type Tempo 12 Tempo 12 LGS 50 LGS 50 LGS 50 LGS 50 Tempo 12 Quantity (g) 5 4 8 9 7 8 3 Water Quantity (g) 44 Parameters HP2A Global ratio Si02 / M20 1.336 1.327 1.317 1.327 1.265 1.321 1.533 Ratio X / M (mol / kg) 5.105 5.10 5.100 5.105 5.213 5.187 5.193 Granules Filler Powder Clay Quantity (45 121 63 12 Roche 0/200 Quantity (g) 52 66 50 Limestone orno Quantity (g) 86 Fine Fine Sand - 0/1 Quantity (g) 618 147 White - 0/1 Quantity (g) 78 77 81 79 Yellow - 0/2 Quantity (g) 240 61 Rose - 0/2 Quantity (g) 391 248 264 394 293 Yellow - 0/4 Quantity (g) 444 454 Rose - 0/4 Quantity (g) Medium Ro se - 2/4 Quantity (g) 221 339 357 221 293 Total for Aggregates (g ) 729 636 742 727 768 756 704 733 1 kg of B ason M atric e + S rol cr activation (g) 266 360 250 264 225 236 252 264 Performance Setting at 24 H Visual OK OK OK OK OK OK OK Resistance to at 71 39 27 25 24 Compression (MP a) at 140> 40 at 28J 28 32> 35> 40 Table 5 LGS 50 is a TEMBEC solution of 50% Sodium Lignosulfonate.
    [0011] Among the fillers tested, the raw clay powder (non-calcined), the limestone powder, or the rock powder (porphyry) have a particle size of less than 200 μm.
    [0012] 3034094 13 For sand, different colors and grain sizes (fine or medium, expressed in mm) were used. On the other hand, it has surprisingly been found that the addition of kaolinite or montmorillonite in small amounts to the matrix, for example a few parts (less than 10 parts) by weight per 100 parts by weight of matrix, in the form of powder (particle size less than 200 μm), contributes in particular to a sharp increase in mechanical performance. This is the case in particular of the compressive strength which reaches or exceeds 30 MPa at 5 days and exceeds 40 10 MPa at 28 days in the HP2A-P12 and HP2A-P13 compositions (in comparison with 24 MPa at 5 days, respectively). and 35 MPa at 28 days for formulation without these additives: HP2A-P11). The results are summarized in Table 6. .. :::::::. . ,. , 34 5 ': - z- - z ... .1knere, - ..- .. ..: 6: 7.1 ... 7 a: 2-- re, 1.:.: - - ep -. .. 1.303 3 e. 1) 93 S 93 - .: tl. :. ':::' '66 ... 66 7.6: _ ..:: .. ..f. 369 36:., ". -, - 1 - e. 681 'FP. :: 1 :: - ,,: ..... 2. +': ..: rran :. There to 1! EXAMPLE 5 Manufacture of Molded Shapes Due to its low dimensional shrinkage, the composition according to the invention is The invention makes it possible to produce very precise moldings of all shapes making it possible to manufacture, in particular, large-sized tiles, molded tiles or various molded decorative shapes. If it increases the setting speed, the presence of blast furnace slag however increases the dimensional shrinkage. This parameter must be taken into account when using formulas containing more than 30% slag. The surface treatment of the products obtained can be carried out after setting to obtain, for example, a water-repellent effect or to increase the hardness. Similarly, the color can be modified by adding suitable pigments. Table 7 below gives two examples of formulations (HP2A-M01 and HP2A-M02) that can be used for applications of this type with the results obtained in terms of color, Mohs hardness, pearling effect and mechanical performance. .
    [0013] The abbreviation "Pieri H 2000" corresponds to the surface-water-repellent agent of the Grace brand, Pieri Hydroxi 2000, which gives excellent results. For colors, all kinds of mineral pigments can be used: iron oxides, ochres, etc ...
    [0014] 3034094 15 HP2A M01 HP2A M02 Resin Matrix MKF Quantity (g) 186 105 LHF Quantity (g) 56 Silicate Solution Molar Ratio 3,384 3,384 Activation% Mass 34.2 34.2 Amount (g) 124 107 Alkaline Type NaOH NaOH% Mass 32 32 Quantity (g) 62 52 Additive 1 Type Tempo 12 Tempo 12 Amount (g) 2 4 Pigment Type Activated Carbon Amount (g) 25 Parameters Global Ratio SiO2f1V120 1; 327 1350 HP2A Ratio KTvI (molfkg) 5,105 5,052 Aggregates Filler Powder Clay Quantity (g) 125 Fine White - 0/1 Quantity (g) 93 Yellow - 0/2 Quantity (g) 188 Ro se - 0/2 Amount (g) 372 Yellow - 0/4 Quantity (g) 313 Medium Rose - 2/4 Quantity (g) 186% Aggregates Aggregates 626 651 Matrix + Activation Solution 372 320 Treatment Type Water Repellent Surface Water Repellent Name Pieri H 2000 Pile H 2000 Spraying Mode Spraying Do se (g / m2) 200 200 Results Color Earth Anthracite Finished product Bead effect Excellent Excellent Hardness Mohs 3 3 Setting 24H OK OK Re sistanc e Compression ( 28J) 27 MPa 35 MPa Table 7 Example 6: Manufacture of Extruded Elements The composition according to the invention, because of its compatibility with raw clays, makes it possible to produce forms by cold extrusion. The very fast setting speed must be taken into account when conducting the process, especially in the presence of accelerator components. Solid forms such as hollow shapes are feasible, the extrusion paste having a behavior very close to conventional raw clay pastes. As with other applications, pigments or other adjuvants may be added to achieve a particular effect. On the other hand, after curing, the products can also be surface treated. Table 8 gives two examples of formulations (HP2A-X01 and HP2A-X02) applicable in extrusion and the mechanical performance obtained. HP2A_X01 HP2A_X02 MKF Matrix Resin Amount (g) 168 181 LHF Amount (g) 45 Silicate Solution Molar Ratio 3,384 3,384 Activation Alkaline% Masic 34.2 34.2 Amount (g) 109 153 Base Type NaOH NaOH Alkaline% M as 32 Quantity (g) 59 74 Additive Type Tempo 12 Tempo 12 Amount (g) 7 6 Parameters Ratio Global SiO2fM2O 1.264 1.407 HP2A Ratio XaV1 (molfkg) 5.075 5.058 Aggregates Powder Clay Amount (g) 285 541 Fine White Sand - 0 / 1 Quantity (g) 372% Aggregates Aggregates 65.7 54.1 Extrusion Pile Matrix + Activation Solution 33.6 45.3 Raw Earth 28.5 54.1 Total Clays 45.3 72.2 Performance Setting at 24H Visual OK OK Resistance at 7J> 30 28 at Account ssion (1V1P a) at 28J> 30> 30 Percentages are percentages by mass.
    [0015] Table 8 Example 7: Manufacture of expanded blocks The process according to the present invention allows the production of expanded blocks by adding to the paste a reagent such as aluminum powder, a foaming agent as well as a foam stabilizer. The aluminum powder is introduced just before the end of the kneading. The advantage of starting from a composition according to the invention is notably related to the setting speed which makes it possible to avoid steaming. Table 9 gives three examples of formulations (HP2A-SPO1 to HP2A-SP03) with the results obtained in particular the mechanical performances and the density of the finished product (before and after maturation). The formulation HP2A-SPO3 (left column) also includes sawdust (medium: 1-5 mm) to obtain a composite material containing plant "aggregates". HP2A SP01 HP2A SP02 HP2A SP03 MKF Matrix Resin Quantity (g) 180 120 330 LHF Quantity (g) 70 80 120 Silicate Solution Molar Ratio 3,384 3,384 3,384 Activation% Mass 34.2 34.2 34.2 Quantity (g) 172 130 300 Alkaline Type NaOH NaOH NaOH% Mass 32 32 32 Amount (g) 83 70 150 Additive 1 Type Tempo 12 Triton X Tempo 12 Amount (g) 4 2.5 6 Additive 1 Type Emulsion Stab Amount (g) 3.5 Additive 1 Type Powder Al Quantity (g) 0.8 Parameters Global Ratio Si028120 1.356 1.268 1.327 HP2A Ratio Mil (mol / kg) 5.220 5.077 5.105 Aggregates Powder Clay Amount (g) 50 Perlite (iril) Volume (ml) 1000 Sawdust (Medium) Quantity (g) 300 Limestone Powder 0/200 pu Quantity (g) 400 Results Density kg / L 1,1 0.9 1.8 Compressive Strength at 28J> 10 MP a> 5 MP to 15 MP a 10 Table EXAMPLE 8 Application for Glues and Putty The composition according to the invention can be used in the form of a two-component formulation to be mixed during use: two exe mples (HP2A-COLO1 and HP2A-COL02) are given in Table 10, with different A and B components.
    [0016] Thus applications for adhesives, sealants, and sealing mortars are quite possible, with a very practical application for the user, comprising the reaction by mixing the two components A and B in the form of ready-to-use pasta. 'employment.
    [0017] Geosil SB is a ready-to-use activation solution marketed by WOELLNER, containing the alkali silicate and the alkaline base. Limestone: here is a fine limestone powder of particle size less than 200pm. HP2A_COD: 11 HP2A COLO2 Component A Campantant B Component A Compass ant BM etaka olin Flashed Quantity (g) 100 50 Slag Blast Furnace Quantity (g) 50 Silicate Ratio Molar 3,384 Ge osi1 SB Alkaline% Mass 34,2 Quantity (g) 65 100 Base Type NaOH Alkaline% Mass 30 Amount (g) 35 Additive Type Tempo 12 Tempo 12 Tempo 12 Tempo 12 Amount (g) 1 2 2 2 Water Amount (g) 40 Limestone Quantity (g) 100 100 Setting 24H Visual Yes Yes Re This 100% mineral "glue" has the advantage of non-flammability and absence of volatile organic compounds, compared with glues containing products and / or organic solvents. It is also compatible with the other mineral building elements and makes it possible, for example by injection with two cartridges containing components A and B, respectively, a repair-type operation, joining of construction elements (sealing ) or coating a surface. In summary, tables 11 and 12 below group together the various advantages found by the inventors between the materials obtained by the process according to the present invention and the process using Portland cement (Table 10) and processes using terracotta (Table 12).
    [0018] 3034094 19 Properties Portland cement Invention Setting time> 3 h 10 - 60 min Time to obtain 50% of Rc28J 7 - 14 J 1 - 2 J Fire resistance 650 ° C 1000 ° C Flame retardant effect Low Strong Sulfate ion resistance Low Very strong Resistance to chloride ions Medium Very strong Anticorrosive protection of reinforcement steel Medium term Long term Dimensional removal Medium Very low Adhesive properties on stone material Medium Very high capacity to integrate clay into formulations Very low Important Mechanical performance with materials Average Very good organic Water vapor exchange capacity Low Important Glossy appearance of the surface No Yes Natural resource consumption (including energy) Medium Low Environmental impact (CO2, S02, etc ...) High Low Table 11 Properties Terracotta Invention Complexity of the plant High Low Production operation Cooking T ° Ambient Compatibility with aggregates var (Non-Vegetable Fibers, ...) Variety of Shapes Achievable Low Significant Variety of colors achievable Low Significant Dimensional Shrinkage Medium Very Low Glossy Surface Appearance No Yes Table 12 5
    权利要求:
    Claims (21)
    [0001]
    REVENDICATIONS1. Composition for a construction material comprising a matrix substantially containing an alumino-silicate-based compound, such as a metakaolin, and an alkaline activation solution, characterized in that it contains a mass proportion of cement or clinker less than 10% (preferably less than 5%, more preferably less than 1% by weight), and in that the metakaolin is a "flashed" metakaolin (that is to say obtained by flash calcination of a clay in powder at a temperature between 600 and 900 ° C for a few seconds, followed by rapid cooling).
    [0002]
    2. Composition according to claim 1, characterized in that the alkaline activation solution comprises a source of sodium or potassium silicate (according to the cement nomenclature containing SiO2 and M20), and an alkaline base, such as NaOH and / or KOH (according to the CIMENTIER nomenclature of formula M20, M being able to represent sodium or potassium).
    [0003]
    3. Composition according to claim 1 or 2, characterized in that the silicate source of the activating solution has an SiO 2 / M 2 O molar ratio greater than 1.5, preferably greater than 3.
    [0004]
    4. Composition according to any one of claims 2 or 3, characterized in that the alkaline activation solution has an overall molar ratio SiO2 / M20 of between 0.8 and 2.5, preferably between 1.0 and 2.0, more preferably between 1.20 and 1.80, more preferably between 1.25 and 1.65.
    [0005]
    5. Composition according to any one of claims 2 to 4, characterized in that the alkaline base of the alkaline activation solution is an aqueous sodium hydroxide solution NaOH.
    [0006]
    6. Composition according to any one of the preceding claims, characterized in that the matrix comprises, mixed with the flashed metakaolin, a non-flashed metakaolin, one or more powdery mineral materials (that is to say of particle size advantageously less than 200 μm) selected from blast furnace slag, class F fly ash, chamotte and / or metakaolin scrap, wollastonite, terracotta powder, resulting, in particular scrap manufacturing brick kilns, mineral powders with pozzolanic activity, recycled glass powder, cullet, Class C fly ash or slaked lime. 3034094 21
    [0007]
    7. The composition as claimed in claim 6, characterized in that the mass concentrations of the powdery materials in said matrix, mixed with at least 20% of metakaolin are the following: less than or equal to 80%, preferably less than 80%, 60% and preferably still less than 50% for blast furnace slag, class F fly ash, chamotte and / or metakaolin scrap, wollastonite and terracotta powder, - less than or equal to at 40%, preferably less than 25%, for mineral powders having pozzolanic activity, recycled glass powder, cullet or fly ash of Class C, and less than or equal to 15%, preferably less than 10%, more preferably less than or equal to 5% for slaked lime.
    [0008]
    8. Composition according to claim 6 or 7, characterized in that the matrix comprises flashed metakaolin and blast furnace slag in a slag mass concentration of less than or equal to 30% of the total weight of the matrix.
    [0009]
    9. Composition according to any one of the preceding claims, characterized in that the relative proportions of the activating solution and the matrix are such that the total sum in moles SiO2 + M20 of the activation solution is between 3 , 5 and 6.5 mol / kg of matrix, preferably between 4.5 and 5.5 mol / kg of matrix.
    [0010]
    10. Composition according to any one of the preceding claims, characterized in that it contains one or more adjuvants, such as a superplasticizer, a water-repellent agent, a water-retaining agent or an anti-shrinkage agent.
    [0011]
    11. Composition according to any one of the preceding claims, characterized in that it contains one or more powdered mineral additives chosen from kaolin, raw clay powder, zinc oxide, plaster. , fused aluminous cement, titanium dioxide, an ettringitic binder, a fluorosilicate such as sodium hexafluorosilicate, in a concentration of preferably less than 20 parts by weight, more preferably between 0.5 and 10 parts by weight, for 100 parts by weight of the matrix.
    [0012]
    12. Composition according to claim 11 characterized in that the raw powdered clay comprises mainly kaolinite or montmorillonite.
    [0013]
    13. A method of producing a building material comprising mixing the constituents of the composition according to any one of the preceding claims 3034094 22 with aggregates selected from fillers, powders, sand, gravel chippings, and / or or fibers, and possibly pigments.
    [0014]
    14. A process for producing a building material comprising mixing the composition according to any one of claims 1 to 12 with raw clay, preferably in proportions of up to 70% by weight, more preferably up to 60% by weight of the material, and cold extrusion or cold molding of said mixture.
    [0015]
    15. A method of producing a building material comprising mixing the composition of any one of claims 1 to 12 with "granules" or fibers of plant origin, such as sawdust, chips and fibers. of wood, straw, hemp, flax, cork or perlite.
    [0016]
    16. Process for producing an expanded construction material comprising mixing the composition according to any one of claims 1 to 12 with an expansive or foaming agent, such as aluminum powder. 15
    [0017]
    17. Use of the composition according to any one of claims 1 to 12 or the method according to one of claims 13 or 14 for the production of coating elements, in particular floor coverings, such as tiles, slabs , pavers or curbs, wall claddings, such as interior or exterior facade elements, cladding boards, cladding elements, or roofing tiles, for producing extruded or molded building modules , such as bricks, or for the realization of various extruded shapes.
    [0018]
    18. Use of the composition according to any one of claims 1 to 12 or the process according to claim 15 for the production of composite materials, such as prefabricated panel construction panels, prefabricated blocks such as lintels of door or window, prefabricated wall elements, or any other prefabricated building element.
    [0019]
    19. Use of the composition according to any one of claims 1 to 12 or the process according to claim 16 for the production of insulation modules, such as partition panels, or light insulating building modules (mass volume less than 1.5 kg / L, preferably less than 1.2 kg / L, more preferably less than 1.0 kg / L, more preferably less than 0.7 kg / L).
    [0020]
    20. Use of the composition according to any one of claims 1 to 12 for the realization by additive manufacturing, such as by means of a 3D printer, building elements, buildings or houses, or objects of decoration.
    [0021]
    21. Use of the composition according to any one of claims 1 to 12 in the form of a two-component system with either on the one hand the constituents in solid form, and on the other hand the constituents in liquid form, either the constituents in the form of two pastes, for the realization of sealant, glue or mortar. 10
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    同族专利:
    公开号 | 公开日
    CN107646025A|2018-01-30|
    HK1249892A1|2018-11-16|
    WO2016156722A1|2016-10-06|
    US20180111878A1|2018-04-26|
    CN107646025B|2021-11-26|
    EP3936487A1|2022-01-12|
    EP3936487A4|2022-01-12|
    EP3274315B1|2021-08-18|
    EP3274315A1|2018-01-31|
    PT3274315T|2021-09-08|
    ES2885865T3|2021-12-15|
    US10544060B2|2020-01-28|
    FR3034094B1|2020-10-09|
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    法律状态:
    2016-03-21| PLFP| Fee payment|Year of fee payment: 2 |
    2016-09-30| PLSC| Publication of the preliminary search report|Effective date: 20160930 |
    2017-03-22| PLFP| Fee payment|Year of fee payment: 3 |
    2018-03-23| PLFP| Fee payment|Year of fee payment: 4 |
    2020-03-19| PLFP| Fee payment|Year of fee payment: 6 |
    2021-03-23| PLFP| Fee payment|Year of fee payment: 7 |
    2021-08-20| OR| Opposition filed|
    优先权:
    申请号 | 申请日 | 专利标题
    FR1552615A|FR3034094B1|2015-03-27|2015-03-27|COMPOSITION FOR CONSTRUCTION MATERIAL BASED ON METAKAOLIN, ASSOCIATED MANUFACTURING PROCESS AND USE FOR THE REALIZATION OF CONSTRUCTION ELEMENTS|FR1552615A| FR3034094B1|2015-03-27|2015-03-27|COMPOSITION FOR CONSTRUCTION MATERIAL BASED ON METAKAOLIN, ASSOCIATED MANUFACTURING PROCESS AND USE FOR THE REALIZATION OF CONSTRUCTION ELEMENTS|
    EP21184111.9A| EP3936487A1|2015-03-27|2016-03-25|Composition for construction material made of metakaolin, associated manufacturing method and use for the production of construction elements|
    CN201680018574.9A| CN107646025B|2015-03-27|2016-03-25|Composition for metakaolin building materials, associated method for manufacturing said composition and use for producing building elements|
    PCT/FR2016/050689| WO2016156722A1|2015-03-27|2016-03-25|Composition for metakaolin construction material, related method for manufacturing said composition, and use for producing construction elements|
    PT167174259T| PT3274315T|2015-03-27|2016-03-25|Composition for metakaolin construction material, related method for manufacturing said composition, and use for producing construction elements|
    US15/561,875| US10544060B2|2015-03-27|2016-03-25|Composition for metakaolin construction material, related method for manufacturing said composition, and use for producing construction elements|
    ES16717425T| ES2885865T3|2015-03-27|2016-03-25|Composition for construction material based on metakaolin, associated manufacturing process and use for the realization of construction elements|
    EP16717425.9A| EP3274315B1|2015-03-27|2016-03-25|Composition for metakaolin construction material, related method for manufacturing said composition, and use for producing construction elements|
    HK18109291.7A| HK1249892A1|2015-03-27|2018-07-18|Composition for metakaolin construction material, related method for manufacturing said composition, and use for producing construction elements|
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