Patent Grant
10544060
This invention relates to the field of construction materials, and more particularly relates to new compositions for construction materials, the associated methods thereof and the uses thereof for the carrying out in particular of construction elements or modules.
Cement, such as Portland cement, is a very widely-used material in the field of construction. However this cement, although it is of high performance, requires, for the manufacture thereof, on the one hand, the consumption of many resources and, on the other hand, produces a non-negligible quantity of pollutants that are responsible, among others, for climate warming and acid rain. Finally, its service life, although long, is limited by the multiple degradations, in particular linked to atmospheric pollution, that it can be subjected to over time. All of these particularities make Portland cement increasingly less present in a sustainable development approach.
There are alternatives to conventional construction materials but they only partially meet the necessary performance requirements. In addition, their high economic cost is often a limit for large use.
For example geopolymers were invented around the end of the 1970's by Professor Davidovits. Their properties in terms of durability, mechanical performance and sustainable development have recently brought these new generation binders to stage front.
A geopolymer is formed from a mineral matrix comprised of silica and of alumina having reaction sites whereon cross-linking agents are made to react contained in a solution referred to as activating, generally alkaline. This reaction produces a gel with a poly(silico-oxo-aluminate) base which coats the granulates and hardens as the reaction progresses, until monolithic block is obtained comprised of a “glass” wherein the granulates are covered. However the methods for producing these geopolymers are either hardly adaptable industrially and/or use expensive products. The reactions are generally carried out with a heating of the constituents.
An example of manufacturing at ambient temperature of geopolymeric cement with a silico-aluminous fly ash (referred to as class F) is described in patent EP 2061732 B1 of J. Davidovits. However the base material, the silica-aluminous fly ash (referred to as class F), coming from coal-fired power plants, is a material that is not widely available in France.
In another more recent patent application FR 2966823 of the same inventor is described a method for manufacturing a binder or geopolymer cement comprising a first step of treatment of geologic elements rich in iron oxides and in ferro-kaolinite at a temperature from 600 to 850° C. for several hours, during which the ferro-kaolinite becomes ferro-metakaolin, then in a second step of having them react with a reaction medium of the Ca-geopolymeric type at ambient temperature or less than 85° C. The examples of this document indicate that the geopolymeric precursor which here is ferro-metakaolin is prepared during a long thermal treatment (calcination at 750° C. for 3 hours, followed by crushing) and therefore consume a substantial amount of energy.
Moreover document US 2012/0192765 A1 presents formulations of geopolymer based on a metakaolin M1200S produced according to the flash furnace AGS method. The calcination characteristics are indicated in the patent as being a temperature chamber 900 to 1000° C. bringing the kaolin to 750 to 850° C. for a very short period of time (not precisely indicated in this text).
This metakaolin M1200S has a high reactivity but its flash calcination mode produces a very fine metakaolin (paragraph [0024] indicates a D50 between 1 and 2 μm) having in particular a very high water demand (1650 g/kg in the Marsh funnel, according to the technical sheet). The required quantity of activation solution is therefore notoriously high: in particular a (M2O+SiO2)/matrix ratio of 11.3 mol/kg (for the formulation “ex1”) and of 10.6 mol/kg with a substantial use of superplasticiser (for the formulation “ex14”), (see the comparative tables further on).
However, the activation solution, containing soda and sodium silicate, represents a substantial proportion of the economic cost and of the environmental impact. As such the production of a tonne of soda requires more than 20 MJ of energy and 1.3 T eq CO2 of a carbon footprint responsible for climate warming. In addition, soda represents, due to its substantial corrosivity, the most dangerous constituent in the formulations of geopolymers. Finally, the activation solution, through its content in saline elements is responsible for the efflorescence effects observed in geopolymers. It is therefore suitable to limit the quantities of activation solutions in the formulations to a minimum.
This invention has for purpose to overcome the disadvantages of prior art by proposing a composition for a construction material from materials that are easily available and reactive, and with a low ecological impact: in particular that do not require any long and expensive thermal treatment.
Another purpose of the invention is to propose a composition for a construction material with a reduced quantity, and even an absence of cement or clinker, that can be used for the confection of various construction modules or elements, by moulding or extrusion.
Another purpose of the invention is to propose a composition for a construction material that can be implemented in a method for manufacturing construction modules or elements in a mixture with unfired clay, without requiring firing.
To this effect, this invention proposes a composition for a construction material comprising a matrix predominantly containing an aluminium silicate compound, such as a metakaolin, and an alkaline activation solution, this composition is characterised in that it contains less than 10 wt. % cement or clinker, preferably less than 5%, more preferably less than 1% by weight, and in that the metakaolin is a “flashed” metakaolin (i.e. obtained via flash calcination of a powdered clay at a temperature between 600 and 900° C. for a few seconds, followed by a fast cooling), and in that the alkaline activation solution comprises a source of sodium or potassium silicate (according to the cement nomenclature containing SiO2 and M2O), and an alkaline base, such as NaOH and/or KOH, (noted as M2O according to the cement nomenclature, with M able to represent the sodium or the potassium), with the relative proportions of the activation solution and of the matrix being such that the total sum in SiO2+M2O moles of the activation solution is between 3.5 and 5.5 mol/kg of matrix.
Flash metakaolin (also called flashed metakaolin) is obtained via flash calcination of a powdered clay at a temperature between 600 and 900° C. for a few seconds, followed by a fast cooling, contrary to “conventional” metakaolin which is obtained by calcination in a rotary furnace for at least 5 hours. The manufacture thereof requires much less energy, is a method with a low CO2 emission and is less complex than that of conventional metakaolin since the heating period lasts only a few seconds and no crushing afterwards is required. In addition, preparation of the clay before the thermal treatment is minimal. Its environmental impact is therefore lower and its cost is not as high.
This flash metakaolin is highly reactive. The inventors have observed that the water demand (less than 600 g/kg measured in a Marsh funnel) and in activating reagents is much less substantial when flashed metakaolin is used, by about at least 50% in activating reagent compared to conventional metakaolins.
(see hereinafter comparative table no. 2)
Flash metakaolin has until now been used as an additive in cement compositions in minority weight proportions (less than 20%) with Portland cement for example.
The inventors surprisingly discovered that such a flash metakaolin can react at ambient temperature (less than 30° C.) with the alkaline activation solution by giving materials with interesting properties, such as that described further on.
The alkaline activation solution advantageously comprises a source of sodium or potassium silicate (according to the cement nomenclature contains SiO2 and M2O), and an alkaline base, such as NaOH and/or KOH, (according to the cement nomenclature of formula M2O, with M able to represent the sodium or the potassium).
Preferably, the source of silicate (i.e. the sodium or potassium silicate) of the activation solution has a SiO2/M2O molar ratio greater than 1.5, preferably greater than 3.
Preferably, the alkaline activation solution has a global SiO2/M2O molar ratio 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.
The activation solutions used in geopolymerisation are generally defined by their silica/alkaline ratio.
When this invention is carried out with activation solutions with silica/alkaline molar ratios (noted as SiO2/M2O) between 1.25 and 1.65 a lower propensity for the phenomenon of efflorescence is observed than with the formulations with the molar ratio less than 1.2, even less than 1, of the geopolymers of prior art, which is a substantial technical advantage. In addition, solutions with a high ratio are more stable and simpler to use.
According to an advantageous alternative of the invention, the alkaline base of the alkaline activation solution is an aqueous solution of soda NaOH. The examples mentioned further on in the description show that it is not necessary to use a very concentrated solution of soda.
In the composition according to the invention, the matrix can include, mixed with the flashed metakaolin, an unflashed metakaolin, one or several powdery mineral materials (i.e. with a granulometry advantageously less than 200 μm) which can be chosen from blast furnace slag, fly ash of class F, scraps from manufacturing chamotte and/or metakaolin, wollastonite, terra-cotta powder, coming, in particular from scraps from brickmaking, mineral powders that have a puzzolanic activity, recycled glass powder, cullet, fly ash of class C or slaked lime.
With regards to the mass concentrations of powdery materials mixed with at least 20% metakaolin in said matrix, these concentrations are advantageously as follows:
According to an advantageous embodiment of the composition of the invention, the matrix comprises flashed metakaolin and blast furnace slag in a mass concentration of slag less than or equal to 30% of the total weight of the matrix.
Preferably, the relative proportions of the activation solution and of the matrix are such that the total sum in SiO2+M2O moles of the activation solution is between 4.5 and 5.5 mol/kg of matrix, preferably between 4.5 and 5.3 mol/kg of matrix.
The activation solution can be a ready-to-use activation solution, such as the activation solution in the GEOSIL category (marketed by WOELLNER). The advantage is a simplification in the implementation since the activation solution no longer needs to be prepared on site.
The composition according to the invention can further contain one or several adjuvants, such as a superplasticiser (for example of the polyacrylate or lignosulfonate type), a water-repellent agent (for example heavy carboxylates of calcium, or with a silicone base), a water-retention agent or an anti-shrinkage agent. The term adjuvant means an addition, in particular of organic nature, with the purpose of modifying certain basic properties, in proportions less than 5% by weight of the composition. The composition can further include colorants or pigments.
The composition according to the invention can also contain one or several powdered mineral additives, chosen from kaolin, powdered unfired clay, zinc oxide, plaster, high aluminous cement, titanium oxide, an ettringite binder, a fluorosilicate such as sodium hexafluorosilicate, with the purpose of modifying certain basic properties, in a concentration 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,
The powdered unfired clay can predominantly contain kaolinite or montmorillonite.
This invention also relates to various methods for producing a construction material using the basic composition described hereinabove. More particularly:
All of these methods can be implemented at temperatures between about 0° C. and about 30° C., without requiring thermal treatment.
More precisely, the matrix, produced using the components presented hereinabove, is mixed with the activation solution, itself prepared according to the formula indicated. The two together thus form the composition according to the invention, having the form of a thick liquid, which is then mixed with one or several neutral compounds such as granulates or fibres, of which it will form the binder. The additives, added to the mixture, make it possible to provide it with certain particular additional properties. This binder, which resembles a resin, makes it possible after reaction, to form with the “granulates” and the “additives” a coherent monolithic assembly that has new properties with respect to the materials of prior art, in particular a short setting time, and very low dimensional shrinkage, a shiny surface appearance.
This present invention also relates to the possible multiple uses of said composition according to the invention or methods described hereinabove, and in particular:
These last two uses are very difficult to implement using compositions with a cement base due to the hydration reaction of this material as soon as it is mixed with water, which requires synchronisation between the adding of water, mixing and depositing the paste,
This invention shall now be described in more detail and illustrated using non-limiting examples, hereinafter.
In the examples, the abbreviations in table 1 are used for the composition of the matrix:
The metakaolin forms the base from which the formulation is established. Several types of metakaolin exist in the market. Table 2 hereinbelow shows a few typical metakaolins.
The chamotte FX is a manufacturing coproduct, this is dust emitted during the manufacture of metakaolin or of chamotte in a rotary furnace. These dusts are captured by a filtration system and conditioned. As “quasi waste”, they have a very low environmental impact and a competitive economic cost.
The two Argeco metakaolins are produced according to the method, of the Argeco Développement company, of flashing described hereinabove. Produced from an impure clay according to a method that does not consume much energy, their environmental impact and their cost are low.
The Metastar 501 and Argical M1000 metakaolins are produced using a very pure kaolinite according to the conventional method of calcination with a ball in a rotary furnace and crushing. They are much more expensive than the preceding products.
Finally, Argical M 1200S is produced using very pure dried and crushed kaolinite in a so-called flash furnace according to the method of Imerys. This method is different from the Argeco method and does not comprise a fast cooling step (of the quenching type). The final product is very expensive due to its purity and the method of manufacture. The reactivity to the lime is however very high.
Table 3 hereinbelow shows the results of the reactivity tests of the various types of metakaolin. This test is carried out according to a simple protocol: to a given quantity of metakaolin is added a sufficient quantity of activation solution (sodium silicate of the N type and soda at 32%, with a SiO2/Na2O molar ratio of 1.15) then a given quantity of fine granulates (sand and filler). The mortar obtained must be rather liquid and there is no granular optimisation in order to correctly distinguish the performance of the metakaolin.
Table 3 shows that metakaolin of the MKF N type (Argicem) has the best mechanical performance for a lower quantity of activation solution.
The granulometry and the particular water demand of Argical M1200S and Metastar 501 metakaolins have the consequence of requiring a very large quantity of catalyst (i.e. alkaline activation solution). At an equivalent quantity of catalyst, the rheology linked to the use of M1200S requires adding a substantial quantity of water with respect to MKF N, which dilutes the catalyst and fully inhibits the reaction.
The activation solution represents a non-negligible portion in the price and in the environmental impact, the formulations with a base of metakaolin MKF N and CFX therefore have the lowest costs and environmental impacts.
The formulations of the examples hereinafter are primarily based on the MKF N from Argeco and the CFX from Imerys.
The “flashed” metakaolin used MKF N of the brand ARGICEM® from Argeco Développement is a product that has a high BET specific surface area (between 5 and 16 m2/g (NF ISO 9277). Its average granulometry is D50=20-30 μm according to the standard NF P 18-513 and it has a low water demand between 300 and 500 g/kg (measured according to the Marsh funnel method).
In all of the examples hereinafter the alkaline silicate as well as the alkaline base are in aqueous solution, the concentrations thereof are expresses as a % by weight in this solution. Most of the time no adding of water other than the water of these solutions that constitute the activation solution is required. The quantity of water is therefore as reduced as possible. The weight ration of the water E over the total dry matter MSR of the binding composition (here denoted as “resin”, or binder) is more preferably less than 1, but variable according to the type of matrix. For example E/MSR is advantageously less than 0.6 for a matrix constituted of flashed metakaolin alone, and an E/MSR ratio close to 0.8 for a matrix containing a mixture of flashed metakaolin and unflashed metakaolin.
Table 4 hereinafter shows varied compositions according to the invention: FR01 to FR11, with an indication of the SiO2/M2O molar ratio of the activation solution and an indication of the X/M ratio in mol/kg (total sum in SiO2+M2O moles of the activation solution per kg of matrix).
The mechanical performance, obtained after mixing the binding composition (denoted here as “resin”, or binder) with the granulates, then moulding and maturing time at a temperature of 20° C. are given in terms of resistance to compression for a cylinder 40 mm in diameter for 80 mm in height. Contrary to the formulas given further on in the applications, the granulates used in these formulas have only a neutral filling role and the stacking thereof was therefore not optimised.
Tempo 12 is a water reducer marketed by Sika, of the polyacrylate type.
The fine sand is Fontainebleau fine sand with a granulometry less than or equal to 1 mm, the fine limestone powder has a granulometry less than 200 μm,
In this example the setting (setting <24 h) was visually estimated.
Table 5 hereinafter shows the formulations FR-N1 and FR-N2 which have lower performance than those of the example 1. It was observed that the resin composition FR_N1 is highly alkaline and produces efflorescences, and the composition FR-N2 with an X/M ratio greater than 2 has a low mechanical resistance (Rc at 28 days <5 MPa). This example shows the importance of the preferred SiO2/M2O and X/M ratios, in order to improve the properties of materials prepared using the composition according to the invention and the performance thereof.
The following examples show various applications (non-limiting) that implement the base composition according to this invention.
In order to produce construction elements such as, for example, building blocks, edging or other prefabricated elements, the composition according to the invention is mixed with granulates of the filler, sables, chippings and gravel type in an optimum manner by complying with the typical formulation rules in order to obtain a granular stack that has a maximum compactness.
Table 6 herein below gives two typical formulations of mortar (HP2A-B1 and HP2A-B2 produced with standardised sand (ISO 679:2003, according to the standard EN 196-1) as well as a comparison with a mortar with a Portland cement base (left column). The mechanical performance as well as the environmental impacts are indicated.
In the environmental impact parameters of this table the meanings are: RM: raw materials; ADP: Abiotic Depletion Potential; Sb: antimony; Human toxicity kg DCB eq: toxicity for Humans expressed in dichlorobenzene equivalent.
The impact values are here calculated using in particular data from ADEME, the American EPA, Life Cycle Analyses from the suppliers and from the Portland Cement Association. A certain number of points however have penalized the technology of this invention in the calculations of this table: the impact of water was not counted for the formula with a cement base, the method of calculation per tonne of concrete produced favours the formula with cement due to the adding of water and the impact data for the sodium silicate reagent date before 2000 for a factory without fume treatment. Currently, in Western Europe sodium silicate production factories have been brought to standard and without a doubt have much less impact on the environment. Despite these penalties, it is observed that the environmental impact of a material produced according to the invention is much less than a conventional material and in particular on CO2.
In this example various formulations are presented (HP2A-P01 to HP2A-P08) in order to produce 1 kg of concrete according to the invention in order to create in particular construction elements of the building block type using a press, or any other application that uses a paste of the concrete type. The mechanical performance is also indicated in table 7 which groups these formulations together.
LGS 50 is a solution of the TEMBEC brand of Sodium Lignosulfonate at 50%. Among the fillers tested, unfired clay powder (non-calcined), lime powder, or rock powder (porphyry) have a granulometry less than 200 μm.
For sands, various colours and granulometries (fine or medium, expressed in mm) were used.
Moreover, it was surprisingly observed that adding kaolinite or montmorillonite, in a small quantity in relation to the matrix, for example a few parts (less than 10 parts) by weight for 100 parts by weight of matrix, in the form of powder (granulometry less than 200 μm), contributes in particular to a sharp increase in mechanical performance. This is the case in particular of the resistance to compression that reaches or exceeds 30 MPa at 5 days and exceeds 40 MPa at 28 days in the HP2A-P12 and HP2A-P13 compositions (in comparison respectively with 24 MPa at 5 days and 35 MPa at 28 days for a formulation without these additives: HP2A-P11). The results are grouped together in table 8.
Thanks to its low dimensional shrinkage, the composition according to the invention makes it possible to produce very precise moldings of all shapes making it possible to manufacture in particular tiles of large size, moulded tiles or various decorative moulded forms. Although it increases the setting speed, the presence of blast furnace slag however increases the dimensional shrinkage. This parameter has to be taken into account in the case of a possible use of formulas containing more than 30% slag,
The surface treatment of the products obtained can be carried out after the setting in order to obtain, for example, a water repellent effect or to increase the hardness thereof. Likewise, the colour can be modified by adding suitable pigments. Table 9 hereinbelow provides 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 colour, Mohs hardness, beading effect and mechanical performance.
The abbreviation “Pieri H 2000” corresponds to the water-repellent surface agent, of the Grace brand, Pieri Hydroxi 2000 which provides excellent results. For the colours, all sorts of mineral pigments can be used: iron oxides, ochres, etc.
The composition according to the invention, due to its compatibility with unfired clays, makes it possible to produce forms via cold extrusion. The very fast setting speed has to be taken into account when using the method especially in the case of the presence of accelerating components. Sold forms as well as hollow forms can be produced, with the paste to be extruded having a behaviour that is very close to pastes of conventional unfired clays.
As with the other applications, pigments or other adjuvants can be added for the purpose of obtaining a particular effect. Moreover, after hardening, the products can also be subjected to a surface treatment. Table 10 provides two examples of formulations (HP2A-X01 and HP2A-X02) that can be applied in extrusion as well as the mechanical performance obtained.
The method according to this invention allows for the production of expanded blocks by adding to the paste a reagent such as aluminium powder, a foaming agent as well as a foam stabiliser. The aluminium powder is introduced just before the end of mixing. The interest in using a composition according to the invention is in particular linked to the setting speed that makes it possible to avoid curing.
Table 11 provides three examples of formulations (HP2A-SP01 to HP2A-SP03) with the results obtained in particular the mechanical performance and the density of the finished product (before and after maturation).
The formulation HP2A-SP03 (left column) furthermore includes sawdust (medium: 1-5 mm environ) which makes it possible to obtain a composite material containing plant “granulates”.
The composition according to the invention can be implemented in the form of a two-component formulation to be mixed at the time of use: two examples (HP2A-COL01 and HP2A-COL02) are provided in table 12, with different components A and B, as well as the examples HP2A-COL3 and HP2A-COL04 in table 13.
Applications for sealing glues, mastics, and mortars can as such be entirely considered, with a very practical implementation for the user, comprising the reaction by mixing two components A and B in the form of ready-to-use pastes.
Geosil SB is a ready-to-use activation solution marketed by WOELLNER, containing the alkaline silicate and the alkaline base.
Lime: this here is a fine lime powder with a granulometry less than 200 μm or 315 μm.
In the two examples of table 12, the ratio global SiO2/M2O of the alkaline solution is 1.25 and the X/M ratio is 5.1 mole/kg of matrix.
Two other formulations of glues according to the invention are presented in table 11 hereinafter.
The Sika® G-225 additive is a thinner of the polycarboxylate type.
The Tempo 12 additive is a superplasticiser with an acrylic copolymer base.
Such 100% mineral glues have the advantage of non-flammability and an absence of Volatile Organic Compounds, with respect to glues containing organic products and/or solvents. They are furthermore compatible with the other mineral construction elements and make it possible to produce, for example by injection by means of two cartridges respectively containing the components A and B, an operation of the repair type, of joining construction elements (sealing) or coating of a surface.
Materials with a low density such as, for example, hemp, wood fibre, expanded clay, pozzolana or perlite are porous. This often results in a problem of cohesion when they are bonded with a hydraulic binder. Indeed, the migration of the water inside the granulate decreases the output of the hydraulic setting reaction in particular at the interface between the granulate and the binding phase. However the geopolymerisation reaction does not consume but produces water. The migration of the water to the granulates will therefore not produce this lack of cohesion.
The other advantages of geopolymers on this application are in particular the good adhesive properties, the very low shrinkage when drying, the inhibition of mould and the repulsive nature for rodents and insects (due to the alkalinity and the presence of carbonates, as well as very high flame-retardant capacities.
Several formulations have therefore been tested that include shive (hemp), or perlite. Table 14 herein below shows a few examples.
It is therefore observed that it is possible to obtain composites that have good performance with low volumes of binder, less than what is usually practiced for conventional binders.
For the composite with a perlite base, the resistance to compression is greater than a building block of class B80 (8 MPa) and is largely sufficient for the block to be able to be considered as a supporting block. There is therefore a margin for manoeuvre for inserting empty spaces up to 50% in a block produced according to the formula PERL02. A supporting block is as such obtained, of a class between a B40 and B60, having an apparent density of approximately 400 kg/m3, i.e. more than 2 times less than the apparent density of a concrete building block B40 (900 kg/m3).
The densities for shive blocks are very satisfactory, the shive fibres are highly integral with the whole and resist pulling off well, including at the angles. Their solidity is sufficient to build large-size insulation plates to be screwed or glued.
In summary, tables 15 and 16 hereinafter group together the various advantages observed by the inventors between the materials obtained by the method according to this invention and respectively the method implementing Portland cement (table 15) and methods using terra-cotta (table 16).
| Number | Date | Country | Kind |
|---|---|---|---|
| 15 52615 | Mar 2015 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/FR2016/050689 | 3/25/2016 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2016/156722 | 10/6/2016 | WO | A |
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|---|---|---|---|
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| 5601643 | Silverstrim et al. | Feb 1997 | A |
| 7229491 | Davidovits et al. | Jun 2007 | B2 |
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| Entry |
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| Number | Date | Country | |
|---|---|---|---|
| 20180111878 A1 | Apr 2018 | US |
