BINDER COMPOSITION COMPRISING POZZOLANIC MATERIAL AND FINE FILLER

Abstract

A binder composition in dry weight percentage comprising a) between 1% and 30% of Portland cement, lime or a mixture thereof, b) between 1% and 40% of ground granulated blast furnace slag, c) between 20% and 50% of at least one pozzolanic material, d) between 20% and 65% of at least one filler, e) between 0.5% and 10%, relative to the total weight of components a, b, c, and d, of at least one activator, f) between 0.05% and 1.5%, relative to the total weight of components a, b, c and d, of at least one water reducer polymer, the filler being a mixture between 10% and 90% in weight of particles having a d.sub.50?0.05 ?m and <8 ?m, and between 10% and 90% in weight of particles having a d.sub.50?8 ?m and <200 ?m, the filler mixture weight percentages in respect to total weight of the filler.

Claims

1. A binder composition comprising: a. between 1% and 30% in dry weight of Portland cement, lime or a mixture thereof; b. between 1% and 40% in dry weight of ground granulated blast furnace slag; c. between 20% and 50% in dry weight of at least one pozzolanic material; d. between 20% and 65% in dry weight of at least one filler; e. between 0.5% and 10% in dry weight, relative to the total weight of components a, b, c and d, of at least one activator; f. between 0.05% and 1.5% in dry weight, relative to the total weight of components a, b, c and d, of at least one water reducer polymer; said filler being a particles mixture of: between 10% and 90% in weight, in respect with the total weight of the filler, of particles having a d.sub.50 greater than or equal to 0.05 ?m and strictly less than 8 ?m, and between 10% and 90% in weight, in respect with the total weight of the filler, of particles having a d.sub.50 greater than or equal to 8 ?m and strictly less than 200 ?m, measurement of d.sub.50 being done by Laser diffraction analysis, also known as Laser diffraction spectroscopy, by means of Laser diffraction analyzer such as Mastersizer 2000 and commercialized by the MALVERN company, with the humid way method.

2. The binder composition according to claim 1, wherein the pozzolanic material is selected in the group comprising, silica fumes, fly ashes, calcinated schists, metakaolin, calcined illite, calcined bentonite, calcined montmorillonite, calcined smectite, biomass ashes, rice husk ashes, diatomaceous earth, grounded opal, carbonated basic oxygen furnace slag, carbonated olivine, carbonated wollastonite and mixtures thereof.

3. The binder composition according to claim 1, wherein the filler is a natural material sourcing from stone-pit.

4. The binder composition according to claim 1, wherein the activator is an alkaline metal salt.

5. The binder composition according to claim 1, wherein the water reducing polymer is selected from the group consisting of lignosulfonate polymers, melamine sulfonate polymers, naphthalene sulfonate polymers, polycarboxylic acid ether polymers, polyoxyethylene phosphonates, vinyl copolymers, methallyl ether polycarboxylic acid ether and mixtures thereof.

6. The binder composition according to claim 1, wherein at least a portion of the ground granulated blast furnace slag has a d.sub.50 less or equal to 2.5 ?m.

7. A dry concrete composition or dry industrial mortar composition comprising at least one aggregate and the binder composition according to claim 1.

8. A wet concrete composition or wet industrial mortar composition comprising at least one aggregate, the binder composition according to claim 1 and water.

9. A hardened concrete composition or hardened industrial mortar composition obtained from the wet concrete composition or the wet industrial mortar composition according to claim 8.

10. A process for preparing the wet concrete composition or wet industrial mortar composition according to claim 8 comprising a step of mixing with water, at least one aggregate and a binder composition comprising: a. between 1% and 30% in dry weight of Portland cement, lime or a mixture thereof; b. between 1% and 40% in dry weight of ground granulated blast furnace slag; c. between 20% and 50% in dry weight of at least one pozzolanic material; d. between 20% and 65% in dry weight of at least one filler; e. between 0.5% and 10% in dry weight, relative to the total weight of components a, b, c and d, of at least one activator; f. between 0.05% and 1.5% in dry weight, relative to the total weight of components a, b, c and d, of at least one water reducer polymer; said filler being a particles mixture of: between 10% and 90% in weight, in respect with the total weight of the filler, of particles having a d.sub.50 greater than or equal to 0.05 ?m and strictly less than 8 ?m, and between 10% and 90% in weight, in respect with the total weight of the filler, of particles having a d.sub.50 greater than or equal to 8 ?m and strictly less than 200 ?m, measurement of d.sub.50 being done by Laser diffraction analysis, also known as Laser diffraction spectroscopy, by means of Laser diffraction analyzer such as Mastersizer 2000 and commercialized by the MALVERN company, with the humid way method, the binder composition being prepared before the mixing step or in situ during the mixing step from at least some of the different components of the binder composition taken separately and/or under the form of premix(es).

11. The process according to claim 10, wherein the ratio water to binder composition is comprised between 0.1 and 0.5.

12. A use of the binder composition according to claim 1 for improving the fresh state rheology of wet concrete composition or wet industrial mortar composition.

13. The use of the binder composition according to claim 12, wherein the paste fresh state yield stress is comprised between 0 Pa and 200 Pa.

14. The use of the binder composition according to claim 12, wherein the paste fresh state viscosity is comprised between 0 Pa.Math.s and 5 Pa.Math.s, advantageously between 0.1 Pa.Math.s and 3 Pa.Math.s and more advantageously between 0.25 Pa.Math.s and 1.5 Pa.Math.s.

15. A use of the binder composition according to claim 1, for the preparation of precast or ready-mix concrete.

Description

DETAILED DESCRIPTION

The Binder Composition

[0046] The binder composition according to the invention comprises: [0047] a. between 1% and 30% in dry weight of Portland cement, lime or a mixture thereof; [0048] b. between 1% and 40% in dry weight of ground granulated blast furnace slag; [0049] c. between 20% and 50% in dry weight of at least one pozzolanic material; [0050] d. between 20% and 65% in dry weight of at least one filler; [0051] e. between 0.5% and 10% in dry weight, relative to the total weight of components a, b, c and d, of at least one activator; [0052] f. between 0.05% and 1.5% in dry weight, relative to the total weight of components a, b, c and d, of at least one water reducer polymer; [0053] said filler being a particles mixture of: [0054] between 10% and 90% in weight, in respect with the total weight of the filler, of particles having a d.sub.50 greater than or equal to 0.05 ?m and strictly less than 8 ?m, and [0055] between 10% and 90% in weight, in respect with the total weight of the filler, of particles having a doc greater than or equal to 8 ?m and strictly less than 200 ?m.

The Component a

[0056] The binder composition according to the invention comprises between 1% and 30% in dry weight of a component a, preferably, between 3% and 25%, more preferably between 5% and 20%.

[0057] Component a, could be Portland cement, lime or a mixture thereof.

The Component b

[0058] The binder composition according to the invention comprises between 1% and 40% in dry weight of a component b, which ground granulated blast furnace slag (GGBS) preferably, between 5% and 40%, more preferably between 15% and 40% and even more preferably between 25% and 40%.

[0059] In an advantageous embodiment, at least a portion of the ground granulated blast furnace slag has a d.sub.50 less or equal to 2.5 ?m. This embodiment is advantageous since it allows enhancing the technical effect of reducing the viscosity and increasing the compressive strength obtained with the binder composition according to the invention.

The Component c

[0060] The binder composition according to the invention comprises between 20% and 50% in dry weight of a component c, which is a pozzolanic material preferably, between 25% and 45%, more preferably between 30% and 40%.

[0061] A pozzolanic material is a material which is able to react with lime or cement, in the presence of water, so as to produce hydrates. In other words, a pozzolanic material is a material that enhances the hydraulic behavior of Portland cement and lime, a hydraulic behavior being the capacity of setting and hardening in t presence of water.

[0062] Preferably, the pozzolanic material is selected in the group comprising, preferably consisting in, silica fumes, fly ashes, calcinated schists, metakaolin, calcined illite, calcined bentonite, calcined montmorillonite, calcined smectite, biomass ashes, rice husk ashes, diatomaceous earth, grounded opal, carbonated basic oxygen furnace slag, carbonated olivine, carbonated wollastonite and mixtures thereof.

The Component d

[0063] The binder composition according to the invention comprises between 20% and 65% in dry weight of a component d, which is a filler preferably, between 25% and 50%, more preferably between 30% and 40%.

[0064] A filler is an inorganic material finely granulated which is inert. In other words, a filler is not able to react with lime or cement, in the presence of water, so as to produce hydrates.

[0065] Preferably, the filler is a limestone filler, more preferably, the filler is a natural material sourcing from stone-pit, such as calcite and its polymorphs, like aragonite or vaterite, and dolomite or precipitated calcium carbonates and mixtures thereof.

[0066] According to the invention, the filler is a particles mixture of: [0067] between 10% and 90% in weight, in respect with the total weight of the filler, of particles having a de greater than or equal to 0.05 ?m and strictly less than 8 ?m, and [0068] between 10% and 90% in weight, in respect with the total weight of the filler, of particles having a d.sub.50 greater than or equal to 8 ?m and strictly less than 200 ?m.

[0069] This filler partition allows obtaining a technical effect of reducing the viscosity and increasing the compressive strength of the binder composition and of the concrete or industrial mortars according to the invention.

[0070] In some embodiments the filler is a particles mixture of: [0071] between 20% and 80%, preferably between 25% and 50%, more preferably between 30% and 40% in weight, in respect with the total weight of the filler, of particles having a d.sub.50 greater than or equal to 0.05 ?m and strictly less than 8 ?m, and [0072] between 20% and 80%, preferably between 30% and 70%, more preferably between 40% and 65% in weight, in respect with the total weight of the filler, of particles having a d.sub.50 greater than or equal to 8 ?m and strictly less than 200 ?m.

The Component e

[0073] According to the invention, the binder composition further comprises between 0.5% and 10% in dry weight, relative to the total weight of components a, b, c and d, of at least one activator.

[0074] The content of the activator is determined in respect with the distribution of components a, b, c and d. In other words, the dry weight percentage of the activator is determined by considering that the sum of contents of components a, b, c and d represents 100% in dry weight.

[0075] Preferably, the activator is an alkaline metal salt, preferably sodium chloride, potassium chloride, lithium chloride, sodium sulfate, potassium sulfate, lithium sulfate, sodium carbonate, potassium carbonate, lithium carbonate, sodium nitrate, potassium nitrate, lithium nitrate, sodium nitrite, potassium nitrite, lithium nitrite, calcium nitrate, calcium nitrite, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, alkanolamines such as triethanolamine (TEA), triisopropanolamine (TIPA), diethanolamine (DEA) or mixture thereof, more preferably sodium sulfate.

The Component f

[0076] According to the invention, the binder composition further comprises between 0.05% and 1.5% in dry weight, relative to the total weight of components a, b, c and d, of at least one water reducer polymer.

[0077] The content of the water reducer polymer is determined in respect with the distribution of components a, b, c and d. In other words, the dry weight percentage of the water reducer polymer is determined by considering that the sum of contents of components a, b, c and d represents 100% in dry weight.

[0078] Preferably, the water reducing polymer is selected from the group consisting of lignosulfonate polymers, melamine sulfonate polymers, naphthalene sulfonate polymers, polycarboxylic acid ether polymers, polyoxyethylene phosphonates, vinyl copolymers, methallyl ether polycarboxylic acid ether, and mixtures thereof.

Optional Other Components

[0079] The binder composition is advantageously enriched with one or several other components which are ingredients, notably functional additives preferably selected in the following list:

Water Retention Agent.

[0080] A water retention agent has the property to keep the water of mixing before the setting. The water is so trapped in the wet formulation paste which improves its bond. To some extent, the water is less absorbed by the support.

[0081] The water retentive agent is preferably chosen in the group comprising: modified celluloses, modified guars, modified cellulose ethers and/or guar ether and their mixes, more preferably consisting of: methylcelluloses, methylhydroxypropylcelluloses, methylhydroxyethyl-celluloses and their mixes.

Rheological Agent

[0082] The possible rheological agent (also named a thickener) is preferably chosen in the group comprising, more preferably consisting in: starch ethers, cellulose ethers and/or gums (e.g. Welan guar xanthane, succinoglycans), modified polysaccharidespreferably among modified starch ethers-, polyvinylic alcohols, polyacrylamides, sepiolites, and their mixes.

Defoamer/Antifoams

[0083] The possible defoamer is preferably chosen in the group comprising, more preferably consisting in: polyether polyols and mixes thereof.

Biocide

[0084] The possible biocide is preferably chosen in the group comprising, more preferably consisting in: mineral oxides like zinc oxide and mixes thereof.

Pigment

[0085] The possible pigment is preferably chosen in the group comprising, more preferably consisting in: TiO.sub.2, iron oxide and mixes thereof.

Flame Retardant

[0086] Flame retardant (or flame proof agent) makes it possible to increase the fire resistance and/or to shrink the speed of flame spreading of the composition.

Air-Entraining Agents

[0087] Air-entraining agents (surfactants) are advantageously chosen in the group comprising, more preferably consisting in, natural resins, sulfated or sulfonated compounds, synthetic detergents, organic fatty acids and their mixes, preferably in the group comprising, more preferably consisting in the lignosulfonates, the basic soaps of fatty acids and their mixes, and, more preferably in the group comprising, more preferably consisting in the sulfonate olefins, the sodium lauryl sulfate and their mixes.

Retarders

[0088] Retarders are advantageously chosen in the group comprising, more preferably consisting in tartric acid and its salts: sodium or potassium salts, citric acid and its salts: sodium (trisodic citrate) and their mixes.

[0089] In addition, other components may be: [0090] Plasticizers [0091] Fibres [0092] Dispersion powders [0093] Wetting agents [0094] Polymeric resins [0095] Complexing agents [0096] Drying shrinkage reducing agents based on polyols.

[0097] The total content of these optional other components in the binder composition is preferably comprised between 0.001% and 10% by weight of the total weight of the binder composition.

The Dry Concrete Composition or Dry Industrial Mortar Composition

[0098] The invention also relates to dry concrete composition or dry industrial mortar composition, in particular tile adhesive, coating, assembling mortars, repair mortars, renders, technical mortars and mortars for floor covering comprising at least one aggregate and the binder composition described above. The dry concrete or industrial mortar composition may eventually contain other admixtures and additions.

[0099] According to the invention, dry concrete composition or dry industrial mortar composition refers to composition that are in the form of powder and ready to be mixed with water. In other words, the dry concrete composition or dry industrial mortar composition of the invention may content some moisture, but it essentially contains solid components which are intended to be mixed with water before its application.

[0100] Aggregates comprise a large category of particulate material used in construction, including sands, gravels, crushed stones, slag (not-granulated), recycled concrete and geosynthetic aggregates. They serve as reinforcement to add strength to the overall composite material.

[0101] Advantageously, said dry concrete composition or dry industrial mortar composition can also include, apart from aggregates, one or several ingredients, especially functional admixtures, additions and fibres, which can be the same as the other optional component mentioned above defined in the detailed description of the binder composition.

[0102] The total content of these optional other components in the dry concrete composition or dry industrial mortar composition is preferably comprised between 0.1% and 10% by weight of the total weight of the binder composition.

The Wet Concrete Composition or Wet Industrial Mortar Composition

[0103] The invention also refers to a wet concrete composition or a wet industrial mortar composition in particular tile adhesive, coating, assembling mortars, repair mortars, renders, technical mortars and mortars for floor covering comprising at least one aggregate, the binder composition described above and water.

[0104] In a specific embodiment, wet industrial mortar compositions are so called Ready to use mortars. Ready to use mortars are used for assembling bricks or blocks on building site. They are obtained by mixing all the elements of the composition (binder, aggregates and others components) with water directly at the mixing plant. They include a set retarding agent, allowing transport and delayed use up to several days, while maintaining its rheological and hardening properties.

The Process for Preparing Wet Concrete Composition or Wet Mortar Composition

[0105] The invention also relates to a process for preparing the wet concrete composition or wet industrial mortar composition described above comprising a step of mixing with water at least one aggregate and the binder composition described above, the binder composition being prepared before the mixing step or in situ during the mixing step from at least some of the different components of the binder composition taken separately and/or under the form of premix(es).

[0106] In other words, wet concrete composition or wet industrial mortar composition could be prepared by two distinct methods.

[0107] In a first method, the binder composition is prepared, and then mixed with the at least one aggregate. The dry concrete composition or dry mortar composition is thereafter mixed with water.

[0108] In a second method, the wet concrete composition or wet industrial mortar composition is prepared by mixing in water each component of the binder composition and the aggregates.

[0109] According to the present disclosure, the term mixing has to be understood as any form of mixing.

[0110] In a preferred embodiment a part of the binder composition and at least a part of the water are mixed together prior to the mixing with the aggregate.

[0111] In a preferred embodiment, the process is implemented with a ratio water to hydraulic binder is comprised between 0.1 and 0.5, advantageously between 0.15 and 0.45, and more advantageously between 0.2 and 0.4.

Hardened Concrete Composition or Hardened Industrial Mortar Composition

[0112] The present invention also refers to hardened concrete composition or hardened industrial mortar composition obtained from the wet concrete composition or wet industrial mortar composition described above.

The Use of the Binder Composition

[0113] The invention is also directed to the use of the binder composition described above for improving the fresh state rheology of wet concrete composition or wet industrial mortar composition in particular tile adhesive, coating, assembling mortars, repair mortars, renders, technical mortars and mortars for floor covering.

[0114] Advantageously, for the use according to the invention, the paste fresh state yield stress is comprised between 0 Pa and 200 Pa, advantageously between 5 Pa and 100 Pa and more advantageously between 10 Pa and 50 Pa.

[0115] Advantageously, for the use according to the invention, the paste fresh state viscosity is comprised between 0 Pa.Math.s and 5 Pa.Math.s, advantageously between 0.1 Pa.Math.s and 3 Pa.Math.s and more advantageously between 0.25 Pa.Math.s and 1.5 Pa.Math.s.

[0116] The invention is also directed to the use of the binder composition described above for the preparation of precast or ready-mix concrete.

EXAMPLES

Example 1: The Synergistic Effect of the Particle Size Distribution of the Filler Particles

[0117] Six pastes were prepared according to standard NF EN 196-3. The compositions are set forth in table 1 below.

TABLE-US-00001 TABLE 1 CE1 CE2 E1 CE3 CE4 E2 Component Portland 20 20 15 0 0 0 a (dry cement weight %) Lime 0 0 0 10 5 5 Component b: Standard 30 30 25 35 37.5 35 GGBS (d.sub.50 = 10 ?m) (dry weight %) Component c: Natural 30 30 30 35 37.5 30 pozzolan (dry weight %) Component Fine 20 0 10 20 0 10 d (dry limestone weight %) filler (d.sub.50 < 2 ?m) Coarse 0 20 20 0 20 20 Limestone filler (d.sub.50 > 40 ?m) Water to components a, b, 0.4 0.4 0.4 0.4 0.4 0.4 c and d weight ratio Component e: Na.sub.2SO.sub.4 (dry 2 2 2 2 2 2 weight % relative to components a, b, c and d total weight) Component f (dry weight % 0.09 0.09 0.09 0.29 0.29 0.29 relative to components a, b, c and d total weight)

[0118] The rheological properties have been determined according to standard NF EN 196-3, the results are set forth in table 2 below.

TABLE-US-00002 TABLE 2 CE1 CE2 E1 CE3 CE4 E2 Paste yield stress (Pa) 21 4 4 9 11 5 Fresh state paste 2.76 0.69 0.32 5.09 4.72 0.97 viscosity (Pa .Math. s)

[0119] The paste yield stress and the fresh state paste viscosity of counter example CE1, containing fine limestone filler but no coarse limestone filler are pretty high. The paste yield stress and the fresh state paste viscosity of counter example CE2, containing coarse limestone filler but no fine limestone filler are strongly lower than the one of CE1. It is surprising that adding fine limestone filler to the paste of CE2, resulting in example E1 according to the invention, gives a composition with a fresh paste viscosity lower and divided by more than a factor 2.

[0120] This synergistic effect is even more notable when the binder composition comprises lime instead of Portland cement. Indeed, the paste yield stress and the fresh state paste viscosity of counter example CE3, containing fine limestone filler but no coarse limestone filler are pretty high as well as the paste yield stress and the fresh state paste viscosity of counter example CE4, containing coarse limestone filler but no fine limestone filler. It is surprising that adding fine limestone filler to the paste of CE4, resulting in example E2 according to the invention, gives a composition with a paste yield stress lower and divided by more than a factor 2 and a fresh paste viscosity strongly lower and divided by a factor of almost 5.

[0121] From these six pastes, six mortars were prepared, by mixing the same with aggregates according to standard NF EN 196-1. The compressive strengths of these mortars have been determined according to standard NF EN 196-1. The results are set forth in table 3 below.

TABLE-US-00003 TABLE 3 Mortar Mortar Mortar Mortar Mortar Mortar from from from from from from CE1 CE2 E1 CE3 CE4 E2 Compressive 6.2 2.9 5.8 3.1 N/M 4.4 strength after 24 hours (MPa) Compressive 12 6.7 14.0 8.0 N/M 9.0 strength after 48 hours (MPa) Compressive 46.6 37.8 35.0 27.0 N/M 22.0 strength after 28 days (MPa)

N/M: Not Measurable

[0122] As can be seen from table 3, the compressive strengths of the mortars are not significantly different.

[0123] Thus, the binder composition according to the invention allows improving the rheology, i.e. decreasing the paste yield stress and the fresh state paste viscosity, and maintaining the compressive strength.

Example 2: Effect of Ultrafine GGBS

[0124] An additional paste was prepared according to standard NF EN 196-3. The composition is set forth in table 4 below, the composition of E1 is reproduced in table 4.

TABLE-US-00004 TABLE 4 E1 E3 Component a (dry weight %): Portland cement 15 15 Component Standard GGBS (d.sub.50 = 10 ?m) 25 15 b(dry weight %) Ultrafine GGBS (d.sub.50 = 2.5 ?m) 0 10 Component c(dry weight %): Natural pozzolan 30 30 Component Fine limestone filler (d.sub.50 < 2 ?m) 10 10 d(dry weight %) Coarse Limestone filler (d.sub.50 > 40 20 20 ?m) Water to components a, b, c and d weight ratio 0.4 0.4 Component e: Na.sub.2SO.sub.4 (dry weight % relative to 2 2 components a, b, c and d total weight) Component f (dry weight % relative to components 0.09 0.09 a, b, c and d total weight)

[0125] The rheological properties have been determined according to standard NF EN 196-3, the results are set forth in table 5 below.

TABLE-US-00005 TABLE 5 E1 E3 Paste yield stress (Pa) 4 4 Fresh state paste viscosity (Pa .Math. s) 0.32 0.29

[0126] The paste yield stress and the fresh state paste viscosity of example E3, containing ultrafine GGBS are similar to the paste yield stress and the fresh state paste viscosity of example E1, not containing ultrafine GGBS.

[0127] From this paste, a mortar was prepared, by mixing the same with aggregates according to standard NF EN 196-1. The compressive strengths of this mortar have been determined according to standard NF EN 196-1. The results are set forth in table 6 below, in which the results for mortar from E1 are reproduced.

TABLE-US-00006 TABLE 6 Mortar Mortar from E1 from E3 Compressive strength after 24 hours 5.8 8.5 (MPa) Compressive strength after 48 hours 14.0 19.6 (MPa) Compressive strength after 28 days 35.0 37.6 (MPa)

[0128] As can be seen from table 6, the compressive strengths of the mortar from E3, comprising ultrafine GGBS are greater than the compressive strengths of the mortar from E1.

[0129] Thus, ultrafine GGBS allows increasing the compressive strength of the composition according to the invention and maintaining the rheology, i.e. decreasing the paste yield stress and the fresh state paste viscosity, obtained thanks to the synergistic effect of the combination of fine fillers and coarse fillers.