WO2023237186A1 - Liant minéral destiné à être utilisé en tant que substitut de ciment dans des matériaux de construction - Google Patents

Liant minéral destiné à être utilisé en tant que substitut de ciment dans des matériaux de construction Download PDF

Info

Publication number
WO2023237186A1
WO2023237186A1 PCT/EP2022/065425 EP2022065425W WO2023237186A1 WO 2023237186 A1 WO2023237186 A1 WO 2023237186A1 EP 2022065425 W EP2022065425 W EP 2022065425W WO 2023237186 A1 WO2023237186 A1 WO 2023237186A1
Authority
WO
WIPO (PCT)
Prior art keywords
mineral binder
binder
mineral
brick
composition
Prior art date
Application number
PCT/EP2022/065425
Other languages
English (en)
Inventor
Gnanli LANDROU
Thibault DEMOULIN
Original Assignee
Oxara Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oxara Ag filed Critical Oxara Ag
Priority to PCT/EP2022/065425 priority Critical patent/WO2023237186A1/fr
Priority to PCT/EP2023/065218 priority patent/WO2023237599A1/fr
Publication of WO2023237186A1 publication Critical patent/WO2023237186A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/001—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing unburned clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/08—Slag cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/18—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type
    • C04B28/186—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step
    • C04B28/188—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step the Ca-silicates being present in the starting mixture
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
    • C04B7/17—Mixtures thereof with other inorganic cementitious materials or other activators with calcium oxide containing activators
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1031—Lime-free or very low lime-content materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1037—Cement free compositions, e.g. hydraulically hardening mixtures based on waste materials, not containing cement as such
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1056—Silica-free or very low silica-content materials

Definitions

  • the invention relates to a mineral binder based on a binder material and an activator as well as a mineral binder composition comprising the mineral binder and aggregates. Furthermore, the invention is related to a workable mineral binder composition, a composition for producing a brick or a block, and a hardened building material. Additional aspects of the invention are a method for processing mineral binder compositions and producing building materials as well as the use of the mineral binder or the mineral binder composition.
  • Concrete typically is made of cement, which is the hydraulic binder, of aggregates and of water.
  • cement in mineral binder compositions can be partially replaced by latent hydraulic and/or pozzolanic materials, such as fly ash, slag or silica fume.
  • latent hydraulic and/or pozzolanic materials such as fly ash, slag or silica fume.
  • Such cement replacements are by-products in various industrial processes and are therefore beneficial, for example in terms of CO 2 balance.
  • setting of mixes comprising considerable proportions of such cement replacements usually takes much longer and workability might be also affected negatively.
  • WO 202 1/ 180318 A1 WO 202 1/ 180318 A1 (ETH Zurich) describing an additive for the production of clay-based hardenable building materials, which consists of: a) a dispersing agent, selected from aluminates, aluminate precursors, phosphates, silicates and/or polyacrylates, which is capable of dispersing clay particles in an aqueous slurry, and b) a coagulating agent, selected from salts of divalent metal cations, preferably salts of alkaline earth metals and/or iron, especially magnesium, calcium and/or iron salts, capable of causing clay particles to agglomerate in a aqueous slurry.
  • a dispersing agent selected from aluminates, aluminate precursors, phosphates, silicates and/or polyacrylates, which is capable of dispersing clay particles in an aqueous slurry
  • a coagulating agent selected from salts of divalent metal
  • a cement replacement shall be provided which is suitable for producing different types of low-cement or cement-free building materials, such as e.g. mortars, concretes, screeds, grout, blocks and bricks and the like in a flexible manner.
  • the inventive mineral binder With the inventive mineral binder, it is possible to produce low-cement or even cement-free building materials in a highly flexible manner.
  • the inventive mineral binder does not require any cement but can be used as a 1 : 1 cement replacement in very different low- cement or cement-free building materials, such as e.g. mortars, concretes, screeds, grouts, renders, blocks and/or clay bricks.
  • the mineral binder can be combined for example with suitable aggregates, e.g. fillers, sand, gravel, demolition waste as a mixture of exclusively mineral construction waste from solid components (such as concrete, brick, sand-lime brick and/or natural stone masonry), and/or excavation material.
  • the activator especially the magnesium oxide, enhances the reactivity of the latent hydraulic and/or pozzolanic material in the innovative mineral binder. Consequently, the new mineral binder can harden at room temperature within about 48 hours, especially within 15 hours, upon contact with water. This comes with surprise. So far, conventional activation of latent hydraulic and/or pozzolanic materials as for example slag usually was done with cement, lime and/or sodium silicate.
  • the mixture of the mineral binder mainly is based on latent hydraulic and/or pozzolanic materials, the environmental impact of the mineral binder is much lower than for ordinary cement that requires calcination at high temperatures. This is in particular true for slag, which is a by-product from steel-industry.
  • the densities of the inventive mineral binders usually are lower than cementbased binders.
  • building materials such as e.g. mortar or concrete produced with the inventive mineral binder can be formulated to have a rather low density too.
  • a first aspect of the present invention relates to a mineral binder comprising a mixture a binder material and an activator, whereby: the binder material is selected from latent hydraulic and/or pozzolanic materials; the activator is selected from magnesium oxide, calcium oxide, magnesium hydroxide and/or calcium hydroxide; and with respect to the weight of the mixture, a proportion of binder material is from 50 - 95 wt.%, especially 70 - 85 wt.%, and a proportion of activator is from 5 - 50 wt.%, especially 15 - 30 wt.%.
  • a proportion of binder material is from 73- 77 wt.%, especially 75 wt.%, and a proportion of activator is from 23 - 37 wt.%, especially 25 wt.%.
  • the binder material is selected from fly ash, slag or silica fume, especially from slag.
  • Slag is a by-product of steel industry. Slag usually is a mixture of metal oxides and silicon dioxide. However, slags can contain metal sulfides and elemental metals. The major components of slag include oxides of calcium, magnesium, silicon, iron, and/or aluminum, optionally with lesser amounts of manganese, phosphorus, and others depending on the specifics of the raw materials used.
  • the particle size of the binder material ranges from 1 - 100 pm, especially 5 - 63 pm.
  • the activator is selected from magnesium oxide.
  • the activator is selected from magnesium oxide and the binder material is selected from slag. This turned out to be a highly suitable combination for a mineral binder.
  • a particle size of the activator, especially magnesium oxide, preferably ranges from 5 - 800 pm, especially 14 - 200 pm.
  • the particle size can e.g. be determined by laser diffraction as described in ISO 13320:2009.
  • a particle size of non-spherical or irregular particles is represented by the equivalent spherical diameter of a sphere of equivalent volume.
  • the lower values of the ranges given for the particle size represent D v1 values whereas the upper values of the ranges given for the particle size represent D v99 values.
  • 1% of the particles have size smaller than the lower value of a range, whereas 1% of the particles have size larger than the upper value of a range.
  • the mineral binder further comprises a clay component selected from crushed fines of clay brick (CFCB) and/or calcined clay, whereby a weight ratio of the clay component to the mixture of binder material and activator is from 5:95 - 70:30, especially 10:90 - 25:75, in particular 10:90 - 15:85.
  • CFCB crushed fines of clay brick
  • CFCB can for example be obtained by crushing and optionally sieving waste of fired clay bricks and/or tiles.
  • Fired clay bricks are burned in a kiln and usually comprise sand and alumina as main components. Additionally, lime and other substances, especially iron oxide and/or magnesia, may be present as minor components.
  • Main component(s) are meant to be the component(s) with the highest weight proportion(s).
  • a fired clay brick may comprise 50 - 60 wt.% sand, 20 - 30 wt.% alumina and 2 - 5 wt.% lime. The balance in particular is made up with iron oxide and/or magnesia.
  • Wasted fired clay bricks and/or tiles can be obtained from brick manufacturers, ceramic producers and/or recycling companies.
  • CFCB can be used to accelerate the hardening reaction, dilute the mineral binder and reduce the density of the mineral binder after hardening. Specifically, by increasing the proportion of CFCB in the mineral binder, the density of the hardened material decreases as well as the late compressive strength.
  • a particle size of the clay component, especially the CFCB is for example > 0 - 4 mm. If the mineral binder is used to prepare a mortar, the grain size can be for example > 500 pm - 4 mm. In a preferred embodiment, a particle size of the clay component, especially the CFCB, is below 500 pm, especially between 50 - 200 pm. The particle size of the clay component allows for controlling the hardening rate of the mineral binder.
  • the mineral binder comprises a phosphate whereby a weight ratio of the phosphate to the mixture of the binder material and the activator is from 0.5:99.5 - 50:50, especially 1 :99 - 30:70, especially 5:95 -25:75.
  • the phosphate improves activation and hardening of the mineral binder. In particular, the phosphate increases and delays the maximum in heat release during the hardening process. Additionally, the phosphate helps dispersing particles, e.g. clay particles, after mixing the mineral binder with water and optionally further components.
  • the phosphate is a solid substance, especially a particulate substance.
  • a particle size of the particulate phosphate preferably is from 30 - 800 pm.
  • the phosphate is a polyphosphate, e.g. with 3 to 20 phosphate groups.
  • the phosphate is a pyrophosphate, an orthophosphate and/or a metaphosphate.
  • Pyrophosphates are phosphorus oxyanions that contain two phosphorus atoms in a P-O-P linkage.
  • Orthophosphates are anions or salts of orthophosphoric acid (H 3 PO 4 ).
  • Polymetaphosphates have a cyclic structure.
  • the phosphate in particular is an alkali and/or ammonium phosphate.
  • An alkali phosphate preferably is selected from sodium phosphate and/or potassium phosphate.
  • the phosphate is a trimetaphosphate and/or a hexametaphosphate, more preferably an alkali metal trimetaphosphate and/or an alkali metal hexametaphosphate, in particular sodium trimetaphosphate (NaTMP) and/or sodium hexametaphosphate (NaHMP).
  • NaTMP sodium trimetaphosphate
  • NaHMP sodium hexametaphosphate
  • each hexametaphosphate preferably comprises six phosphorous groups comprising a central phosphor atom, which is bound on average to three oxygen atoms, i.e. six NaPO 3 monomers.
  • each trimetaphosphate preferably comprises three phosphorous groups comprising a central phosphor atom, which is bound on average to three oxygen atoms, i.e. three NaPO 3 monomers.
  • the mineral binder comprises an additional binder compound which is different form the binder material in the mixture and whereby the additional binder compound is selected from a hydraulic binder, a pozzolanic compound or a mixture thereof, whereby, preferably, a weight ratio of the additional binder compound to the mixture is from 1 :99- 60:40, especially 2:98 - 50:50, in particular 5:95 - 15:85.
  • the additional binder compound is selected from gypsum and/or fly ash.
  • the additional binder compound can be used to reduce the proportion of the activator, especially the magnesium oxide, while maintaining the activation of the binder material, e.g. slag, and/or to further improve the activation of the binder material.
  • the mineral binder might comprise cement, lime and/or silicates, especially an alkali metal silicate, in particular sodium silicate and/or potassium silicate.
  • the silicate is a sodium silicate with a ratio of SiO 2 :Na 2 O in the range of 1 - 2.8 and/or a potassium silicate with a ratio of SiO 2 :K 2 O in the range of 1 - 2.8
  • a proportion of cement, lime and/or silicates, especially alkali metal silicates, in the mineral binder is below 10 wt.%, especially below 5 wt.%, in particular below 1 wt.% or 0 % by weight, with respect to the total weight of the mineral binder.
  • mineral binder is cement-free, lime-free and/or silicate-free.
  • the mineral binder does not comprise a silicate, especially an alkali metal silicate, in particular sodium silicate and/or potassium silicate.
  • the mineral binder does not comprise a sodium silicate with a ratio of SiO 2 :Na 2 O in the range of 1 - 2.8 and/or a potassium silicate with a ratio of SiO 2 :K 2 O in the range of 1 - 2.8.
  • the mineral binder comprises or consist of:
  • binder material especially slag
  • the mineral binder comprises or consist of:
  • binder material especially slag
  • phosphate especially hexametaphosphate
  • the mineral binder can be provided as a one-component mixture comprising the mixture of binder material and activator, especially slag and magnesium oxide.
  • one or more of the above-mentioned optional components can be comprised in the one-component mixture as well. As it turned out, such kind of one-component mixtures are storage stable up to six months, especially if all of the components are added in dry form.
  • the mineral binder can be provided in the form of a two- or multicomponent mixture if desired. This allows for flexibly adjusting the mineral binder to specific needs.
  • a further aspect of the present invention is directed to a mineral binder composition
  • a mineral binder composition comprising: a) a mineral binder as described above, and b) aggregates, especially sand, gravel, fines, silt, clay, excavation material, a mineral fraction of soil and/or sludge.
  • the mineral binder composition is a mortar, a concrete, a screed, a grout, a render or a composition for producing a brick.
  • Sludge in particular is selected from aggregate sludge, concrete sludge and/or sewage sludge.
  • sludge is in the form of a slurry, a semi-solid material or in the form of a dry powder.
  • a particle size of solid particles in the sludge is ⁇ 63 pm.
  • Aggregate sludge is a slurry comprising water and solid particulate aggregate, e.g. obtained as a waste during the process of washing aggregates, such as e.g. sand and/or gravel.
  • Concrete sludge is a construction waste in the form of a slurry comprising water and solid concrete particles. Sewage sludge is the residual that is produced as a by-product during sewage treatment of industrial or municipal wastewater.
  • Sludge in the form of a semi-solid material or a dry powder can be obtained by reducing or removing the proportion of liquids, especially water, by drying.
  • the clay used as aggregates is uncalcined clay, e.g. hydrated aluminosilicate particles.
  • the mineral binder composition is a composition for producing a brick, especially a clay brick
  • the aggregates preferably comprise clay, sand and/or sludge.
  • clays consist of particles with a particle size smaller than 4 pm, more preferably smaller than 2 pm.
  • the particle sizes are d 90 -values, which are determined by laser diffraction, especially according to standard ISO 13320:2009. Thus, 90% of the particles are smaller than the given particle sizes.
  • Clay particles are preferably hydrated aluminosilicate particles.
  • clays comprise phyllosilicate minerals.
  • clays are described by presence of two-dimensional sheets, tetrahedral (SiO 4 ) and octahedral (AI 2 O 3 ). They are classified 2: 1 clays when an octahedral sheet is sandwiched between two tetrahedral sheets, whereas if there is only one tetrahedral and one octahedral group in each layer the clay is classified as a 1 : 1 clay.
  • the clays comprise or consist of kaolinite, smectite, montmorillonite, illite, bentonite, and/or hectorite.
  • a mineral fraction of soil, excavation material and/or sludge can be used as aggregates. In this case, no neat sands and/or gravel is required.
  • clay-containing materials in the form of a clay-containing mineral fraction of soil can be used as the aggregates.
  • Such clay containing materials can for example be obtained from clay quarries or clay pits.
  • further aggregates such as e.g. sands. Nevertheless, this is of course possible if desired.
  • the clay and/or clay containing materials is used as aggregate and the mineral binder comprises a clay component
  • the clay and/or clay containing material(s) used as aggregate is/are different from the clay component of the mineral binder.
  • a weight ratio of the aggregates to the mineral binder in the mineral binder composition is from 500: 1 - 1 :20, especially 300: 1 - 1 : 1.
  • a weight ratio of the aggregates to the mineral binder in the mineral binder composition from 200: 1 - 50: 1 and the aggregates are selected from excavation material.
  • the mineral binder composition in particular comprises: the binder material and the activator, especially slag and magnesium oxide, whereby, with respect to the weight of the mixture of the binder material and the activator, a proportion of binder material, especially slag, is from 70 - 85 wt.%, and a proportion of activator, especially magnesium oxide, is from 15 - 30 wt.%; phosphate, especially hexametaphosphate, whereby a weight ratio of the phosphate to the mixture of binder material and activator is from 10:90 - 20:80.
  • a weight ratio of the aggregates to the mineral binder in the mineral binder composition from 200: 1 - 100: 1 and the aggregates are selected from sand, gravel, silt and/or clay excavation material.
  • the mineral binder composition in particular comprises: the binder material and the activator, especially slag and magnesium oxide, whereby, with respect to the weight of the mixture of binder material and activator, a proportion of binder material, especially slag, is from 70 - 85 wt.%, and a proportion of activator, especially magnesium oxide, is from 15 - 30 wt.%; phosphate, especially hexametaphosphate, whereby a weight ratio of the phosphate to the mixture of binder material and activator is from 10:90 - 20:80;
  • Such a mineral binder composition is for example suitable as cement-free concrete.
  • a weight ratio of the aggregates to the mineral binder in the mineral binder composition from 10: 1 - 1 : 1, especially from 3: 1 - 1 : 1 , and the aggregates are selected from sand, gravel, and/or sludge, especially with particle sizes of > 0 - 16 mm.
  • the mineral binder composition in particular comprises: the binder material and the activator, especially slag and magnesium oxide, whereby, with respect to the weight of the mixture of binder material and activator, a proportion of binder material, especially slag, is from 70 - 85 wt.%, and a proportion of activator, especially magnesium oxide, is from 15 - 30 wt.%; phosphate, especially hexametaphosphate, whereby a weight ratio of the phosphate to the mixture of binder material and activator is from 1 :99 - 10:90;
  • Such a mineral binder composition is for example suitable as cement-free structural concrete.
  • a weight ratio of the aggregates to the mineral binder in the mineral binder composition from 1 :2 - 1 : 10 and the aggregates are selected from sand and/or sludge, especially sludge.
  • the mineral binder composition in particular comprises: the binder material and the activator, especially slag and magnesium oxide, whereby, with respect to the weight of the mixture of binder material and activator, a proportion of binder material, especially slag, is from 70 - 85 wt.%, and a proportion of activator, especially magnesium oxide, is from 15 - 30 wt.%; phosphate, especially hexametaphosphate, whereby a weight ratio of the phosphate to the mixture of binder material and activator is from 10:90 - 30:70;
  • Such a mineral binder composition is for example suitable as cement-free mortar. If desired, in the these mineral binder compositions an additional binder compound can be used as described above, such as e.g. gypsum and/or fly ash.
  • the mineral binder composition might comprise cement, lime and/or silicates, especially an alkali metal silicate, in particular sodium silicate and/or potassium silicate.
  • the silicate is a sodium silicate with a ratio of SiO 2 :Na 2 O in the range of 1 - 2.8 and/or a potassium silicate with a ratio of SiO 2 :K 2 O in the range of 1 - 2.8
  • a proportion of cement, lime and/or silicates, especially alkali metal silicates, in the mineral binder composition is below 10 wt.%, especially below 5 wt.%, in particular below 1 wt.% or 0 % by weight, with respect to the total weight of the mineral binder composition.
  • the mineral binder composition does not comprise a silicate, especially an alkali metal silicate, in particular sodium silicate and/or potassium silicate.
  • the mineral binder composition does not comprise a sodium silicate with a ratio of SiO 2 :Na 2 O in the range of 1 - 2.8 and/or a potassium silicate with a ratio of SiO 2 :K 2 O in the range of 1 - 2.8.
  • mineral binder composition is cement-free, lime-free and/or silicate-free.
  • the mineral binder composition can be provided as a one-component mixture, especially in the form of a ready-mix product.
  • a ready-mix product can be simply mixed with water in order to produce the mineral binder composition in workable state.
  • mineral binder compositions in the form of two- or multi-component compositions are possible as well.
  • the mineral binder can be provided in a first component and the aggregates in a second component.
  • the mineral binder is provided as a two-component composition as described above and the aggregates are provided as a further component.
  • Another aspect of the present invention is related to a workable building material, comprising a mineral binder as described above or a mineral binder composition as described above, and water.
  • the workable building material is a screed, mortar, concrete, grout, render or a composition for producing a brick.
  • a ratio of water to the mineral binder in the workable building material is from 0.25 - 0.8, especially 0.3 - 0.6, in particular 0.3 - 0.5.
  • the proportion of water can in particular be adjusted based on the intended application.
  • the inventive mineral binder improves the mechanical properties, especially the compressive strength, significantly without need of high temperatures.
  • the process can be performed with much less energy.
  • a further aspect of the invention is related to a hardened building material obtainable by hardening a workable building material as described above.
  • the hardened building material is a formed body, e.g. a wall, a floor, a ceiling, a roof, a brick, a panel, a slab and/or a pillar.
  • the hardened building material is a brick, especially a clay brick.
  • the hardened building material can have a compressive strength of at least 1.4 MPa, and more particularly of at least 3 MPa or of 3 to 25 MPa. Thereby, no hydraulic binder, especially cement, is required.
  • a compressive strength in this range makes it possible to manufacture building blocks or vertical walls suitable for the construction of houses or buildings with up to four storeys without the use of materials such as hydraulic binders. It is important to mention that a compressive strength of at least 1.4 MPa can be obtained after 24 hours of hardening, which allows construction progress with approximately the same speed as if the building material used is mortar or concrete.
  • tests for the determination of the compressive strength are carried out following standard EN 12390-1 :2012, EN 12390-2:2019, EN 12390- 3:2019 and 12390-4:2000 with prisms (40x40x 160 mm).
  • a still further aspect of the invention is concerned with the use of a mineral binder as defined above or a mineral binder composition as described above for producing a hardenable building material.
  • the hardenable building material is in particular a mortar, concrete, screed, grout, render, and/or a composition for producing a brick.
  • the hardenable building material is a screed for flooring, a plaster for non- structural wall applications, a mortar, or a concrete composition.
  • the mineral binder or the mineral binder composition is used for producing a formed body, e.g. a wall, a floor, a ceiling, a roof, a brick, a panel, a slab and/or a pillar.
  • Another aspect of the invention is related to a method comprising the steps of: a) Providing or producing a mineral binder or a mineral binder composition as described above; b) Mixing the mineral binder or the mineral binder composition with water in order to produce a workable building material, whereby, preferably, a ratio of water to the mineral binder preferably is from 0.25 - 0.8, especially 0.3 - 0.6, in particular 0.3 -0.5;
  • the method further comprises the step of: c) Processing the workable building material by:
  • a grout especially a tiling grout and/or a repair grout, whereby the grout in particular is used to fill a cavity, especially a crack and/or a joint.
  • the invention is concerned with a method for producing a brick and/or a block, especially a clay brick and/or clay block, comprising the steps of: a) Providing aggregates, especially clay containing mineral fraction of soil, clay, sand and/or sludge; b) Mixing the aggregates with a phosphate as described above, especially with an alkali and/or ammonium phosphate, in particular a trimetaphosphate and/or a hexametaphosphate; c) Optionally storing the mix of aggregates and phosphate for 0.5 - 30 days, especially 1 - 3 days.
  • humidity is controlled such that it does not change by more than 1.5%, especially 0.5% with respect to the initial humidity; d) Blending the mix of aggregates and phosphate with a mineral binder comprising the binder material and the activator, especially slag and magnesium oxide, as described above; e) Forming the brick or the block from the blend obtained in step d), especially by moulding and/or extrusion, in particular by additionally compacting the blend, e.g. by vibrocompacting, compressing and/or vibration; f) Curing the formed brick or block, especially at a temperature in the range of room temperature to 150 °C. More preferably, the formed brick or block in a first period, e.g. 0.5 - 30 days, is cured at room temperature, and in a subsequent second period, the formed brick or block is cured at a temperature of 50 - 150°C, especially 60 - 120°C.
  • first period e.g. 0.5 - 30 days
  • Fig. 1 time resolved isothermal calorimetry measurements of mineral binders based on slag and MgO recorded during the hardening process
  • Fig. 2 time resolved isothermal calorimetry measurements of mineral binders based on slag, MgO and sodium hexametaphosphate recorded during the hardening process;
  • Fig. 3 a comparison of the evolution of hardness of a sample with phosphate and a sample without phosphate
  • Fig. 4 time resolved isothermal calorimetry measurements (23 °C) of mineral binders based on slag, MgO and gypsum recorded during the hardening process.
  • Table 1 shows several compositions of different mineral binders based on slag and magnesium oxide, which were mixed with water in order to produce workable mineral binders. All substances used are commercially available.
  • Fig. 1 shows time-resolved isothermal calorimetry measurements of the mineral binders R 1 and M2 - M5 recorded during the hardening process.
  • MgO is capable of activating the slag within a few hours when compared to the reference R1.
  • Most effective is mixture M4 with 75 g of slag and 25 g of MgO.
  • Table 3 shows further mineral binders which are based on a mixture of 75 wt.% of slag and
  • MgO similar to mineral binder M4 and additionally comprise sodium hexmetaphosphate (NaHMP).
  • NaHMP sodium hexmetaphosphate
  • Mineral binders M4 (no NaHMP) and M 12 (only NaHMP) are listed for reasons of comparison.
  • Fig. 2 shows time-resolved isothermal calorimetry measurements of these binders.
  • addition of further mineral binders NaHMP increases the heat release and give rise to a delay, which depends on the proportion of NaHMP.
  • the high heat release is representative of a higher compressive strength.
  • Table 4 shows two examples of mineral binders comprising slag, MgO, and CFCB with and without NaHMP.
  • Table 4 Mineral binders based on stag, MgO, CFCB and NaHMP
  • Fig. 3 shows the evolution of compressive strength of the two samples M 12 and M 13. All measurements were carried out following standard EN 12390-1 :2012, EN 12390-2:2019, EN 12390-3:2019 and 12390-4:2000 with prisms (40x40x 160 mm). As evident, the addition of phosphate drastically increases the compressive strength by about a factor of 2.
  • Table 5 shows further mineral binders which are based on a mixture of slag 75 wt.% of slag and 25 wt.% of MgO (similar to mineral binder M4) and additionally comprise gypsum.
  • the mineral binder M4 (no gypsum) is listed for reasons of compfarison.
  • Table 6 shows a formulation of workable mineral binder compositions MB1 und MB2 comprising an inventive binder and aggregates in the form of excavation soil.
  • Table 7 shows a formulation of workable mineral binder compositions MB3 and MB4 comprising an inventive binder and aggregates in the form of sludge, sand and gravel. Such compositions can be used as concrete replacement.
  • Table 7 Workable mineral binder composition for use as concrete
  • Table 8 shows further formulations of mineral binder compositions MB5, MB6 and MB7 comprising an inventive binder and various aggregates. Such compositions can be used as concrete replacement.
  • Table 8 Mineral binder composition for use as concrete
  • Clay bricks were produced as follows: a) Sodium phosphate was added to a mixture comprising clay containing earth, sand (0-4 mm) and sludge. The mixture was agitated for 3 min. b) The blended material of step a) (initial water content about 9.4 - 17 wt.% with respect to overall weight of the material) was left for rest for 2 days with control of humidity and temperature. Specifically, humidity was controlled such that it did not change by more than 1.5%, with respect to the initial humidity. c) The material of step b) was mixed with a blend of magnesium oxide and slag. d) A brick was formed by compression in a mold. e) Curing the brick of step d) for 2 days at room temperature.
  • a brick was produced in a similar manner but without addition of phosphate, MgO and slag.
  • the compressive strength was as low as 3.8 MPa.
  • the method for producing bricks can be performed in a similar manner to produce blocks.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention porte sur un liant minéral comprenant un mélange d'un matériau liant et d'un activateur. Le matériau liant est choisi parmi des matériaux hydrauliques et/ou pouzzolaniques latents ; l'activateur est choisi parmi l'oxyde de magnésium, l'oxyde de calcium, l'hydroxyde de magnésium et/ou l'hydroxyde de calcium ; et, par rapport au poids du mélange, une proportion de matériau liant est de 50 à 95 % en poids, en particulier de 70 à 85 % en poids, et une proportion d'activateur est de 5 à 50 % en poids, en particulier de 15 à 30 % en poids.
PCT/EP2022/065425 2022-06-07 2022-06-07 Liant minéral destiné à être utilisé en tant que substitut de ciment dans des matériaux de construction WO2023237186A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/EP2022/065425 WO2023237186A1 (fr) 2022-06-07 2022-06-07 Liant minéral destiné à être utilisé en tant que substitut de ciment dans des matériaux de construction
PCT/EP2023/065218 WO2023237599A1 (fr) 2022-06-07 2023-06-07 Liant minéral destiné à être utilisé en tant que remplacement du ciment dans des matériaux de construction

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2022/065425 WO2023237186A1 (fr) 2022-06-07 2022-06-07 Liant minéral destiné à être utilisé en tant que substitut de ciment dans des matériaux de construction

Publications (1)

Publication Number Publication Date
WO2023237186A1 true WO2023237186A1 (fr) 2023-12-14

Family

ID=82196419

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2022/065425 WO2023237186A1 (fr) 2022-06-07 2022-06-07 Liant minéral destiné à être utilisé en tant que substitut de ciment dans des matériaux de construction

Country Status (1)

Country Link
WO (1) WO2023237186A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070221100A1 (en) * 2006-03-22 2007-09-27 Sanjay Kumar Process for the preparation of self-glazed geopolymer tile from fly ash and blast furnace slag
WO2014118242A1 (fr) * 2013-02-04 2014-08-07 Refratechnik Holding Gmbh Système de liant géopolymère pour bétons réfractaires, composition de béton sèche renfermant le système de liant, et utilisation de la composition
KR20190013061A (ko) * 2017-07-31 2019-02-11 전의현 활성화슬래그를 활용한 무시멘트 컬러콘크리트용 바인더 및 이를 이용해 제조되는 콘크리트
KR20200070701A (ko) * 2018-12-10 2020-06-18 한국과학기술원 지오폴리머성 하이브리드 제올라이트-ldh 복합체 및 그 제조 방법
WO2021067920A1 (fr) * 2019-10-04 2021-04-08 Premier Magnesia, Llc Ciment géopolymère
CN112876147A (zh) * 2021-02-08 2021-06-01 大连理工大学 一种氧化镁激发矿渣地聚物人工鱼礁及其制备方法
WO2021180318A1 (fr) 2020-03-11 2021-09-16 ETH Zürich Additif pour matériaux de construction exempts de ciment

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070221100A1 (en) * 2006-03-22 2007-09-27 Sanjay Kumar Process for the preparation of self-glazed geopolymer tile from fly ash and blast furnace slag
WO2014118242A1 (fr) * 2013-02-04 2014-08-07 Refratechnik Holding Gmbh Système de liant géopolymère pour bétons réfractaires, composition de béton sèche renfermant le système de liant, et utilisation de la composition
KR20190013061A (ko) * 2017-07-31 2019-02-11 전의현 활성화슬래그를 활용한 무시멘트 컬러콘크리트용 바인더 및 이를 이용해 제조되는 콘크리트
KR20200070701A (ko) * 2018-12-10 2020-06-18 한국과학기술원 지오폴리머성 하이브리드 제올라이트-ldh 복합체 및 그 제조 방법
WO2021067920A1 (fr) * 2019-10-04 2021-04-08 Premier Magnesia, Llc Ciment géopolymère
WO2021180318A1 (fr) 2020-03-11 2021-09-16 ETH Zürich Additif pour matériaux de construction exempts de ciment
CN112876147A (zh) * 2021-02-08 2021-06-01 大连理工大学 一种氧化镁激发矿渣地聚物人工鱼礁及其制备方法

Similar Documents

Publication Publication Date Title
US10355278B2 (en) Binder based on a solid mineral compound rich in alkaline-earth metal oxide with phosphate-containing activators
US8709150B2 (en) Composition for building material and a process for the preparation thereof
AU2018202064B2 (en) Composition for use as a two component back filled grout comprising extracted silicate
CN111868002A (zh) 基于粒化的高炉矿渣粉的黏结剂，由其制得的干式制剂和湿式制剂及其制备方法
ZA200104431B (en) Inorganic cementitious material.
JP2009504545A (ja) 石灰非依存性セメント混合物
US20230150876A1 (en) Additive for cement-free building materials
CZ2005211A3 (cs) Pojivová smes obsahující druhotnou surovinu, zpusob její výroby a její pouzití
KR20220054304A (ko) 무기 폴리머들 및 합성 재료에서의 이의 용도
JP4201265B2 (ja) 超速硬・高流動モルタル組成物および超速硬・高流動モルタル
WO2023237186A1 (fr) Liant minéral destiné à être utilisé en tant que substitut de ciment dans des matériaux de construction
WO2023237599A1 (fr) Liant minéral destiné à être utilisé en tant que remplacement du ciment dans des matériaux de construction
JP2006027937A (ja) グラウト用セメント組成物及びグラウト材料
JP2022176037A (ja) グラウト材料、グラウトモルタル組成物及び硬化体
WO2021215509A1 (fr) Adjuvant du ciment, matériau d'expansion et composition de ciment
JP4627120B2 (ja) 水硬性粉体組成物
JP4798734B2 (ja) 水硬性組成物
WO2017089899A1 (fr) Ciment activé chimiquement à l'aide de déchets industriels
JP6985547B1 (ja) グラウト材料、グラウトモルタル組成物及び硬化体
RU2074144C1 (ru) Сырьевая смесь для приготовления химически стойкого кремнебетона автоклавного твердения
JP6475579B2 (ja) プレキャストコンクリート用膨張材、その製造方法およびプレキャストコンクリートの製造方法
WO2024089406A1 (fr) Matériau activé par un alcali
TW202335996A (zh) 包含粒化高爐礦渣、鹼金屬硫酸鹽活化劑及pce型減水聚合物之廠拌混凝土或砂漿或預鑄混凝土組成物
JP2023028441A (ja) グラウト材料、グラウトモルタル組成物及び硬化体
JP3543273B2 (ja) コンクリート製品及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22733346

Country of ref document: EP

Kind code of ref document: A1